Hair spray composition comprising a pseudo-block polymer in an aqueous medium, method of use and application.

The present invention relates to a styling cosmetic composition comprising, in a cosmetically acceptable medium containing predominantly water, at least one pseudo-block polymer. The invention also relates to a process for shaping or maintaining the hairstyle in which this composition is used, as well as the uses of this composition.

Cosmetic compositions for shaping and / or maintaining the hairstyle most common in the cosmetics market are spray compositions consisting essentially of a solution that is usually alcoholic and one or more components, referred to as components. fixants, which are generally random polymeric resins whose function is to form welds between the hair. These fixing components are often formulated in admixture with various cosmetic adjuvants. This composition is generally packaged either in a suitable aerosol container pressurized with a propellant, or in a pump bottle.

The aerosol systems for fixing the hair contain on the one hand a liquid phase (or juice) and on the other hand a propellant. The liquid phase contains the fixing components and a suitable solvent.

Once applied to the hair the liquid phase dry, allowing the formation of welds necessary for fixing the hair by the fixing components. The welds must be sufficiently rigid to ensure the maintenance of the hair and with sufficient persistence of effects including moisture. However, they must also be fragile enough that the user can, by painting or brushing the hair, destroy them without hitting the scalp or damage the hair. The compositions must also be stable over time. We are also looking for a good cosmetic effect on the hair, especially in terms of softness and disentangling.

It is also sought to reduce the amount of volatile solvents present in these compositions for environmental reasons. The total or partial replacement of volatile solvents such as alcohol with water generally results in a dramatic decrease in binding properties, persistence of the styling effect over time and cosmetic properties.

Surprisingly and advantageously, the Applicant has discovered that pseudo-block polymers can be used to prepare predominantly aqueous styling compositions which are stable for several months and which allow good fixation and maintenance of the hair, that is to say -Tell a styling effect that persists throughout the day, even days, with good resistance to moisture and is easily removed by shampooing. These compositions also make it possible to impart good cosmetic properties to the hair, such as softness or disentangling.

In addition, their predominantly aqueous base makes these compositions according to the invention very advantageous ecologically.

The subject of the present invention is therefore a cosmetic hair styling composition comprising, in a cosmetically acceptable medium containing predominantly water, at least one pseudo-block polymer.

Another object of the invention consists in a cosmetic treatment method for shaping or maintaining the hairstyle comprising the use of this cosmetic composition.

Another subject of the invention concerns the uses of pseudo-block polymers in predominantly aqueous cosmetic compositions to obtain a hair retention that is persistent over time and / or a fixation of the hair exhibiting good resistance to moisture and / or good cosmetic level.

Other objects, features, aspects and advantages of the invention will emerge even more clearly on reading the description and examples which follow.

By "styling composition" within the meaning of the present application is meant a composition for shaping or maintaining the hairstyle.

By "medium containing predominantly water" within the meaning of the present application means a medium containing strictly more than 50%, preferably more than 70%, and even more preferably more than 85% by weight of water. relative to the total weight of the styling composition. Preferably, this medium will contain less than 99.9% by weight of water relative to the total weight of the styling composition.

The cosmetically acceptable medium is a medium containing mainly water and optionally one or more organic solvents.

For the purposes of the present invention, the term "organic solvent" is intended to mean an organic compound having a molecular weight of less than 500 at a temperature of 25 ° C. and at atmospheric pressure. Preferably, the organic compound is polar.

Preferably, this organic solvent is an alcohol. This is especially chosen from lower alcohols in C₁-C₄ such as ethanol, isopropanol, t-butanol, n-butanol; polyols such as propylene glycol, polyol ethers and mixtures thereof, the particularly preferred alcohol being ethanol.

Advantageously, the compositions according to the invention contain less than 15% of organic solvents and in particular of ethanol.

The pseudo-block polymer used in the compositions according to the present invention is a block polymer, comprising at least a first sequence and at least a second sequence incompatible with each other and having different glass transition temperatures (Tg), said first and second sequences being 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 and said polymer having a polydispersity index I greater than 2.

By "at least" a sequence is meant one or more sequences.

By "sequences incompatible with each other", it is meant that the mixture formed of the polymer corresponding to the first block and the polymer corresponding to the second block, is not miscible in the majority polymerization solvent by weight of the polymer. sequenced at room temperature (25 ° C) and atmospheric pressure (10 ° C).⁵ Pa), for a content of the polymer mixture greater than or equal to 5% by weight, relative to the total weight of the mixture (polymers and solvent), it being understood that:<ul id="ul0001" list-style="none" compact="compact"><li>i) said polymers are present in the mixture in a content such that the respective weight ratio ranges from 10/90 to 90/10, and that</li><li>ii) each of the polymers corresponding to the first and second blocks has an average molecular weight (in weight or in number) equal to that of the sequenced polymer +/- 15%.</li></ul>

In the case of a mixture of polymerization solvents, assuming two or more solvents present in identical mass proportions, said polymer mixture is immiscible in at least one of them.

Of course, in the case of a polymerization carried out in a single solvent, the latter is the majority solvent.

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, it makes it possible to "compatibilize" these blocks.

The block polymer of the composition according to the invention is advantageously a film-forming linear ethylenic block polymer.

By "ethylenic" polymer is meant a polymer obtained by polymerization of monomers comprising ethylenic unsaturation.

By "sequenced" polymer is meant a polymer comprising at least 2 distinct sequences, preferably at least 3 distinct sequences.

The polymer is a linear structure polymer. In contrast, a nonlinearly structured polymer is, for example, a branched, star-shaped, grafted, or other 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.

Preferably, the polymer according to the invention does not comprise silicon atoms in its backbone. By "skeleton" is meant the main chain of the polymer, as opposed to the pendant side chains.

Preferably, the polymer according to the invention is not water-soluble, that is to say that the polymer is not soluble in water or in a mixture of water and linear or branched lower monoalcohols with 2 to 5 carbon atoms such as ethanol, isopropanol or n-propanol, without pH modification, with an active ingredient content of at least 1% by weight, at room temperature (25 ° C.).

Preferably, the polymer according to the invention is not an elastomer.

By "non-elastomeric polymer" is meant a polymer which, when subjected to a stress aimed at stretching it (for example by 30% relative to its initial length), does not return to a length substantially identical to its length. initial when the constraint stops.

More specifically, "non-elastomeric polymer" denotes a polymer having an instantaneous recovery R_i &lt;50% and delayed recovery R_{2 hours} &lt;70% after undergoing a 30% elongation. Preferably, R_i is &lt;30%, and R_{2 hours} &lt;50%.

More specifically, the non-elastomeric nature of the polymer is determined according to the following protocol:

A polymer film is prepared by pouring a solution of the polymer into a teflon matrix and drying for 7 days in a controlled atmosphere at 23 ± 5 ° C and 50 ± 10% relative humidity.

A film approximately 100 μm thick in which are cut rectangular specimens (for example by punch) of a width of 15 mm and a length of 80 mm are then obtained.

This sample is imposed a tensile stress using an apparatus marketed under the reference Zwick, under the same conditions of temperature and humidity as for drying.

The specimens are stretched at a speed of 50 mm / min and the distance between the jaws is 50 mm, which corresponds to the initial length (I₀) of the test piece.

The instantaneous recovery Ri is determined as follows:<ul id="ul0002" list-style="dash" compact="compact"><li>the specimen is stretched by 30% (ε_max) that is about 0.3 times its initial length (I₀)</li><li>the stress is released by imposing a return speed equal to the tensile speed, ie 50 mm / min, and the residual elongation of the specimen is measured in percentage, after returning to zero load stress (ε_i).</li></ul>

The instantaneous recovery in% (R_i) is given by the following formula:<maths id="math0001" num=""><math display="block"><mrow><msub><mrow><mtext>R</mtext></mrow><mrow><mtext>i</mtext></mrow></msub><msub><mrow><mtext> = (ε</mtext></mrow><mrow><mtext>max</mtext></mrow></msub><msub><mrow><mtext> - ε</mtext></mrow><mrow><mtext>i</mtext></mrow></msub><msub><mrow><mtext>) / E</mtext></mrow><mrow><mtext>max</mtext></mrow></msub><mtext>) X 100</mtext></mrow></math><img file="EP1586299A1_D0001.tif" /></maths>

To determine the delayed recovery, after 2 hours the residual elongation ratio of the specimen is measured in percentage (ε_{2 hours}), 2 hours after return to the zero load stress.

Recovery delayed in% (R_{2 hours}) is given by the following formula:<maths id="math0002" num=""><math display="block"><mrow><msub><mrow><mtext>R</mtext></mrow><mrow><mtext>2 hours</mtext></mrow></msub><msub><mrow><mtext> = (ε</mtext></mrow><mrow><mtext>max</mtext></mrow></msub><msub><mrow><mtext> - ε</mtext></mrow><mrow><mtext>2 hours</mtext></mrow></msub><msub><mrow><mtext>) / ε</mtext></mrow><mrow><mtext>max</mtext></mrow></msub><mtext>) x 100</mtext></mrow></math><img file="EP1586299A1_D0002.tif" /></maths>

By way of indication only, a polymer according to one embodiment of the invention preferably has an instantaneous recovery R_i 10% and delayed recovery R_{2 hours} 30%.

The polymer used in the compositions according to the invention comprises at least a first sequence (or block) and at least a second block (or block) incompatible with each other and having different glass transition temperatures (Tg), said first and second sequences being 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, said polymer having a polydispersity index I greater than 2.

It is specified that in what precedes and what follows the terms "first" and "second" sequences do not condition the order of said sequences (or blocks) in the structure of the polymer.

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 polymer used in the composition according to the invention is preferably less than or equal to 300,000, it ranges, for example, from 35,000 to 200,000, and more preferably from 45,000 to 150,000.

The number average mass (Mn) of the polymer used in the composition according to the invention 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.

Preferably, the polydispersity index of the polymer used in the composition according to the invention is greater than 2, for example ranging from 2 to 9, preferably greater than or equal to 2.5, for example ranging from 2.5 to 8. , and better still or equal to 2.8 and in particular, ranging from 2.8 to 6.

Each block or block of the polymer used in the compositions according to the invention is derived from one type of monomer or from several different types of monomer.

This means that each sequence may consist of a homopolymer or a copolymer, this copolymer constituting the sequence may in turn be statistical or alternating.

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.

According to the invention, the first and second sequences have different glass transition temperatures.

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 the Polymer Handbook, 3^rd ed, 1989, John Wiley, according to the following relationship, known as Fox's Law:<maths id="math0003" num=""><img file="EP1586299A1_D0003.tif" /></maths>

<maths id="math0004" num=""><math display="inline"><mrow><mover accent="true"><mrow><mtext>ω</mtext></mrow><mo>¯</mo></mover></mrow></math><img file="EP1586299A1_D0004.tif" /></maths>_i being the mass fraction of the monomer i in the sequence under consideration and Tg_i 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 10 ° C, preferably greater than 20 ° C, and more preferably greater than 30 ° C.

In particular, the first sequence may be chosen from:<ul id="ul0003" list-style="none" compact="compact"><li>a) a sequence having a Tg greater than or equal to 40 ° C,</li><li>b) a sequence having a Tg of less than or equal to 20 ° C,</li><li>c) a sequence having a Tg of between 20 and 40 ° C,</li></ul>    and the second sequence selected from a category a), b) or c) different from the first sequence.

a) Sequence having a Tg greater than or equal to 40 ° C

The sequence having a Tg greater than or equal to 40 ° C has for example a Tg ranging from 40 to 150 ° C, preferably greater than or equal to 50 ° C, ranging for example from 50 ° C to 120 ° C, in particular ranging from 50 ° C to 100 ° C, and better still or equal to 60 ° C, for example from 60 ° C to 120 ° C.

The sequence having a Tg greater than or equal to 40 ° C may be a homopolymer or a copolymer.

In the case where this sequence is a homopolymer, it is derived from monomers, which are such that the homopolymers prepared from these monomers have glass transition temperatures greater than or equal to 40 ° C. This first block may be a homopolymer consisting of a single type of monomer (the Tg of the corresponding homopolymer is greater than or equal to 40 ° C.).

In the case where the first block is a copolymer, it may be issued in whole or in part from one or more monomers, the nature and concentration of which are chosen such that the Tg of the resulting copolymer is greater than or equal to 40%. ° C. The copolymer may for example comprise:<ul id="ul0004" list-style="dash" compact="compact"><li>monomers which are such that the homopolymers prepared from these monomers have Tg greater than or equal to 40 ° C, for example a Tg ranging from 40 to 150 ° C, preferably greater than or equal to 50 ° C, for example from 50 ° C to 120 ° C, and more preferably greater than or equal to 60 ° C, for example from 60 ° C to 120 ° C, and</li><li>monomers which are such that the homopolymers prepared from these monomers have Tg's lower than 40 ° C, chosen from monomers having a Tg of between 20 to 40 ° C and monomers having a Tg of less than or equal to 20 ° C for example a Tg ranging from -100 to 20 ° C, preferably below 15 ° C, in particular ranging from -80 ° C to 15 ° C and better still below 10 ° C, for example ranging from -50 ° C to 0 ° C to, as described below,.</li></ul>

The monomers whose homopolymers have a glass transition temperature greater than or equal to 40 ° C. are preferably chosen from the following monomers, also called main monomers:<ul id="ul0005" list-style="dash" compact="compact"><li>methacrylates of formula CH₂ = C (CH₃) COOR₁   in which R₁ represents a linear or branched, unsubstituted alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group or R₁ represents a cycloalkyl group C₄ at C₁₂,</li><li>acrylates of formula CH₂ = CH-COOR₂   in which R₂ represents a C-cycloalkyl group₄ at C₁₂ such as an isobornyl group or a tert-butyl group,</li><li>the (meth) acrylamides of formula:<chemistry id="chem0001" num="0001"><img file="EP1586299A1_D0005.tif" /></chemistry>    where R₇ and R₈ identical or different, each represents a hydrogen atom or a C-alkyl group₁ at C₁₂ linear or branched, such as n-butyl, t-butyl, isopropyl, isohexyl, isooctyl, or isononyl; or R₇ represents H and R₈ represents a 1,1-dimethyl-3-oxobutyl group,    and R 'denotes H or methyl. Examples of monomers that may be mentioned include N-butylacrylamide, Nt-butylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide and N, N-dibutylacrylamide,</li><li>and their mixtures.</li></ul>

Particularly preferred main monomers are methyl methacrylate, isobutyl (meth) acrylate, isobornyl (meth) acrylate and mixtures thereof.

b) Sequence with a Tg less than or equal to 20 ° C

The sequence having a Tg less than or equal to 20 ° C has for example a Tg ranging from -100 to 20 ° C, preferably less than or equal to 15 ° C, in particular ranging from -80 ° C to 15 ° C and better still or equal to 10 ° C, for example ranging from -100 ° C to 0 ° C, in particular ranging from -50 ° C to 0 ° C.

The sequence having a Tg of less than or equal to 20 ° C may be a homopolymer or a copolymer.

In the case where this sequence is a homopolymer, it is derived from monomers, which are such that the homopolymers prepared from these monomers have glass transition temperatures less than or equal to 20 ° C. This second block may be a homopolymer, consisting of a single type of monomer (whose Tg of the corresponding homopolymer is less than or equal to 20 ° C.).

In the case where the sequence having a Tg less than or equal to 20 ° C is a copolymer, it may be issued in whole or in part from one or more monomers, the nature and concentration of which are chosen so that the Tg the resulting copolymer is less than or equal to 20 ° C.

She can for example understand<ul id="ul0006" list-style="dash" compact="compact"><li>one or more monomers whose corresponding homopolymer has a Tg less than or equal to 20 ° C, for example a Tg ranging from -100 ° C to 20 ° C, preferably less than 15 ° C, in particular ranging from -80 ° C at 15 ° C. and better still below 10 ° C., for example ranging from -50 ° C. to 0 ° C., and</li><li>one or more monomers whose homopolymer corresponds to a Tg greater than 20 ° C., such as monomers having a Tg greater than or equal to 40 ° C., for example a Tg ranging from 40 to 150 ° C., preferably greater than or equal to at 50 ° C, for example from 50 ° C to 120 ° C, and more preferably greater than or equal to 60 ° C, ranging for example from 60 ° C to 120 ° C and / or monomers having a Tg between 20 and 40 ° C, as described above.</li></ul>

Preferably, the sequence having a Tg of less than or equal to 20 ° C is a homopolymer.

The monomers whose homopolymer has a Tg of less than or equal to 20 ° C. are preferably chosen from the following monomers, or main monomer:<ul id="ul0007" list-style="dash" compact="compact"><li>acrylates of formula CH₂ = CHCOOR₃,    R₃ representing an unsubstituted C-alkyl group₁ at C₁₂, linear or branched, with the exception of the tert-butyl group, in which is (are) optionally intercalated (s) one or more heteroatoms chosen from O, N, S,</li><li>methacrylates of formula CH₂ = C (CH₃) COOR₄,    R₄ representing an unsubstituted C-alkyl group₆ at C₁₂ linear or branched, wherein is (are) optionally intercalated (s) one or more heteroatoms selected from 0, N and S;</li><li>vinyl esters of formula R₅-CO-O-CH = CH₂   where R₅ represents a C-alkyl group₄ at C₁₂ linear or branched;</li><li>the vinyl alcohol and C alcohol ethers₄ at C₁₂,</li><li>N-C alkyl₄ at C₁₂ acrylamides, such as N-octylacrylamide,</li><li>and their mixtures.</li></ul>

The main monomers that are particularly preferred for the sequence having a Tg of less than or equal to 20 ° C. are the alkyl acrylates whose alkyl chain comprises from 1 to 10 carbon atoms, with the exception of the tert-butyl group, such as acrylate. of methyl, isobutyl acrylate, 2-ethylhexyl acrylate and mixtures thereof.

c) Sequence with a Tg between 20 and 40 ° C

The sequence which has a Tg of between 20 and 40 ° C can be a homopolymer or a copolymer.

In the case where this sequence is a homopolymer, it is derived from monomers (or main monomer), which are such that the homopolymers prepared from these monomers have glass transition temperatures of between 20 and 40 ° C. This first block may be a homopolymer, consisting of a single type of monomer (whose Tg of the corresponding homopolymer ranges from 20 ° C. to 40 ° C.).

The monomers whose homopolymer has a glass transition temperature of between 20 and 40 ° C. are preferably chosen from n-butyl methacrylate, cyclodecyl acrylate, neopentyl acrylate and isodecylacrylamide. mixtures.

In the case where the sequence having a Tg between 20 and 40 ° C is a copolymer, it is derived in whole or in part from one or more monomers (or main monomer), the nature and concentration of which are chosen from so that the Tg of the resulting copolymer is between 20 and 40 ° C.

Advantageously, the sequence having a Tg of between 20 and 40 ° C is a copolymer resulting in whole or in part:<ul id="ul0008" list-style="dash" compact="compact"><li>main monomers whose homopolymer corresponding to a Tg greater than or equal to 40 ° C, for example a Tg ranging from 40 ° C to 150 ° C, preferably greater than or equal to 50 ° C, ranging for example from 50 to 120 ° C, and more preferably greater than or equal to 60 ° C, for example from 60 ° C to 120 ° C, as described above, and</li><li>of main monomers whose homopolymer corresponding to a Tg less than or equal to 20 ° C, for example a Tg ranging from -100 to 20 ° C, preferably less than or equal to 15 ° C, in particular ranging from -80 ° C to 15 ° C and better still less than or equal to 10 ° C, for example ranging from -50 ° C to 0 ° C, as described above,</li></ul>    said monomers being chosen so that the Tg of the copolymer forming the first block is between 20 and 40 ° C.

Such main monomers are for example chosen from methyl methacrylate, acrylate and isobornyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate and mixtures thereof.

Preferably, the proportion of the second block having a Tg of less than or equal to 20 ° C ranges from 10 to 85% by weight of the polymer, more preferably from 20 to 70% and more preferably from 20 to 50%.

Each of the sequences may nevertheless contain, in a minority proportion, at least one constituent monomer of the other sequence.

Thus the first sequence may contain at least one constituent monomer of the second sequence and vice versa.

Each of the first and / or second sequences may comprise, in addition to the monomers indicated above, one or more other monomers called additional monomers, different from the main monomers mentioned above.

The nature and amount of this additional monomer (s) are chosen so that the sequence in which they are located has the desired glass transition temperature.

This additional monomer is for example chosen from:<ul id="ul0009" list-style="none" compact="compact"><li>a) hydrophilic monomers such as:<ul id="ul0010" list-style="dash" compact="compact"><li>monomers containing ethylenic unsaturation (s) comprising at least one carboxylic or sulphonic acid function, for example:<ul id="ul0011" list-style="none" compact="compact"><li>acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, acrylamidopropanesulfonic acid, vinylbenzoic acid, vinylphosphoric acid and the salts thereof,</li></ul></li><li>ethylenically unsaturated monomers containing at least one tertiary amine functional group such as 2-vinylpyridine, 4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide and salts thereof,</li><li>methacrylates of formula CH₂ = C (CH₃) COOR₆in which R₆ represents a linear or branched alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, said alkyl group being substituted by one or more substituents chosen from hydroxyl groups (such as methacrylate); 2-hydroxypropyl, 2-hydroxyethyl methacrylate) and halogen atoms (Cl, Br, I, F), such as trifluoroethyl methacrylate,</li><li>methacrylates of formula CH₂ = C (CH₃) COOR₉,    R₉ representing a C-alkyl group₆ at C₁₂ linear or branched, in which is optionally interspersed one or more heteroatoms selected from O, N and S, said alkyl group being substituted by one or more substituents selected from hydroxyl groups and halogen atoms ( Cl, Br, I, F);</li><li>acrylates of formula CH₂ = CHCOOR₁₀,    R₁₀ representing a C-alkyl group₁ at C₁₂ linear or branched substituted by one or more substituents selected from hydroxyl groups and halogen atoms (Cl, Br, I and F), such as 2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate, or R₁₀ represents a C-alkyl₁ at C₁₂O-POE (polyoxyethylene) with repeating oxyethylene unit 5 to 30 times, for example methoxy-POE, or R₈ represents a polyoxyethylenated group comprising from 5 to 30 ethylene oxide units</li></ul></li><li>b) ethylenically unsaturated monomers comprising one or more silicon atoms such as methacryloxypropyl trimethoxy silane, methacryloxypropyl tris (trimethylsiloxy) silane,<ul id="ul0012" list-style="dash" compact="compact"><li>and their mixtures.</li></ul></li></ul>

Particularly preferred additional monomers are acrylic acid, methacrylic acid, trifluoroethyl methacrylate and mixtures thereof.

According to a preferred embodiment, the polymer used in the compositions according to the invention is a non-silicone polymer, that is to say a polymer free of silicon atom.

This or these additional monomers generally represent an amount of less than or equal to 30% by weight, for example from 1 to 30% by weight, preferably from 5 to 20% by weight and, more preferably, from 7 to 15% by weight. % by weight of the total weight of the first and / or second sequences.

Preferably, each of the first and second blocks comprises at least one monomer chosen from (meth) acrylic acid esters, and optionally at least one monomer chosen from (meth) acrylic acid, and mixtures thereof.

Advantageously, each of the first and second blocks is derived entirely from at least one monomer chosen from acrylic acid, (meth) acrylic acid esters, and optionally from at least one monomer chosen from (meth) acrylic acid. ) acrylic, and mixtures thereof

Preferably, the polymer used in the compositions according to the invention is free of styrene. By "styrene-free polymer" is meant a polymer containing less than 10% by weight, based on the total weight of the polymer, preferably less than 5% by weight, better still less than 2% by weight, better less than 1% by weight, or even not containing, styrene monomer such as styrene, styrene derivatives such as methylstyrene, chlorostyrene or chloromethylstyrene.

The polymer used in the compositions according to the invention can be obtained by radical polymerization in solution according to the following preparation method:<ul id="ul0013" list-style="dash" compact="compact"><li>a part of the polymerization solvent is introduced into a suitable reactor and heated to reach the temperature suitable for the polymerization (typically between 60 and 120 ° C.),</li><li>once this temperature is reached, the constituent monomers of the first block are introduced in the presence of a part of the polymerization initiator,</li><li>at the end of a time T corresponding to a maximum conversion of 90%, the constituent monomers of the second block and the other part of the initiator are introduced,</li><li>the mixture is allowed to react for a time T '(ranging from 3 to 6 hours) at the end of which the mixture is brought to room temperature,</li><li>the polymer in solution is obtained in the polymerization solvent.</li></ul>

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, alcohols such as isopropanol, ethanol, aliphatic alkanes such as isododecane and mixtures thereof. Preferably, the polymerization solvent is a mixture of butyl acetate and isopropanol or isododecane.

First embodiment

According to a first embodiment, the polymer used in the compositions according to the invention comprises at least one (in particular a) first block having a Tg greater than or equal to 40 ° C, as described in paragraph a) and at least a (in particular a) second block having a Tg of less than or equal to 20 ° C, as described in paragraph b) above.

Preferably, the first block having a Tg greater than or equal to 40 ° C is a copolymer derived from monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ° C., such than the monomers described above.

Advantageously, the second block having a Tg of less than or equal to 20 ° C. is a homopolymer derived from monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20 ° C. , such as the monomers described above.

Preferably, the proportion of the sequence having a Tg greater than or equal to 40 ° C ranges from 20 to 90% by weight of the polymer, more preferably from 30 to 80% and more preferably from 50 to 70%.

Preferably, the proportion of the sequence having a Tg of less than or equal to 20 ° C ranges from 5 to 75% by weight of the polymer, preferably from 15 to 50% and more preferably from 25 to 45%.

Thus, according to a first variant, the polymer used in the compositions according to the invention can comprise:<ul id="ul0014" list-style="dash" compact="compact"><li>a first sequence of Tg greater than or equal to 40 ° C, for example having a Tg ranging from 70 to 110 ° C, which is a methyl methacrylate / acrylic acid copolymer,</li><li>a second sequence of Tg less than or equal to 20 ° C, for example ranging from 0 to 20 ° C, which is a homopolymer of methyl acrylate and</li><li>an intermediate block which is a methyl methacrylate / acrylic acid / methyl acrylate copolymer.</li></ul>

According to a second variant, the polymer used in the compositions according to the invention may comprise:<ul id="ul0015" list-style="dash" compact="compact"><li>a first sequence of Tg greater than or equal to 40 ° C, for example ranging from 70 to 100 ° C, which is a copolymer of methyl methacrylate / acrylic acid / trifluoroethyl methacrylate,</li><li>a second sequence of Tg less than or equal to 20 ° C, for example ranging from 0 to 20 ° C, which is a homopolymer of methyl acrylate and</li><li>an intermediate block which is a random methyl methacrylate / acrylic acid / methyl acrylate / trifluoroethyl methacrylate copolymer.</li></ul>

According to a third variant, the polymer used in the compositions according to the invention may comprise:<ul id="ul0016" list-style="dash" compact="compact"><li>a first sequence of Tg greater than or equal to 40 ° C, for example ranging from 85 to 115 ° C, which is an isobornyl acrylate / isobutyl methacrylate copolymer,</li><li>a second sequence of Tg less than or equal to 20 ° C, for example ranging from -85 to -55 ° C, which is a homopolymer of 2-ethylhexyl acrylate and</li><li>an intermediate block which is a random copolymer of isobornyl acrylate / isobutyl methacrylate / 2-ethylhexyl acrylate.</li></ul>

According to a fourth variant, the polymer used in the compositions according to the invention may comprise:<ul id="ul0017" list-style="dash" compact="compact"><li>a first sequence of Tg greater than or equal to 40 ° C, for example ranging from 85 to 115 ° C, which is an isobornyl acrylate / methyl methacrylate copolymer,</li><li>a second sequence of Tg less than or equal to 20 ° C, for example ranging from -85 to -55 ° C, which is a homopolymer of 2-ethylhexyl acrylate and</li><li>an intermediate block which is a random copolymer of isobornyl acrylate / methyl methacrylate / 2-ethylhexyl acrylate.</li></ul>

According to a fifth variant, the polymer used in the compositions according to the invention may comprise:<ul id="ul0018" list-style="dash" compact="compact"><li>a first sequence of Tg greater than or equal to 40 ° C, for example ranging from 95 to 125 ° C, which is an isobornyl acrylate / isobornyl methacrylate copolymer,</li><li>a second sequence of Tg less than or equal to 20 ° C, for example ranging from -85 to -55 ° C, which is a homopolymer of 2-ethylhexyl acrylate and</li><li>an intermediate block which is a random copolymer of isobornyl acrylate / isobornyl methacrylate / 2-ethylhexyl acrylate.</li></ul>

According to a sixth variant, the polymer used in the compositions according to the invention may comprise:<ul id="ul0019" list-style="dash" compact="compact"><li>a first sequence of Tg greater than or equal to 40 ° C, for example ranging from 85 to 115 ° C, which is a copolymer of isobornyl methacrylate / isobutyl methacrylate,</li><li>a second sequence of Tg less than or equal to 20 ° C, for example ranging from -35 to -5 ° C, which is a homopolymer of isobutyl acrylate and</li><li>an intermediate block which is a random copolymer of isobornyl methacrylate / isobutyl methacrylate / isobutyl acrylate.</li></ul>

According to a seventh variant, the polymer used in the compositions according to the invention may comprise:<ul id="ul0020" list-style="dash" compact="compact"><li>a first sequence of Tg greater than or equal to 40 ° C, for example ranging from 95 to 125 ° C, which is an isobornyl acrylate / isobornyl methacrylate copolymer,</li><li>a second sequence of Tg less than or equal to 20 ° C, for example ranging from -35 to -5 ° C, which is a homopolymer of isobutyl acrylate and</li><li>an intermediate block which is a random copolymer of isobornyl acrylate / isobornyl methacrylate / isobutyl acrylate.</li></ul>

According to an eighth variant, the polymer used in the compositions according to the invention may comprise:<ul id="ul0021" list-style="dash" compact="compact"><li>a first sequence of Tg greater than or equal to 40 ° C, for example ranging from 60 to 90 ° C, which is an isobornyl acrylate / isobutyl methacrylate copolymer,</li><li>a second sequence of Tg less than or equal to 20 ° C, for example ranging from -35 to -5 ° C, which is a homopolymer of isobutyl acrylate and</li><li>an intermediate block which is a random isobornyl acrylate / isobutyl methacrylate / isobutyl acrylate copolymer.</li></ul>

According to a ninth variant, the polymer used in the compositions according to the invention may comprise:<ul id="ul0022" list-style="dash" compact="compact"><li>a first sequence of Tg greater than or equal to 40 ° C, for example having a Tg ranging from 70 to 110 ° C, which is a copolymer acrylic acid / methyl acrylate,</li><li>a second sequence of Tg less than or equal to 20 ° C, for example ranging from 0 to 20 ° C, which is a homopolymer of methyl acrylate and</li><li>an intermediate block which is an acrylic acid / methyl acrylate / polyacrylate copolymer.</li></ul>

Second embodiment

According to a second embodiment, the polymer used in the compositions according to the invention comprises at least one (in particular a) first block having a glass transition temperature (Tg) of between 20 and 40.degree. in accordance with the sequences described in paragraph c) and at least one (in particular one) second sequence having a glass transition temperature of less than or equal to 20 ° C, as described above in paragraph b) or a glass transition temperature greater than or equal to 40 ° C, as described in paragraph a) above.

Preferably, the proportion of the first block having a Tg of between 20 and 40 ° C ranges from 10 to 85% by weight of the polymer, more preferably from 30 to 80% and more preferably from 50 to 70%.

When the second block is a block having a Tg greater than or equal to 40 ° C, it is preferably present in a proportion ranging from 10 to 85% by weight of the polymer, better still from 20 to 70% and even more preferably from 30 to 70%. %.

When the second block is a block having a Tg of less than or equal to 20 ° C, it is preferably present in a proportion ranging from 10 to 85% by weight of the polymer, better still from 20 to 70% and even more preferably from 20 to 50%. %.

Preferably, the first block having a Tg of between 20 and 40 ° C. is a copolymer derived from monomers which are such that the homopolymer corresponding to a Tg of greater than or equal to 40 ° C. and of monomers which are such ( s) that the corresponding homopolymer has a Tg less than or equal to 20 ° C.

Advantageously, the second block having a Tg less than or equal to 20 ° C or having a Tg greater than or equal to 40 ° C is a homopolymer.

Thus, according to a first variant of this second embodiment, the polymer used in the compositions according to the invention may comprise:<ul id="ul0023" list-style="dash" compact="compact"><li>a first Tg sequence of between 20 and 40 ° C, for example having a Tg of 25 to 39 ° C, which is a copolymer comprising at least one methyl acrylate monomer, at least one methyl methacrylate monomer and at least one monomer acrylic acid,</li><li>a second sequence of Tg greater than or equal to 40 ° C, for example ranging from 85 to 125 ° C, which is a homopolymer composed of monomers methyl methacrylate and</li><li>an intermediate block comprising at least one monomer methyl acrylate, methyl methacrylate and</li><li>an intermediate sequence comprising methyl methacrylate, at least one acrylic acid monomer and at least one methyl acrylate monomer.</li></ul>

According to the second variant of this second embodiment, the polymer used in the compositions according to the invention may comprise:<ul id="ul0024" list-style="dash" compact="compact"><li>a first Tg sequence of between 20 and 40 ° C, for example having a Tg of 21 to 39 ° C, which is a copolymer comprising isobornyl acrylate / isobutyl methacrylate / 2-ethylhexyl acrylate,</li><li>a second Tg sequence less than or equal to 20 ° C, for example ranging from -65 to -35 ° C, which is a homopolymer of methyl methacrylate and</li><li>an intermediate block which is a random copolymer of isobornyl acrylate / isobutyl methacrylate / 2-ethylhexyl acrylate.</li></ul>

According to a third variant of this second embodiment, the polymer used in the compositions according to the invention may comprise:<ul id="ul0025" list-style="dash" compact="compact"><li>a first Tg sequence of between 20 and 40 ° C, for example having a Tg of 21 to 39 ° C, which is an isobornyl acrylate / methyl acrylate / acrylic acid copolymer,</li><li>a second sequence of Tg greater than or equal to 40 ° C, for example ranging from 85 to 115 ° C, which is a homopolymer of isobornyl acrylate and</li><li>an intermediate block which is a random copolymer of isobornyl acrylate / methyl acrylate / acrylic acid.</li></ul>

The cosmetic composition according to the invention preferably comprises the polymer (s) pseudo-block (s) in an amount ranging from 0.1 to 60% by weight, preferably from 0.5 to 50% by weight and from even more preferably from 1 to 40% by weight relative to the total weight of the composition.

The cosmetic styling composition according to the invention may also contain at least one additive chosen from the other non-pseudo-block fixing polymers (additional fixing polymers), silicones in soluble form, dispersed, micro-dispersed, thickening polymers, gelling agents, nonionic surfactants, anionic, cationic and amphoteric, ceramides and pseudo-ceramides, vitamins and pro-vitamins including panthenol, vegetable oils, animal, mineral and synthetic, waxes other than ceramides and pseudo-ceramides, water-soluble and fat-soluble sunscreens, silicone or non-silicone, glycerol, permanent or temporary dyes, pearlescent and opacifying agents, sequestering agents, plasticizers, solubilizing agents, pH modifiers, the mineral thickeners, antioxidants, the hydroxy acids, penetration agents, the perfumes, the solubilizing agents of the perfume (peptizer), preservatives, anti-corrosion agents.

These additives are present in the cosmetic composition according to the invention in an amount ranging from 0 to 20% by weight relative to the total weight of the cosmetic composition.

Those skilled in the art will take care to choose the possible additives and their amount so that they do not adversely affect the properties of the compositions of the present invention.

Advantageously, the compositions according to the present invention contain at least one additional cosmetic additive chosen from thickening polymers, gelling agents and surfactants.

According to a first preferred embodiment, the compositions according to the present invention contain at least one thickening polymer also called "rheology adjusting agents".

The rheology adjusting agents may be chosen from fatty acid amides (diethanol or coconut monoethanolamide), oxyethylenated alkyl ether carboxylic acid monoethanolamide), cellulosic thickeners (hydroxyethylcellulose, hydroxypropyl cellulose, carboxymethylcellulose), guar gum and its derivatives (hydroxypropylguar), gums of microbial origin (xanthan gum, scleroglucan gum), crosslinked homopolymers or copolymers of acrylic acid or acrylamidopropanesulfonic acid and associative thickening polymers as described below.

These associative polymers are water-soluble polymers capable, in an aqueous medium, of reversibly associating with each other or with other molecules.

Their chemical structure comprises hydrophilic zones, and hydrophobic zones characterized by at least one fatty chain.

The associative polymers may be of anionic, cationic, amphoteric or nonionic type.

Their concentration may vary from about 0.01 to 10%, preferably 0.1 to 5% by weight relative to the total weight of the composition according to the invention.

Among the associative polymers of the anionic type, mention may be made of:<ul id="ul0026" list-style="dash" compact="compact"><li>(I) those comprising at least one hydrophilic unit, and at least one fatty-chain allyl ether unit, more particularly those whose hydrophilic unit is constituted by an ethylenic unsaturated anionic monomer, more particularly by a vinyl carboxylic acid and any particularly with an acrylic acid or a methacrylic acid or mixtures thereof, and whose fatty-chain allyl ether unit corresponds to the following monomer of formula (XV):         CH₂ = CR 'CH₂ OB_not R (XV)    in which R 'denotes H or CH₃, B denotes the ethyleneoxy radical, n is zero or denotes an integer ranging from 1 to 100, R denotes a hydrocarbon radical chosen from alkyl, arylalkyl, aryl, alkylaryl and cycloalkyl radicals, comprising from 8 to 30 carbon atoms, preferably 10 to 24, and more particularly 12 to 18 carbon atoms. A more particularly preferred unit of formula (XV) is a unit in which R 'denotes H, n is equal to 10, and R denotes a stearyl radical (C₁₈). Anionic associative polymers of this type are described and prepared according to an emulsion polymerization process in patent EP-0 216 479. Among these anionic associative polymers, it is particularly preferred according to the invention, polymers formed from 20 to 60% by weight of acrylic acid and / or methacrylic acid, from 5 to 60% by weight of lower alkyl (meth) acrylates, from 2 to 50% by weight of fatty-chain allyl ether of formula (XV), and from 0 to 1% by weight of a crosslinking agent which is a well-known copolymerizable polyethylenic unsaturated monomer, like diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate, and methylene-bis-acrylamide. Among these, the crosslinked terpolymers of methacrylic acid, ethyl acrylate, polyethylene glycol (10 EO) and stearyl alcohol (Steareth 10) are particularly preferred, in particular those sold by the company ALLIED COLLOIDS under the names SALCARE SC80® and SALCARE SC90® which are 30% aqueous emulsions of a crosslinked terpolymer of methacrylic acid, ethyl acrylate and steareth-10-allyl ether (40/50/10).</li><li>(II) those comprising at least one hydrophilic unit of unsaturated olefinic carboxylic acid type, and at least one hydrophobic unit of alkyl ester type (C₁₀-C₃₀) unsaturated carboxylic acid. Preferably, these polymers are chosen from those whose hydrophilic unit of unsaturated olefinic carboxylic acid type corresponds to the following monomer of formula (XVI):<chemistry id="chem0002" num="0002"><img file="EP1586299A1_D0006.tif" /></chemistry>    in which, R₁ denotes H or CH₃ or C₂H₅that is to say, acrylic acid, methacrylic acid or ethacrylic acid units, and whose hydrophobic unit of alkyl ester type (C₁₀-C₃₀) unsaturated carboxylic acid corresponds to the monomer of formula (XVII) below:<chemistry id="chem0003" num="0003"><img file="EP1586299A1_D0007.tif" /></chemistry>    in which, R₂ denotes H or CH₃ or C₂H₅ (ie acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH₃ (methacrylate patterns), R₃ designating a C-alkyl radical₁₀-C₃₀, and preferably in C₁₂-C₂₂. Alkyl esters (C₁₀-C₃₀) unsaturated carboxylic acids according to the invention include, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl acrylate, and corresponding methacrylates lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate. Anionic polymers of this type are, for example, described and prepared according to US Pat. Nos. 3,915,921 and 4,509,949. Among this type of anionic associative polymers, there will be used more particularly polymers formed from a monomer mixture comprising:<ul id="ul0027" list-style="none" compact="compact"><li>(i) essentially acrylic acid,</li><li>(ii) an ester of formula (XVII) described above and in which R₂ denotes H or CH₃, R₃ designating an alkyl radical having from 12 to 22 carbon atoms, and</li><li>(iii) a crosslinking agent, which is a well-known copolymerizable polyethylenic unsaturated monomer, such as diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate, and methylenebisacrylamide .</li></ul>Among this type of anionic associative polymers, use will more particularly be made of 95 to 60% by weight of acrylic acid (hydrophilic unit), 4 to 40% by weight of C-alkyl acrylate.₁₀-C₃₀ (Hydrophobic unit), and 0 to 6% by weight of polymerizable crosslinking monomer, or those consisting of 98 to 96% by weight of acrylic acid (hydrophilic unit), 1 to 4% by weight of alkyl acrylate in C₁₀-C₃₀ (Hydrophobic unit), and 0.1 to 0.6% by weight of crosslinking polymerizable monomer such as those described above. Among the above polymers, the products sold by the company GOODRICH under the trade names PEMULEN TR1®, PEMULEN TR2® and CARBOPOL 1382®, and even more preferentially PEMULEN TR1®, are particularly preferred according to the present invention. product sold by the company SEPPIC under the name COATEX SX®.</li><li>(III) terpolymers of maleic anhydride / α-olefin in C₃₀-C₃₈alkyl maleate such as the product (maleic anhydride / C-α-olefin copolymer)₃₀-C₃₈isopropyl maleate) sold under the name PERFORMA V 1608® by the company NEWPHASE TECHNOLOGIES.</li><li>(IV) acrylic terpolymers comprising:<ul id="ul0028" list-style="none" compact="compact"><li>(a) about 20% to 70% by weight of an α, β-monoethylenically unsaturated carboxylic acid,</li><li>(b) about 20 to 80% by weight of a non-surfactant α, β-monoethylenically unsaturated monomer different from (a),</li><li>(c) about 0.5 to 60% by weight of a nonionic mono-urethane which is the reaction product of a monohydric surfactant with a monoethylenically unsaturated monoisocyanate,</li></ul>    such as those described in the patent application EP-A-0173109 and more particularly that described in Example 3, namely, a terpolymer methacrylic acid / methyl acrylate / dimethyl metaisopropenyl benzyl isocyanate alcohol ethoxylated behenate (400E) in 25% aqueous dispersion.</li><li>(V) copolymers comprising, among their monomers, an α, β-monoethylenically unsaturated carboxylic acid and an α, β-monoethylenically unsaturated carboxylic acid ester and an oxyalkylenated fatty alcohol.</li></ul>

Preferentially, these compounds also comprise, as monomer, a carboxylic acid ester with α, β-monoethylenic unsaturation and C-alcohol₁-C₄.

By way of example of this type of compound, mention may be made of Aculyn 22® sold by the company Rohm and Haas, which is a methacrylic acid / ethyl acrylate / stearyl methacrylate oxyalkylenated terpolymer.

Among the associative polymers of cationic type, mention may be made of:<ul id="ul0029" list-style="dash"><li>(I) cationic associative polyurethanes whose family has been described by the Applicant in the French patent application No. 0009609; it can be represented by the following general formula (XVIII):         RX- (P) n- [L- (Y) m] r-L '- (P') p-X'-R '(XVIII)    in which :<ul id="ul0030" list-style="none" compact="compact"><li>R and R ', which may be identical or different, represent a hydrophobic group or a hydrogen atom;</li><li>X and X ', which may be identical or different, represent a group comprising an amine functional group which may or may not carry a hydrophobic group, or the group L ";</li><li>L, L 'and L ", identical or different, represent a group derived from a diisocyanate;</li><li>P and P ', which may be identical or different, represent a group comprising an amine functional group which may or may not carry a hydrophobic group;</li><li>Y represents a hydrophilic group;</li><li>r is an integer between 1 and 100, preferably between 1 and 50 and in particular between 1 and 25,</li><li>n, m, and p are each independently from 0 to 1000;</li><li>the molecule containing at least one protonated or quaternized amine function and at least one hydrophobic group.</li></ul> In a preferred embodiment of these polyurethanes, the only hydrophobic groups are the R and R 'groups at the chain ends. A preferred family of cationic associative polyurethanes is that corresponding to formula (XVIII) described above and wherein:<ul id="ul0031" list-style="none" compact="compact"><li>R and R 'both independently represent a hydrophobic group,</li><li>X, X 'each represent a group L ",</li><li>n and p are between 1 and 1000 and</li><li>L, L ', L ", P, P', Y and m have the meaning indicated above.</li></ul>Another preferred family of cationic associative polyurethanes is that corresponding to formula (XVIII) above in which:<ul id="ul0032" list-style="none" compact="compact"><li>R and R 'are each independently a hydrophobic group, X, X' are each L ", n and p are 0, and L, L ', L", Y and m are as defined above.</li></ul>The fact that n and p are 0 means that these polymers do not contain units derived from an amine-functional monomer incorporated in the polymer during the polycondensation. The protonated amine functions of these polyurethanes result from the hydrolysis of isocyanate functional groups, in excess, at the end of the chain, followed by the alkylation of the primary amine functions formed by alkylation agents with a hydrophobic group, that is to say to say compounds of the type RQ or R'Q, in which R and R 'are as defined above and Q denotes a leaving group such as a halide, a sulphate, etc. Yet another preferred family of cationic associative polyurethanes is that corresponding to formula (Ia) above wherein:<ul id="ul0033" list-style="none" compact="compact"><li>R and R 'both independently represent a hydrophobic group,</li><li>X and X 'each independently represent a group comprising a quaternary amine,</li><li>n and p are zero, and</li><li>L, L ', Y and m have the meaning indicated above.</li></ul>The number-average molecular weight of the cationic associative polyurethanes is preferably between 400 and 500,000, in particular between 1,000 and 400,000 and ideally between 1,000 and 300,000. Hydrophobic group is understood to mean a radical or polymer with a hydrocarbon chain, saturated or unsaturated, linear or branched, which may contain one or more heteroatoms such as P, O, N, S, or a perfluorinated or silicone chain radical. When it refers to a hydrocarbon radical, the hydrophobic group comprises at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferably from 18 to 30 carbon atoms. Preferably, the hydrocarbon group comes from a monofunctional compound. By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It can also denote a hydrocarbon polymer such as for example polybutadiene. When X and / or X 'denote a group containing a tertiary or quaternary amine, X and / or X' may represent one of the following formulas:<chemistry id="chem0004" num="0004"><img file="EP1586299A1_D0008.tif" /></chemistry><chemistry id="chem0005" num="0005"><img file="EP1586299A1_D0009.tif" /></chemistry>    in which :<ul id="ul0034" list-style="none" compact="compact"><li>R₂ represents an alkylene radical having 1 to 20 carbon atoms, linear or branched, with or without a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms may be replaced by a heteroatom selected from N, S, O, P;</li><li>R₁ and R₃, identical or different, denote a C 1 alkyl or alkenyl radical₁-C₃₀, linear or branched, an aryl radical, at least one of the carbon atoms may be replaced by a heteroatom selected from N, S, O, P;</li><li>AT^- is a physiologically acceptable counterion.</li></ul>The groups L, L 'and L "represent a group of formula:<chemistry id="chem0006" num="0006"><img file="EP1586299A1_D0010.tif" /></chemistry>    in which :<ul id="ul0035" list-style="none" compact="compact"><li>Z represents -O-, -S- or -NH-; and</li><li>R₄ represents an alkylene radical having 1 to 20 carbon atoms, linear or branched, with or without a saturated or unsaturated ring, an arylene radical, one or more of the carbon atoms may be replaced by a heteroatom selected from N, S, O and P.</li></ul>The groups P and P ', comprising an amine function, may represent at least one of the following formulas:<chemistry id="chem0007" num="0007"><img file="EP1586299A1_D0011.tif" /></chemistry><chemistry id="chem0008" num="0008"><img file="EP1586299A1_D0012.tif" /></chemistry><chemistry id="chem0009" num="0009"><img file="EP1586299A1_D0013.tif" /></chemistry>    in which :<ul id="ul0036" list-style="none" compact="compact"><li>R₅ and R₇ have the same meanings as R₂ previously defined;</li><li>R₆, R₈ and R₉ have the same meanings as R₁ and R₃ previously defined;</li><li>R₁₀ represents a linear or branched, optionally unsaturated, alkylene group which may contain one or more heteroatoms chosen from N, O, S and P,</li><li>and A^- is a physiologically acceptable counterion.</li></ul>As regards the meaning of Y, the term "hydrophilic group" means a water-soluble polymeric group or not. By way of example, non-polymers include ethylene glycol, diethylene glycol and propylene glycol. When it comes, according to a preferred embodiment, a hydrophilic polymer, there may be mentioned by way of example polyethers, sulfonated polyesters, sulfonated polyamides, or a mixture of these polymers. Preferably, the hydrophilic compound is a polyether and especially a poly (ethylene oxide) or poly (propylene oxide). The cationic associative polyurethanes of formula (XVIII) that can be used according to the invention are formed from diisocyanates and from various compounds having functions with a labile hydrogen. The functions with a labile hydrogen may be alcohol, primary or secondary amine or thiol functions giving, after reaction with the diisocyanate functions, respectively polyurethanes, polyureas and polythioureas. The term "polyurethanes" usable according to the present invention encompasses these three types of polymers namely polyurethanes themselves, polyureas and polythioureas as well as copolymers thereof. A first type of compound used in the preparation of the polyurethane of formula (XVIII) is a compound comprising at least one amine-functional unit. This compound can be multifunctional, but preferentially the compound is difunctional, that is to say that according to a preferred embodiment, this compound comprises two labile hydrogen atoms carried for example by a hydroxyl function, primary amine, secondary amine or thiol. It is also possible to use a mixture of multifunctional and difunctional compounds in which the percentage of multifunctional compounds is low. As indicated above, this compound may comprise more than one amine-functional unit. It is then a polymer bearing a repetition of the amine functional unit. This type of compound can be represented by one of the following formulas:         HZ- (P) n ZH,    or         HZ- (P ') p-ZH    in which Z, P, P ', n and p are as defined above. As an example of an amine-functional compound, mention may be made of N-methyldiethanolamine, N-tert-butyl diethanolamine and N-sulfoethyldiethanolamine. The second compound used in the preparation of the polyurethane of formula (XVIII) is a diisocyanate corresponding to the formula:         O = C = NR₄-N = C = O    in which R₄ is defined above. By way of example, mention may be made of methylenediphenyldiisocyanate, methylenecyclohexane diisocyanate, isophorone diisocyanate, toluene diisocyanate, naphthalene diisocyanate, butane diisocyanate and hexane diisocyanate. A third compound used in the preparation of the polyurethane of formula (XVIII) is a hydrophobic compound intended to form the terminal hydrophobic groups of the polymer of formula (XVIII). This compound consists of a hydrophobic group and a function with labile hydrogen, for example a hydroxyl function, primary or secondary amine, or thiol. By way of example, this compound may be a fatty alcohol, such as in particular stearyl alcohol, dodecyl alcohol or decyl alcohol. When this compound comprises a polymeric chain, it may be, for example, hydrogenated polybutadiene alpha-hydroxyl. The hydrophobic group of the polyurethane of formula (XVIII) can also result from the quaternization reaction of the tertiary amine of the compound comprising at least one tertiary amine unit. Thus, the hydrophobic group is introduced by the quaternizing agent. This quaternizing agent is a compound of the type RQ or R'Q, in which R and R 'are as defined above and Q denotes a leaving group such as a halide, a sulphate, etc. The cationic associative polyurethane may further comprise a hydrophilic block. This sequence is provided by a fourth type of compound used in the preparation of the polymer. This compound can be multifunctional. It is preferably difunctional. One can also have a mixture where the percentage of multifunctional compound is low. The functions with a labile hydrogen are alcohol, primary or secondary amine or thiol functions. This compound may be a polymer terminated at the chain ends by one of these functions with labile hydrogen. By way of example, non-polymers include ethylene glycol, diethylene glycol and propylene glycol. When it is a hydrophilic polymer, mention may be made by way of example of polyethers, sulphonated polyesters, sulphonated polyamides, or a mixture of these polymers. Preferably, the hydrophilic compound is a polyether and especially a poly (ethylene oxide) or poly (propylene oxide). The hydrophilic group Y in formula (XVIII) is optional. Indeed, the quaternary or protonated amine functional units may be sufficient to provide the solubility or hydrodispersibility necessary for this type of polymer in an aqueous solution. Although the presence of a hydrophilic Y group is optional, cationic associative polyurethanes having such a group are preferred.</li><li>(II) quaternized cellulose derivatives and polyacrylates with non-cyclic amine side groups.</li></ul>

The quaternized cellulose derivatives are in particular<ul id="ul0037" list-style="dash" compact="compact"><li>quaternized celluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups containing at least 8 carbon atoms, or mixtures thereof,</li><li>quaternized hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups containing at least 8 carbon atoms, or mixtures thereof.</li></ul>

The alkyl radicals borne by the above-quaternized celluloses or hydroxyethylcelluloses preferably contain from 8 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups.

Examples of quaternized alkylhydroxyethylcelluloses with C-fatty chains may be indicated.₈-C₃₀, QUATRISOFT LM 200® products, QUATRISOFT LM-X 529-18-A®, QUATRISOFT LM-X 529-18B® (C-alkyl)₁₂) and QUATRISOFT LM-X 529-8® (C-alkyl)₁₈) sold by the company Amerchol and the products CRODACEL QM®, CRODACEL QL® (C12 alkyl) and CRODACEL QS® (C-alkyl)₁₈) marketed by the company CRODA.

The amphoteric associative polymers are preferably chosen from those comprising at least one non-cyclic cationic unit. Even more particularly, those prepared from or comprising 1 to 20 mole% of monomer having a fatty chain, and preferably 1.5 to 15 mole% and more particularly 1.5 to 6 mole%, based on the number, are preferred. total moles of monomers.

The preferred amphoteric associative polymers according to the invention comprise, or are prepared by copolymerizing:<ul id="ul0038" list-style="none"><li>1) at least one monomer of formula (XIX) or (XX):<chemistry id="chem0010" num="0010"><img file="EP1586299A1_D0014.tif" /></chemistry><chemistry id="chem0011" num="0011"><img file="EP1586299A1_D0015.tif" /></chemistry>    in which, R₁ and R₂, identical or different, represent a hydrogen atom or a methyl radical, R₃, R₄ and R₅, identical or different, represents a linear or branched alkyl radical having from 1 to 30 carbon atoms,<ul id="ul0039" list-style="none" compact="compact"><li>Z represents an NH group or an oxygen atom,</li><li>n is an integer from 2 to 5,</li><li>AT^- is an anion derived from an organic or inorganic acid, such as a methosulphate anion or a halide such as chloride or bromide;</li></ul></li><li>2) at least one monomer of formula (XXI)         R₆-CH = CR₇-COOH (XXI)    in which, R₆ and R₇, identical or different, represent a hydrogen atom or a methyl radical;    and</li><li>3) at least one monomer of formula (XXII):         R₆-CH = CR₇-COXR₈     (XXII)</li></ul>    in which R₆ and R₇, identical or different, represent a hydrogen atom or a methyl radical, X denotes an oxygen or nitrogen atom and R₈ denotes a linear or branched alkyl radical having from 1 to 30 carbon atoms;    at least one of the monomers of formula (XIX), (XX) or (XXII) comprising at least one fatty chain.    The monomers of formula (XIX) and (XX) of the present invention are preferably chosen from the group consisting of:<ul id="ul0040" list-style="dash" compact="compact"><li>dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate,</li><li>diethylaminoethyl methacrylate, diethylaminoethyl acrylate,</li><li>dimethylaminopropylmethacrylate, dimethylaminopropylacrylate,</li><li>dimethylaminopropylmethacrylamide, dimethylaminopropylacrylamide,</li></ul>    these monomers being optionally quaternized, for example by a C 4 alkyl halide₁-C₄ or C-dialkyl sulphate₁-C₄.

More particularly, the monomer of formula (XIX) is chosen from acrylamidopropyltrimethylammonium chloride and methacrylamidopropyltrimethylammonium chloride.

The monomers of formula (XXI) of the present invention are preferably selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid and 2-methylcrotonic acid. More particularly, the monomer of formula (XXI) is acrylic acid.

The monomers of formula (XXII) of the present invention are preferably selected from the group consisting of C-alkyl acrylates or methacrylates.₁₂-C₂₂ and more particularly in C₁₆-C₁₈.

The monomers constituting the amphoteric fatty-chain polymers of the invention are preferably already neutralized and / or quaternized.

The ratio of the number of cationic charges / anionic charges is preferably equal to about 1.

The amphoteric associative polymers according to the invention preferably comprise from 1 to 10 mol% of the monomer comprising a fatty chain (monomer of formula (XIX), (XX) or (XXII)), and preferably from 1.5 to 6% mol.

The weight average molecular weight of the amphoteric associative polymers according to the invention can vary from 500 to 50,000,000 and are preferably between 10,000 and 5,000,000.

The amphoteric associative polymers according to the invention may also contain other monomers such as nonionic monomers and in particular such as C-alkyl acrylates or methacrylates.₁-C₄.

Amphoteric associative polymers according to the invention are for example described and prepared in the patent application WO9844012.

Among the amphoteric associative polymers according to the invention, acrylic acid / (meth) acrylamidopropyltrimethylammonium chloride / stearyl methacrylate terpolymers are preferred.

The nonionic associative polymers that may be used according to the invention are preferably chosen from:<ul id="ul0041" list-style="dash" compact="compact"><li>(1) celluloses modified with groups comprising at least one fatty chain;    we can cite as an example:<ul id="ul0042" list-style="dash" compact="compact"><li>hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably in the form of C₈-C₂₂, like the product NATROSOL PLUS GRADE 330 CS® (C-alkyles₁₆) sold by the company AQUALON, or the product BERMOCOLL EHM 100® sold by the company BEROL NOBEL,</li><li>those modified with alkyl phenol polyalkylene glycol ether groups, such as the product AMERCELL POLYMER HM-1500® (polyethylene glycol (15) nonylphenol ether) sold by the company Amerchol.</li></ul></li><li>(2) hydroxypropyl guars modified with groups comprising at least one fatty chain such as the product ESAFLOR HM 22® (C 1 -C 4 alkyl chain₂₂) sold by LAMBERTI, the products RE210-18® (C alkyl chain₁₄) and RE205-1® (C-alkyl chain₂₀) sold by RHONE POULENC.</li><li>(3) vinyl pyrrolidone copolymers and hydrophobic fatty-chain monomers, which may be exemplified by:<ul id="ul0043" list-style="dash" compact="compact"><li>ANTARON V216® or GANEX V216® (vinylpyrrolidone / hexadecene copolymer) sold by ISP</li><li>the ANTARON V220® or GANEX V220® products (vinylpyrrolidone / eicosene copolymer) sold by ISP</li></ul></li><li>(4) copolymers of methacrylates or alkyl acrylates in C₁-C₆ and amphiphilic monomers comprising at least one fatty chain, such as, for example, the oxyethylenated methyl acrylate / stearyl acrylate copolymer sold by GOLDSCHMIDT under the name ANTIL 208®.</li><li>(5) copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain, such as, for example, polyethylene glycol methacrylate / lauryl methacrylate copolymer.</li><li>(6) polyether polyurethanes comprising in their chain, both hydrophilic sequences of mostly polyoxyethylenated nature and hydrophobic sequences which may be aliphatic sequences alone and / or cycloaliphatic and / or aromatic sequences.</li><li>(7) polymers having an aminoplast ether skeleton having at least one fatty chain, such as the PURE THIX® compounds provided by the company SUD-CHEMIE.</li></ul>

Preferably, the polyether polyurethanes comprise at least two hydrocarbon-based lipophilic chains having from 6 to 30 carbon atoms, separated by a hydrophilic sequence, the hydrocarbon chains possibly being pendant chains or chains at the end of the hydrophilic sequence. In particular, it is possible that one or more pendant chains are provided. In addition, the polymer may comprise a hydrocarbon chain at one end or at both ends of a hydrophilic block.

The polyether polyurethanes may be multiblocked, in particular in the form of a triblock. The hydrophobic sequences may be at each end of the chain (for example: hydrophilic central block triblock copolymer) or distributed at both the ends and in the chain (multiblock copolymer for example). These same polymers may also be graft or star.

The nonionic polyurethane polyethers with a fatty chain may be triblock copolymers whose hydrophilic sequence is a polyoxyethylenated chain containing from 50 to 1000 oxyethylenated groups. Nonionic polyurethane polyethers have a urethane bond between the hydrophilic blocks, hence the origin of the name.

By extension are also included among the nonionic polyurethane fatty chain polyethers those whose hydrophilic sequences are linked to the lipophilic blocks by other chemical bonds.

As examples of fatty-chain nonionic polyurethane polyethers that may be used in the invention, it is also possible to use also the urea-functional Rheolate 205® sold by Rheox or the Rheolates® 208, 204 or 212, as well as Acrysol RM 184®.

Mention may also be made of the product ELFACOS T210® with an alkyl chain in C_12-14 and the product ELFACOS T212® with C-alkyl chain₁₈ from AKZO.

The product DW 1206B® from ROHM &amp; HAAS with C alkyl chain₂₀ and urethane bond, proposed at 20% dry matter in water, can also be used.

It is also possible to use solutions or dispersions of these polymers, especially in water or in an aqueous-alcoholic medium. By way of example, such polymers include, for example, Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by Rheox. It is also possible to use the product DW 1206F and the DW 1206J proposed by the company Rohm &amp; Haas.

The polyether polyurethanes that can be used according to the invention are in particular those described in the article by G. Fonnum, J. Bakke and Fk. Hansen - Colloid Polym. Sci 271, 380, 389 (1993).

More particularly still it is preferred to use a polyether polyurethane obtainable by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 moles of ethylene oxide, (ii) alcohol stearyl or decyl alcohol and (iii) at least one diisocyanate.

Such polyether polyurethanes are sold in particular by the company ROHM &amp; HAAS under the names Aculyn 46® and Aculyn 44® [ACULYN 46® is a polycondensate of polyethylene glycol with 150 or 180 moles of ethylene oxide, of stearyl alcohol and methylenebis (4-cyclohexylisocyanate) (SMDI), 15% by weight in a matrix of maltodextrin (4%) and water (81%); ACULYN 44® is a polycondensate of polyethylene glycol with 150 or 180 moles of ethylene oxide, decyl alcohol and methylene bis (4-cyclohexylisocyanate) (SMDI), to 35% by weight in a mixture of propylene glycol (39%) and water (26%)].

As thickeners, non-associative gelling agents may also be used; these include polymers or copolymers of unsaturated organic carboxylic acids or unsaturated esters, polysaccharide derivatives, gums, colloidal silicates, polyethylene glycols, polyvinylpyrrolidones, hydrophilic silica gels.

The amount of thickening agents present in the composition according to the invention is between 0.01 and 10% and preferably between 0.1 and 5% by weight relative to the total weight of the composition.

According to a second preferred embodiment, the composition according to the present invention additionally contains at least one surfactant.

Surfactants suitable for the implementation of the present invention are in particular the following:

(i) Anionic surfactant (s):

As an example of usable anionic surfactants, alone or mixtures, in the context of the present invention, mention may be made in particular (non-limiting list) of the salts (in particular alkaline salts, including sodium, ammonium salts, amine salts, salts of amino alcohols or magnesium salts) of the following compounds: alkyl sulphates, alkyl ether sulfates, alkylamido, alkylaryl, monoglycerides sulphates; the alkylsulfonates, alkyl phosphates, alkylamidesulphonates, alkylarylsulfonates, α-olefin sulfonates, paraffin sulfonates; the alkyls (C₆-C₂₄) sulfosuccinates, alkyls (C₆-C₂₄) ethersulfosuccinates, alkyls (C₆-C₂₄) amidesulfosuccinates; the alkyls (C₆-C₂₄) sulfoacetates; acyl (C₆-C₂₄) sarcosinates and acyls (C₆-C₂₄) glutamates. It is also possible to use the alkyl esters (C₆-C₂₄) carboxylic polyglycosides such as alkylglucoside citrates, alkylpolyglycoside tartrate and alkylpolyglycoside sulfosuccinates, alkylsulfosuccinamates; acylisethionates and N-acyltaurates, the alkyl or acyl radical of all these different compounds preferably comprising from 12 to 20 carbon atoms, and the aryl radical preferably denoting a phenyl or benzyl group. Among the anionic surfactants that can still be used, mention may also be made of fatty acid salts such as the salts of oleic, ricinoleic, palmitic and stearic acids, coconut oil acid or hydrogenated coconut oil acid; acyl lactylates whose acyl radical has 8 to 20 carbon atoms. It is also possible to use alkyl D galactoside uronic acids and their salts, alkyl acids (C₆-C₂₄polyoxyalkylenated carboxylic ether, alkyl acids (C₆-C₂₄) polyoxyalkylenated carboxylic aryl ether, alkyl acids (C₆-C₂₄) polyoxyalkylenated amido ether carboxylic acid and their salts, in particular those containing from 2 to 50 alkylene oxide groups, in particular ethylene, and mixtures thereof.

(ii) Nonionic surfactant (s):

Nonionic surfactants are also well known compounds per se (see in particular in this regard "Handbook of Surfactants" by MR PORTER, Blackie &amp; Son editions (Glasgow and London), 1991, pp 116-178) and their nature does not, in the context of the present invention, of a critical nature. Thus, they may be chosen in particular from (non-limiting list) alcohols, alpha-diols, polyethoxylated alkylphenols, polypropoxylated, having a fatty chain comprising for example 8 to 18 carbon atoms, the number of ethylene oxide groups or propylene oxide ranging in particular from 2 to 50. Mention may also be made of copolymers of ethylene oxide and of propylene oxide, condensates of ethylene oxide and propylene oxide on fatty alcohols; the polyethoxylated fatty amides preferably having from 2 to 30 moles of ethylene oxide, polyglycerolated fatty amides comprising on average 1 to 5 glycerol groups and in particular 1.5 to 4; oxyethylenated sorbitan fatty acid esters having from 2 to 30 moles of ethylene oxide; fatty acid esters of sucrose, the fatty acid esters of polyethylene glycol, alkylpolyglycosides, N-alkyl glucamine derivatives, amine oxides such as alkyl oxides (C₁₀ - C₁₄) amines or N-acylaminopropylmorpholine oxides.

(iii) Amphoteric (s) or zwitterionic surfactant (s):

Amphoteric or zwitterionic surfactants, the nature of which does not fall within the scope of the present invention of a critical nature, may be in particular (non-limiting list) derivatives of aliphatic secondary or tertiary amines, in which the aliphatic radical is a linear or branched chain containing 8 to 18 carbon atoms and containing at least one water-soluble anionic group (for example carboxylate, sulfonate, sulfate, phosphate or phosphonate); mention may also be made of alkyl (C₈-C₂₀) betaines, sulfobetaines, alkyls (C₈-C₂₀) amidoalkyl (C)₁-C₆) betaines or alkyl (C₈-C₂₀) amidoalkyl (C)₁-C₆) sulfobetaines.

Among the amine derivatives, mention may be made of the products sold under the name MIRANOL, as described in US Pat. Nos. 2,528,378 and 2,781,354 and classified in the CTFA dictionary, 3rd edition, 1982, under the names Amphocarboxyglycinates and Amphocarboxypropionates of respective structures:         R₂ -CONHCH₂CH₂ -N (R₃) (R₄) (CH₂COO)    in which: R₂ denotes an alkyl radical of an acid R₂-COOH present in the hydrolysed coconut oil, a heptyl, nonyl or undecyl radical, R₃ denotes a beta-hydroxyethyl group and R₄ a carboxymethyl group;    and         R₂'-CONHCH₂CH₂-N (B) (C)    in which :<ul id="ul0044" list-style="none" compact="compact"><li>B represents -CH₂CH₂OX ', C represents - (CH₂)_z -Y ', with z = 1 or 2,</li><li>X 'denotes the grouping -CH₂CH₂-COOH or a hydrogen atom</li><li>Y 'is -COOH or the radical -CH₂ - CHOH - SO₃H</li><li>R₂'is an alkyl radical of a R-acid₉ -COOH present in coconut oil or in hydrolysed linseed oil, an alkyl radical, especially in C₇, C₉, C₁₁ or C₁₃, an alkyl radical in C₁₇ and its iso form, a radical C₁₇ unsaturated.</li></ul>

These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names disodium cocoamphodiacetate, disodium Lauroamphodiacetate, caprylamphodiacetate Disodium, Disodium capryloamphodiacetate, Cocoamphodipropionate Disodium, Disodium Lauroamphodipropionate, Caprylamphodipropionate Disodium, Disodium capryloamphodipropionate, Lauroamphodipropionic acid, Cocoamphodipropionic acid.

By way of example, mention may be made of cocoamphodiacetate sold under the trade name MIRANOL® C2M concentrated by Rhodia Chimie.

(iv) Cationic surfactants:

Among the cationic surfactants, mention may be made in particular (non-limiting list) of the salts of primary, secondary or tertiary fatty amines, optionally polyoxyalkylenated; quaternary ammonium salts such as tetraalkylammonium, alkylamidoalkyltrialkylammonium, trialkylbenzylammonium, trialkylhydroxyalkylammonium or alkylpyridinium chlorides or bromides; imidazoline derivatives; or oxides of amines with a cationic character.

The amount of surfactants present in the composition according to the invention is between 0.01 and 40% and preferably between 0.1 and 30% by weight relative to the total weight of the composition.

The present invention also relates to a cosmetic process for shaping or holding the hair, comprising applying the composition according to the invention to the hair followed by optional rinsing and drying.

The drying can be done in the open air or under the action of a heating device such as a hair dryer or a helmet

The invention also relates to the use of the composition according to the invention in a formulation chosen from hair lotions, hair gels, hair mousse without propellants ("foamers"), hair creams, or capillary sprays in a pump bottle. without propellants for shaping or maintaining the hair.

The following examples illustrate the present invention and should not be construed in any way as limiting the invention.

EXAMPLE 1 Preparation of a Pseudo-Block Poly (Acrylic Acid / Methyl Acrylate) Polymer

100 g of butyl acetate are introduced into a 1 liter reactor, and the temperature is then raised from room temperature (25 ° C) to 90 ° C in 1 hour.

30 g of acrylic acid, 30 g of methyl acrylate, 40 g of butyl acetate, 70 g of isopropanol and 1.8 g of 2.5-Bis are then added at 90 ° C. and over 1 hour. (2-ethylhexanoylperoxy) -2,5-dimethylhexane (Trigonox® 141 from Akzo Nobel).

The mixture is maintained for 1 hour at 90 ° C.

90 g of methyl acrylate, 70 g of butyl acetate, 20 g of isopropanol and 1.2 g of 2.5-bis (2-4 g) are then introduced into the above mixture, again at 90 ° C. and over 1 hour. ethylhexanoylperoxy) -2,5-dimethyl hexane.

The mixture is kept at 90 ° C. for 3 hours, then diluted with 105 g of butyl acetate and 45 g of isopropanol, and the mixture is then cooled.

A 40% solution of active polymer material is obtained in the mixture of butyl acetate and isopropanol.

A polymer is obtained comprising a first poly (acrylic acid / methyl acrylate) block or block having a Tg of 80 ° C., a second methyl polyacrylate block having a Tg of 10 ° C. and an intermediate block which is an acidic statistical polymer. acrylic / methyl acrylate / methyl polyacrylate.

This polymer has a weight average weight of 50,000 g / mol and a number average mass of 17,000, a polydispersity index I of 2.95.

It has a glass transition temperature (Tg) of 49 ° C.

Example 2

The Applicant has prepared a composition according to the invention in the form of a styling lotion: <tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="2" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="left">Polymer pseudo block poly (acrylic acid / methyl acrylate)</entry><entry namest="col2" nameend="col2" align="center">2% MA</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Ethanol</entry><entry namest="col2" nameend="col2" align="center">5% MA</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Demineralized Water</entry><entry namest="col2" nameend="col2" align="center">qs 100%</entry></row></tbody></tgroup></table></tables>

Data in percentages by weight

Example 3

The Applicant has prepared a composition according to the invention in the form of a styling gel: <tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="2" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Polymer pseudo block poly (acrylic acid / methyl acrylate)</entry><entry namest="col2" nameend="col2" align="center">4% MA</entry></row><row><entry namest="col1" nameend="col1" align="left">Jaguar HP 105 (Rhodia)</entry><entry namest="col2" nameend="col2" align="center">1% MA.</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Demineralized Water</entry><entry namest="col2" nameend="col2" align="center">Qs 100%</entry></row></tbody></tgroup></table></tables>

Data in percentages by weight