WO2014147038A2

WO2014147038A2 - Cosmetic process for treating the hair with a composition comprising hollow or porous particles, a monoalcohol and a thickening polymer, and use thereof

Info

Publication number: WO2014147038A2
Application number: PCT/EP2014/055341
Authority: WO
Inventors: Samira Khenniche; Mélodie PERRIN
Original assignee: L'oreal
Priority date: 2013-03-19
Filing date: 2014-03-17
Publication date: 2014-09-25
Also published as: WO2014147038A3; FR3003464B1; FR3003464A1; BR112015021656A2

Abstract

The present invention relates to a cosmetic hair treatment process comprising the application of a cosmetic composition comprising hollow and/or porous particles with a mean particle size of from 10 to 300 microns, thickening polymers and monoalcohols comprising 2 to 6 carbon atoms, present in an amount of from 5% to 40% by weight, relative to the total weight of the composition. This process makes it possible in particular to slow down or even prevent the regreasing of the hair.

Description

Cosmetic process for treating the hair with a composition comprising hollow or porous particles, a monoalcohol and a thickening polymer, and use thereof

The present invention relates to a cosmetic hair treatment process, using a cosmetic composition, especially a hair composition, comprising a combination of hollow or porous particles, thickening polymer and monoalcohol, and also to the haircare use of the said composition.

Hair has a tendency to lose some of its qualities due to the action of factors especially such as natural regreasing, sweat, the removal of squamae, pollution or humidity. The visual appearance and the feel of the hair can thus be damaged. Regreasing, for example, makes the hair lank, which then has a tendency to clump together. The hair may be increasingly difficult to style, and may have an unpleasant greasy sheen or an unpleasant waxy feel.

In order to combat these drawbacks, use may be made of detergent compositions, for example shampoos, in order to remove soiling (sebum, sweat, pollution, etc.) or dandruff, and to loosen the hair. The hair is subsequently rinsed and then dried. However, the beneficial effect of shampooing fades out and, within a few days, the problems described above once again arise. Consequently, there is a tendency to increase the frequency of shampooing. Shampooing must be repeated regularly, for example after a few days, indeed even after a few hours.

However, shampoos, based on large amounts of anionic surfactants, may give rise to unpleasant effects such as stinging of the scalp or the eyes.

Shampoos may also be combined with surfactants or sebum absorbers for prolonging over time the perception of cleanliness of the hair. However, it has been found that the efficacy of these products is still insufficient with respect to consumer expectations. This is because they do not make it possible to significantly reduce the frequency of washing of the hair, which frequency can differ according to the country or even the region concerned and which can range from one to two shampoo washes per day to one or two shampoo washes per week. Moreover, to use a shampoo, a source of water, preferably hot or warm water, is needed. To cleanse the hair more rapidly and to avoid wetting the hair, it has already been proposed to use "dry" shampoos. This technique consists in applying absorbent particles to the hair and then in actively brushing the head of hair to remove the particles therefrom. However, in general, total removal of the particles is very difficult to obtain. The results are not very satisfactory: the hair has poor sheen and a coarse, crunchy feel. To date, no hygienic cosmetic haircare composition makes it possible to significantly slow down regreasing of the hair.

The aim of the present invention is to propose such cosmetic compositions, the use of which makes it possible to overcome these drawbacks.

One subject of the invention is a cosmetic hair treatment process comprising the application to the hair of a cosmetic composition comprising:

- hollow and/or porous particles with a mean particle size of from 10 to 300 mi- crons (μιτι);

- one or more thickening polymers; and

- one or more monoalcohols comprising 2 to 6 carbon atoms and especially 2 to 4 carbon atoms, the said monoalcohol(s) being present in the composition in an amount ranging from 5% to 40% by weight relative to the total weight of the composition;

the said application step preferably not being followed by a rinsing step.

The invention also relates to the use of a cosmetic composition comprising:

- one or more monoalcohols comprising 2 to 6 carbon atoms and especially 2 to 4 carbon atoms, present in an amount ranging from 5% to 40% by weight relative to the total weight of the composition; and

- one or more thickening polymers;

for the grease-removal treatment of the hair, especially for slowing down, or even preventing, the regreasing of the hair and/or for lengthening the interval between shampoo washes; the said use preferably being leave-in use.

The use according to the invention makes it possible to significantly reduce the regreasing of the hair, and thus the greasy look and greasy feel of the hair, and thus makes it possible to reduce the washing frequency and to lengthen the interval between shampoo washes.

The compositions according to the invention make it possible to maintain a perception of clean hair for a longer time than with a normal shampoo; by way of example, this perception of clean hair can be a week, for people who usually wash their hair 2 to 3 times per week, and can be at least three days for people who usually wash their hair every day.

In addition, the compositions according to the invention spread easily over the hair, from the end to the root, and thus allow better removal of soiling, over the entire head of hair.

As an end result, the head of hair has a natural, soft, silky feel, and the hairs are better disentangled and shinier. The head of hair is easy to shape and feels light.

In the present description, the term "at least one" is equivalent to the term "one or more" and can be replaced therewith.

In the present description, the term "between" is equivalent to the expression "ranging from" and can be replaced therewith; in these terms, the limits are considered as being included. Hollow or porous particles

The composition according to the invention thus comprises particles chosen from hollow particles and porous particles, and also a mixture thereof.

For the purposes of the present invention, the term "hollow particles" means particles formed from a solid envelope enclosing a space that is empty or partially or totally filled with one or more gases and/or one or more liquids (at room pressure and temperature, 1 atm., 25°C).

For the purposes of the present invention, the term "porous particles" means particles with a structure comprising pores or interstices that are accessible to external agents. The structure of the particles may be of matrix type like a sponge.

Preferably, the porous particles according to the invention have a specific surface area measured via the BET method ranging especially from 1 to 1000 m²/g, in particular from 2 to 750 m²/g, more particularly greater than or equal to 300 m²/g or even greater than or equal to 500 m²/g. The BET (Brunauer- Emmet-Teller) method is a method that is well known to those skilled in the art, and is described especially in the Journal of the American Chemical Society, vol. 60, page 309, February 1938, and corresponds to international standard ISO 5794/1 (appendix D). The specific surface area measured according to the BET method corresponds to the total specific surface area, i.e. it includes the area formed by the pores.

The particles according to the invention have a mean particle size ranging from 10 to 300 microns (μιτι), for example from 10 to 200 μιτι, preferably from 10 to 100 μιτι and better still from 15 to 40 m.

The particles according to the invention may have a density ranging from 0.0001 to 2; preferably, they have a density of less than 0.1 , especially less than 0.09, better still less than 0.06 and even better still less than 0.04; prefer- entially between 0.0001 and 0.04. To obtain this low density, hollow particles optionally filled with a gas are advantageously used. This gas may especially be air, nitrogen, isobutane or isopentane.

Preferably, the particles are spherical or ovoid, preferably of spherical shape, and may be in the form of beads. It is, however, possible to use particles in the form of fibres or needles.

The particles may be made of various inert materials that do not react chemically with the medium; preferably, these particles do not react with the oils, surfactants, water or various other constituents of the cosmetic composition, such as the active agents.

The particles may be organic or mineral, preferably organic.

The particles that may be used in the context of the present invention may be dry or hyd rated.

The porous particles according to the invention may be chosen from silica (mi- cro)particles, crosslinked or non-crosslinked (meth)acrylic polymer particles, and polyamide particles, and mixtures thereof.

As organic porous particles that may be used, mention may be made of polyamide particles, in particular Nylon 6, Nylon 6-6, Nylon 12 or Nylon 6-12, such as those sold by the company Arkema under the name Orgasol.

Mention may also be made of acrylic polymer porous particles, such as poly- methyl methacrylate (PMMA) particles, which are especially spherical, such as those sold under the name Covabead® by the company LCW.

Mention may also be made of crosslinked acrylic polymer porous particles, such as those having the INCI name: Acrylates/ethylhexyl acrylate crosspolymer, and in particular those sold under the name Techpolymer ACP 8-G by the company Sekisui Plastics; or alternatively particles of a copolymer of ethylene glycol di- methacrylate and of methyl methacrylate and also particles of polyallyl methacrylate and of ethylene glycol dimethacrylate. As porous mineral particles, mention may be made of silica particles, which are especially spherical, sold under the name Silica Beads SB-700 by the company Miyoshi or Sunsphere® H33 by the company Asahi Glass.

The hollow particles according to the invention may be chosen from glass parti- cles; polymer particles, especially of crosslinked or non-crosslinked, optionally thermoplastic, optionally expanded vinyl or (meth)acrylic polymer; and mixtures thereof.

As glass particles that may be used, mention may be made of hollow glass par- tides and especially those sold by the company 3M under the reference Scotchlite Glass Bubbles S 22. As hollow polymer particles, especially of crosslinked or non-crosslinked vinyl, preferably acrylic, polymer, mention may be made in particular of crosslinked polymethyl methacrylate particles, and especially those sold by the company Sunjin Chemical under the name SUNPMMA H.

The hollow particles may also be hollow particles of one or more expanded thermoplastic polymers. They may be advantageously chosen from hollow particles of expanded thermoplastic copolymers of acrylonitrile, of vinylidene chlo- ride, of vinyl chloride and/or of (meth)acrylic or styrene monomer. The (meth)acrylic monomer is, for example, a C1 -C4 alkyl acrylate or methacrylate, especially methyl or ethyl acrylate or methacrylate. The styrene monomer is, for example, a-methylstyrene or styrene. Preferably, the particles according to the invention are particles of an expanded thermoplastic copolymer of vinylidene chloride and acrylonitrile or of vinylidene chloride, acrylonitrile and a C1 -C4 alkyl (meth)acrylate, or of styrene monomer. Preferentially, the expanded polymer particles according to the invention are particles of an expanded copolymer of vinylidene chloride, acrylonitrile and a C1 -C4 alkyl (meth)acrylate, especially of methyl or ethyl (meth)acrylate, and better still of methyl methacrylate.

It is possible, for example, to use a polymer containing 0-60% of units derived from vinylidene chloride, 20-90% of units derived from acrylonitrile and 0-50% of units derived from a C1 -C4 alkyl (meth)acrylate or styrene monomer, the sum of the percentages (by weight) being equal to 100%.

It is most particularly possible to use a polymer containing 0-60% of units de- rived from vinylidene chloride, 20-90% of units derived from acrylonitrile and 0- 50% of units derived from a C1 -C4 alkyl (meth)acrylate monomer; especially from methyl or ethyl (meth)acrylate and better still from methyl methacrylate; the sum of the percentages (by weight) being equal to 100%.

Preferentially, the particles are hollow particles of an expanded polymer of vi- nylidene chloride and acrylonitrile or of vinylidene chloride, acrylonitrile and methyl methacrylate; with a mean particle size of from 10 to 300 μιτι, for example from 10 to 200 μιτι, preferably from 10 to 100 m and better still from 15 to 40 μιτι; preferably, the particles being hollow and optionally filled with a gas, chosen especially from air, nitrogen, isobutane and isopentane, preferentially isobutane.

Preferentially, the mass per unit volume of these particles is chosen in the range from 15 to 200 kg/m³, better still from 40 to 120 kg/m³ and even better still from 60 to 80 kg/m³.

The particles that may be used in the context of the invention may be micro- spheres of an expanded terpolymer of vinylidene chloride, acrylonitrile and methyl methacrylate, such as those sold under the brand name Expancel by the company Nobel Casco and in particular under the references 551 DE 12 (particle size D(0.5) of about 12 μιτι and mass per unit volume of about 40 kg/m³), 551 DE 20 (particle size D(0.5) of about 15 to 25 μιτι and mass per unit volume of about 60 kg/m³), 551 DE 50 (particle size D(0.5) of about 40 μηη), 461 DE 50 and 642 WE 50 of about 50 μηη of particle size D(0.5), 551 DE 80 (particle size D(0.5) of about 50 to 80 μιτι). It is also possible to use particles of this same expanded terpolymer with a particle size D(0.5) of about 18 μιτι and a mass per unit volume of about 60 to 80 kg/m³ (Expancel EL23) or with a particle size D(0.5) of about 34 μιτι and a mass per unit volume of about 20 kg/m³. Mention may also be made of the Expancel particles 551 DE 40 d42 (particle size D(0.5) of approximately 30 to 50 μιτι and density of approximately 42 kg/m³), 551 DE 80 d42 (particle size D(0.5) of approximately 50 to 80 μιτι and density of approximately 42 kg/m³), 461 DE 20 d70 (particle size D(0.5) of approximately 15 to 25 μιτι and mass per unit volume of approximately 70 kg/m³), 461 DE 40 d25 (particle size D(0.5) of approximately 35 to 55 μιτι and mass per unit volume of approximately 25 kg/m³), 461 DE 40 d60 (particle size D(0.5) of approximately 20 to 40 μιτι and mass per unit volume of approximately 60 kg/m³), 461 DET 40 d25 (particle size D(0.5) of approximately 35 to 55 μιτι and mass per unit volume of approximately 25 kg/m³), 051 DE 40 d60 (particle size D(0.5) of ap- proximately 20 to 40 μιτι and mass per unit volume of approximately 60 kg/m³), 091 DE 40 d30 (particle size D(0.5) of approximately 35 to 55 μιτι and mass per unit volume of approximately 30 kg/m³) or 091 DE 80 d30 (particle size D(0.5) of approximately 60 to 90 μιτι and mass per unit volume of approximately 30 kg/m³).

Preferably, the composition according to the invention comprises hollow particles, alone or as a mixture with porous particles.

In a preferred embodiment, the composition comprises hollow particles of one or more expanded thermoplastic polymers.

The composition according to the invention preferably comprises the hollow particles and/or the porous particles in an amount ranging from 0.01 % to 20% by weight, especially ranging from 0.05% to 10% by weight and better still from 0.1 % to 5% by weight, relative to the total weight of the composition.

Monoalcohol

The composition according to the invention also comprises one or more monoalcohols comprising 2 to 6 carbon atoms and especially 2 to 4 carbon atoms. They may be linear or branched.

The term "monoalcohol" denotes, in a manner known per se, an alcohol comprising only one hydroxyl (-OH) function. Preferably, the monoalcohols according to the invention have the formula R-OH with R denoting a linear or branched, saturated or unsaturated hydrocarbon- based group comprising from 2 to 6 carbon atoms, and preferably from 2 to 4 carbon atoms.

The monoalcohols that are particularly preferred are ethanol and isopropanol, and mixtures thereof; and most particularly, the monoalcohol is ethanol.

The composition according to the invention comprises the monoalcohol(s) in an amount ranging from 5% to 40% by weight, preferably from 5% to 35% by weight and better still from 5% to 30% by weight, relative to the total weight of the composition.

Thickening polymers

The composition according to the invention also comprises one or more thickening polymers.

For the purposes of the present invention, the term "thickening polymer" means a polymer having, in solution or in dispersion containing 1 % by weight of active material in water or in ethanol at 25°C, a viscosity greater than 0.2 poise at a shear rate of 1 s^~1. The viscosity is measured with a Haake RS600 viscometer from Thermo Electron. This viscometer is a controlled-stress viscometer with cone-plate geometry (for example having a diameter of 60 mm).

The said thickening polymer may be chosen from acrylic thickening polymers, thickening polymers bearing a sugar unit, and mixtures thereof.

For the purposes of the present invention, the term "acrylic polymer" means a polymer resulting from a polymerization reaction using one or more monomers of structure:

with R3 denoting a hydrogen atom or a linear or branched C1 -C4 alkyl radical, and R4 denoting a hydrogen atom, a linear or branched C1 -C4 alkyl radical, a radical NR5R6, or a linear or branched C1 -C30 alkoxy radical, the said radicals being optionally substituted with one or more OH radicals and/or with a quaternary ammonium radical;

R5 and R6 denoting, independently of each other, a hydrogen atom or an optionally oxyalkylenated linear or branched C1 -C30 alkyl radical, optionally comprising a sulfonic group. Preferably, R3 denotes a hydrogen atom or a methyl radical.

The acrylic thickening polymers that may be used in the present invention may be chosen from:

(a) (meth)acrylic associative thickeners;

(b) crosslinked acrylic acid homopolymers;

(c) crosslinked copolymers of (meth)acrylic acid and of (C1 -C6)alkyl acrylate;

(d) nonionic homopolymers and copolymers containing ethylenically unsaturated monomers of ester and/or amide type;

(e) ammonium acrylate homopolymers or copolymers of ammonium acrylate and of acrylamide;

(f) (meth)acrylamido(C1 -C4)alkylsulfonic acid homopolymers and copolymers;

(g) crosslinked methacryloyloxy(C1 -C4)alkyltri(C1 -C4)alkylammonium homopolymers and copolymers.

(a) According to the invention, the term "associative thickener" means an am- phiphilic thickener comprising both hydrophilic units and hydrophobic units, in particular comprising at least one C8-C30 fatty chain and at least one hydrophilic unit.

The (meth)acrylic associative thickening polymers according to the invention may be nonionic, anionic, cationic or amphoteric.

Preferably, the nonionic associative thickening polymers according to the invention are chosen from:

- copolymers of C1 -C6 alkyl methacrylates or acrylates and of amphiphilic monomers comprising at least one fatty chain (for example oxyethylenated (C8-

C22)alkyl acrylates), for instance the oxyethylenated methyl methacry- late/stearyl acrylate copolymer sold by the company Goldschmidt under the name Antil 208; and

- copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain (for example (C8-C22)alkyl

(meth)acrylates), for instance polyethylene glycol methacrylate/lauryl methacry- late copolymer.

The anionic associative thickening polymers according to the invention may be chosen from those comprising at least one hydrophilic unit of unsaturated ole- finic carboxylic acid type, and at least one hydrophobic unit of the type such as a (C10-C30) alkyl ester of an unsaturated carboxylic acid. They are preferably chosen from those in which the hydrophilic unit of unsaturated olefinic carboxylic acid type corresponds to the monomer of formula (I) below: H₂C= C— C— OH

L I I 0

R O

in which R¹ denotes H, CH3 or C2H5, i.e. acrylic acid, methacrylic acid or ethacrylic acid units, and in which the hydrophobic unit of (C10-C30)alkyl ester of unsaturated carboxylic acid type corresponds to the monomer of formula (II) below:

H₂C= C C OR²

L I I (II)

R O

in which R¹ denotes H or CH3 or C2H5 (i.e. acrylate, methacrylate or ethacry- late units) and preferably H or CH3; and R² denotes a C10-C30 and preferably C12-C22 alkyl radical.

(C10-C30) alkyl esters of unsaturated carboxylic acids in accordance with the invention comprise, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.

Such anionic amphiphilic polymers are described, for example, in patents US-3 915 921 and 4 509 949.

The anionic amphiphilic polymers that may be used in the context of the present invention may more particularly denote polymers formed from a mixture of monomers comprising:

(i) either acrylic acid and one or more esters of formula (III) below:

H₂C= C C OR

L i i (Hi)

R O

in which R¹ denotes H or CH3, and R² denotes an alkyl radical containing from 12 to 22 carbon atoms, and optionally a crosslinking agent, for instance those consisting of from 60% to 95% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of C10-C30 alkyl acrylate (hydrophobic unit), and 0 to 6% by weight of crosslinking polymerizable monomer, or those consisting of from 96% to 98% by weight of acrylic acid, 1 % to 4% by weight of C10-C30 alkyl acrylate and 0.1 % to 0.6% by weight of crosslinking polymerizable monomer,

(ii) or essentially acrylic acid and lauryl methacrylate, such as the product formed from 66% by weight of acrylic acid and 34% by weight of lauryl methacrylate.

H₂C = C\

The said crosslinking agent is a monomer containing a group with at least one other polymerizable group whose unsaturated bonds are not conjugated with each other. Mention may be made especially of polyallyl ethers, especially such as polyallyl sucrose and polyallylpentaerythritol.

Among the abovesaid polymers, the ones that are most particularly preferred are the products sold by the company Goodrich under the trade names Pe- mulen TR1 , Pemulen TR2 and Carbopol 1382, and even more preferentially Pemulen TR1 , and the product sold by the company SEPC under the name Coatex SX. As fatty-chain anionic amphiphilic polymers, mention may also be made of the methacrylic acid/methyl acrylate/ethoxylated alcohol di methyl -meta- isopropenylbenzylisocyanate copolymer in particular sold under the name Vis- cophobe DB 1000 by the company Amerchol.

Fatty-chain anionic amphiphilic polymers that may also be mentioned include those comprising at least one acrylic monomer containing sulfonic group(s), in free or partially or totally neutralized form and comprising at least one hydrophobic portion.

The hydrophobic portion present in the polymers of the invention preferably comprises from 8 to 22 carbon atoms, preferentially from 8 to 18 carbon atoms and more particularly from 12 to 18 carbon atoms.

Preferably, the sulfonic polymers in accordance with the invention are partially or totally neutralized with a mineral base (sodium hydroxide, potassium hydroxide or aqueous ammonia) or an organic base such as mono-, di- or triethanola- mine, an aminomethylpropanediol, N-methylglucamine, basic amino acids, for instance arginine and lysine, and mixtures of these compounds.

The sulfonic amphiphilic polymers in accordance with the invention generally have a number-average molecular weight (Mn) ranging from 1000 to 20 000 000 g/mol, preferably ranging from 20 000 to 5 000 000 and preferentially from 100 000 to 1 500 000 g/mol.

The sulfonic amphiphilic polymers according to the invention may be crosslinked or non-crosslinked. Crosslinked amphiphilic polymers are preferably selected.

When they are crosslinked, the crosslinking agents may be selected from poly- olefinically unsaturated compounds commonly used for the crosslinking of polymers obtained by free-radical polymerization. Mention may be made, for example, of divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, poly- glycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, ethylene glycol di(meth)acrylate or tetraethylene glycol di(meth)acrylate, trimethylolpropane triacrylate, methylenebisacrylamide, methylenebis- methacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallylethyl- enediamine, tetraallyloxyethane, trimethylolpropane diallyl ether, allyl (meth)acrylate, allyl ethers of alcohols of the sugar series, or other allyl or vinyl ethers of polyfunctional alcohols, and also allyl esters of phosphoric and/or vi- nylphosphonic acid derivatives, or mixtures of these compounds.

Methylenebisacrylamide, allyl methacrylate or trimethylolpropane triacrylate (TMPTA) will be used more particularly. The degree of crosslinking generally ranges from 0.01 mol% to 10 mol% and more particularly from 0.2 mol% to 2 mol% relative to the polymer.

The acrylic monomers bearing sulfonic group(s) are chosen especially from (meth)acrylamido(Ci-C22)alkylsulfonic acids and N-(Ci- C22)alkyl(meth)acrylamido(Ci-C22)alkylsulfonic acids, for instance undecy- lacrylamidomethanesulfonic acid, and also partially or totally neutralized forms thereof.

(Meth)acrylamido(Ci-C22)alkylsulfonic acids, for instance acrylamidomethane- sulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2- methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido- 2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid or 2- acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and also partially or totally neutralized forms thereof, will more preferentially be used.

2-acrylamido-2-methylpropanesulfonic acid (AMPS), and also partially or totally neutralized forms thereof, will more particularly be used.

The amphiphilic polymers in accordance with the invention may be chosen especially from random amphiphilic AMPS polymers modified by reaction with a C6-C22 n-monoalkylamine or di-n-alkylamine, and such as those described in patent application WO 00/31 154. These polymers may also contain other ethylenically unsaturated hydrophilic monomers chosen, for example, from (meth)acrylic acids, β-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.

The preferred polymers of the invention are selected from amphiphilic copolymers of AMPS and of at least one ethylenically unsaturated hydrophobic monomer comprising at least one hydrophobic portion containing from 8 to 50 carbon atoms, more preferably from 8 to 22 carbon atoms, more preferably still from 8 to 18 carbon atoms and more particularly 12 to 18 carbon atoms.

These same copolymers may also contain one or more ethylenically unsaturated monomers not comprising a fatty chain, such as (meth)acrylic acids, β- substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds. These copolymers are described especially in patent application EP-A-750 899, patent US 5 089 578 and in the following publications by Yotaro Morishima:

- Self-assembling amphiphilic polyelectrolytes and their nanostructures, Chinese Journal of Polymer Science, Vol. 18, No. 40, (2000), 323-336;

- Micelle formation of random copolymers of sodium 2-(acrylamido)-2- methylpropanesulfonate and a nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering, Macromolecules, 2000, Vol. 33, No. 10, 3694-3704;

- Solution properties of micelle networks formed by nonionic moieties covalently bound to a polyelectrolyte: salt effects on rheological behavior - Langmuir,

2000, Vol. 16, No. 12, 5324-5332;

- Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2- methylpropanesulfonate and associative macromonomers, Polym. Preprint, Div. Polym. Chem. 1999, 40(2), 220-221 .

The ethylenically unsaturated hydrophobic monomers of these particular copolymers are preferably chosen from the acrylates or acrylamides of formula (IV) below:

—

0= C

Y ^CH₂-CH(R₃)-0^ R₂

in which R1 and R3, which may be identical or different, denote a hydrogen atom or a linear or branched C1-C6 alkyl radical (preferably methyl); Y denotes O or NH; R₂ denotes a hydrocarbon-based radical containing at least from 8 to 50 carbon atoms, preferentially from 8 to 22 carbon atoms, better still from 6 to 18 carbon atoms and more particularly from 12 to 18 carbon atoms; x denotes a number of moles of alkylene oxide and ranges from 0 to 100.

The radical R2 is preferably selected from linear C6-C18 alkyl radicals (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl or n-dodecyl radicals); branched or cyclic C6-C18 alkyl radicals (for example cyclododecane (C12) or adamantane (C10)); C6-C18 alkylperfluoro radicals (for example the group of formula -(CH₂)2- (CF₂)9-CF₃); the cholesteryl (C2₇) radical or a cholesterol ester residue, such as the cholesteryl oxyhexanoate group; or polycyclic aromatic groups, such as naphthalene or pyrene. Among these radicals, the ones that are more particu- larly preferred are linear alkyl radicals and more particularly the n-dodecyl radi- cal.

According to one particularly preferred form of the invention, the monomer of formula (IV) comprises at least one alkylene oxide unit (x > 1 ) and preferably a polyoxyalkylenated chain. The polyoxyalkylenated chain is preferentially formed from ethylene oxide units and/or propylene oxide units and even more particularly formed from ethylene oxide units. The number of oxyalkylenated units generally ranges from 3 to 100, preferentially from 3 to 50 and even more preferentially from 7 to 25.

Among these polymers, mention may be made of:

- crosslinked or non-crosslinked, neutralized or non-neutralized copolymers, comprising from 15% to 60% by weight of AMPS units and from 40% to 85% by weight of (C8-Ci6)alkyl(meth)acrylamide units or (C8-Ci6)alkyl(meth)acrylate units relative to the polymer, such as those described in patent application EP-A 750 899;

- terpolymers comprising from 10 mol% to 90 mol% of acrylamide units, from 0.1 mol% to 10 mol% of AMPS units and from 5 mol% to 80 mol% of

n-(C6-Ci8)alkylacrylamide units, such as those described in patent US-5 089 578.

Mention may also be made of copolymers of totally neutralized AMPS and of dodecyl methacrylate, and also crosslinked and non-crosslinked copolymers of AMPS and of n-dodecylmethacrylamide, such as those described in the Mor- ishima articles mentioned above.

Mention will be made more particularly of the copolymers consisting of 2- acrylamido-2-methylpropanesulfonic acid (AMPS) units of formula (V) below:

in which X⁺ is a proton, an alkali metal cation, an alkaline-earth metal cation or the ammonium ion,

and of units of formula (VI) below:

in which x denotes an integer from 3 to 100, preferably from 5 to 80 and preferentially from 7 to 25; R1 has the same meaning as that indicated above in the formula (IV), and R4 denotes a linear or branched C6-C22 and preferentially C10-

C22 alkyl.

The polymers that are particularly preferred are those for which x = 25, R1 denotes methyl and R4 represents n-dodecyl; they are described in the Morishima articles mentioned above. The polymers for which X⁺ denotes sodium or ammonium are more particularly preferred.

The cationic associative thickening polymers according to the present invention may be chosen from polyacrylates bearing amine side groups.

The polyacrylates bearing quaternized or non-quaternized amine side groups contain, for example, hydrophobic groups of the type of steareth-20 (poly- oxyethylenated (20) stearyl alcohol) or (Cio-C3o)alkyl PEG-20 itaconate.

Examples of polyacrylates bearing amine side chains that may be mentioned are the polymers 8781 -124B or 9492-103 or Structure Plus from the company National Starch. The amphoteric associative thickening polymers according to the invention may be chosen from methacrylamidopropyltrimethylammonium chloride/acrylic acid/C10-C30 alkyl methacrylate copolymers, the alkyl radical preferably being a stearyl radical. (b) Among the crosslinked acrylic acid homopolymers, mention may also be made of the products sold under the names Carbopol 980, 981 , 954, 2984 and 5984 by the company Goodrich or the products sold under the names Syntha- len M and Synthalen K by the company 3 VSA. (c) Mention may be made, among crosslinked copolymers of (meth)acrylic acid and of C1-C6 alkyl acrylate, of the product sold under the name Viscoatex 538C by the company Coatex, which is a crosslinked copolymer of methacrylic acid and of ethyl acrylate as an aqueous dispersion containing 38% active material, or the product sold under the name Aculyn 33 by the company Rohm & Haas, which is a crosslinked copolymer of acrylic acid and of ethyl acrylate as an aqueous dispersion containing 28% active material. Mention may be made more particularly of the crosslinked methacrylic acid/ethyl acrylate copolymer in the form of an aqueous 30% dispersion manufactured and sold under the name Carbopol Aqua SF-1 by the company Noveon.

(d) Among the nonionic homopolymers or copolymers containing ethylenically unsaturated monomers of ester and/or amide type, mention may be made of the products sold under the names Cyanamer P250 by the company Cytec (poly- acrylamide); PMMA MBX-8C by the company US Cosmetics (methyl methacry- late/ethylene glycol dimethacrylate copolymer); Acryloid B66 by the company Rohm & Haas (butyl methacrylate/methyl methacrylate copolymer); BPA 500 by the company Kobo (polymethyl methacrylate).

(e) Among the ammonium acrylate homopolymers, mention may be made of the product sold under the name Microsap PAS 5193 by the company Hoechst.

Among the copolymers of ammonium acrylate and of acrylamide, mention may be made of the product sold under the name Bozepol C Nouveau or the product PAS 5193 sold by the company Hoechst (they are described in documents FR- 2 416 723, US-2 798 053 and US-2 923 692).

(f) The (meth)acrylamido(C1 -C4)alkyl sulfonic acid homopolymers or copolymers are preferably crosslinked. More particularly, they are partially or totally neutralized. These are water-soluble or water-swellable polymers.

Among these polymers, mention may especially be made of:

- polyacrylamidomethanesulfonic acid,

- polyacrylamidoethanesulfonic acid,

- polyacrylamidopropanesulfonic acid,

- poly-(2-acrylamido-2-methylpropanesulfonic acid),

- poly-(2-methylacrylamido-2-methylpropanesulfonic acid),

- poly-(2-acrylamido-n-butanesulfonic acid).

Polymers of this type and especially crosslinked and partially or totally neutralized poly(2-acrylamido-2-methylpropanesulfonic acids) are known, described and prepared in patent application DE-196 25 810.

They are generally characterized in that they comprise, randomly distributed:

- from 90% to 99.9% by weight of units of formula (A) below: CH,

(A)

O NH- CH₂SO₃ ^'

in which X⁺ denotes a cation or a mixture of cations, including H+, and

- from 0.01 % to 10% by weight of at least one crosslinking unit containing at least two olefinic double bonds, the weight proportions being defined relative to the total weight of the polymer.

Preferably, the crosslinked and neutralized poly(2-acrylamido-2- methylpropanesulfonic acid) comprises from 98% to 99.5% by weight of units of formula (A) and from 0.5% to 2% by weight of crosslinking units.

Preferably, X⁺ represents a cation or a mixture of cations chosen in particular from a proton, an alkali metal cation, a cation equivalent to that of an alkaline- earth metal, or an ammonium ion.

Preferably, the crosslinking units containing at least two olefinic double bonds are chosen from dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyloxyethane or other polyfunctional alcohol allyl or vinyl ethers, tetraethylene glycol diacrylate, triallylamine, trimethylolpropane diallyl ether, methylenebisacrylamide or divi- nylbenzene.

The crosslinking units bearing at least two olefinic double bonds are more particularly chosen from those corresponding to the general formula (B) below:

in which Ri denotes a hydrogen atom or a Ci-C₄ alkyl and more particularly methyl (trimethylolpropane triacrylate).

The crosslinked and partially or totally neutralized poly(2-acrylamido-2- methylpropanesulfonic acids) are generally known under the names Ammonium polyacrylamido-2-methylpropanesulfonate or Ammonium polyacryldimethyltau- ramide (INCI name).

A product that is particularly preferred according to the invention is the one sold by the company Clahant under the trade name Hostacerin AMPS; this is a crosslinked poly(2-acrylamido-2-methylpropanesulfonic acid) partially neutralized with aqueous ammonia. (g) Among the crosslinked polymers of methacryloyloxy(Ci-C₄)alkyltri(Ci- C₄)alkylammonium salts, mention may be made of the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homopolymerization or co- polymerization being followed by crosslinking with an olefinically unsaturated compound, more particularly methylenebisacrylamide. Use may be made more particularly of a crosslinked acryla- mide/methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion containing 50% by weight of the said co- polymer in mineral oil. This dispersion is sold especially under the name Salcare® SC 92 by the company Ciba. Use may also be made of a crosslinked homopolymer of methacryloyloxyethyltrimethylammonium chloride containing about 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are sold under the names Salcare® SC 95 and Salcare® SC 96 by the company Ciba.

Preferably, the acrylic thickening polymer(s) are chosen from crosslinked acrylic acid homopolymers. The polymers bearing sugar units according to the invention may be of natural or synthetic origin. They may be nonionic, anionic, amphoteric or cationic. The base units of the polymers bearing sugar units of the invention may be monosaccharides or disaccharides.

The term "sugar unit" means a unit derived from a carbohydrate of formula Cn(H₂O)_n-i or (CH₂O)_n, which may be optionally modified by substitution and/or by oxidation and/or by dehydration.

The sugar units that may be included in the composition of the polymers of the invention are preferably derived from the following sugars: glucose, galactose, arabinose, rhamnose, mannose, xylose, fucose, fructose, anhydrogalactose, galacturonic acid, glucuronic acid, mannuronic acid, galactose sulfate, anhydrogalactose sulfate.

As polymers that may be used, mention may be made especially of the following native gums, and also derivatives thereof:

a) tree or shrub exudates, including:

- gum arabic (branched polymer of galactose, arabinose, rhamnose and glucuronic acid);

- ghatti gum (polymer derived from arabinose, galactose, mannose, xylose and glucuronic acid);

- karaya gum (polymer derived from galacturonic acid, galactose, rham- nose and glucuronic acid);

- gum tragacanth (or tragacanth) (polymer of galacturonic acid, galactose, fucose, xylose and arabinose);

and derivatives thereof;

b) gums derived from algae, including:

- agar (polymer derived from galactose and anhydrogalactose);

- alginates (polymers of mannuronic acid and of glucuronic acid);

- carrageenans and furcellerans (polymers of galactose sulfate and of anhydrogalactose sulfate);

and derivatives thereof;

c) gums derived from seeds or tubers, including:

- guar gum (polymer of mannose and galactose);

- locust bean gum (polymer of mannose and galactose);

- fenugreek gum (polymer of mannose and galactose);

- tamarind gum (polymer of galactose, xylose and glucose);

- konjac gum (polymer of glucose and mannose);

and derivatives thereof;

d) microbial gums, including:

- xanthan gum (polymer of glucose, mannose acetate, mannose/pyruvic acid and glucuronic acid);

- gellan gum (polymer of partially acylated glucose, rhamnose and glucuronic acid);

- scleroglucan gum (glucose polymer);

and derivatives thereof;

e) plant extracts, including:

- cellulose (glucose polymer);

- starch (glucose polymer);

- inulin (polymer of fructose and glucose);

and derivatives thereof. These polymers may be physically or chemically modified. A physical treatment that may especially be mentioned is the temperature. Chemical treatments that may be mentioned include esterification, etherification, amidation or oxidation reactions. These treatments can lead to polymers that may be nonionic, anionic, cationic or amphoteric.

Preferably, these chemical or physical treatments are applied to guar gums, locust bean gums, starches and celluloses. The nonionic guar gums that may be used according to the invention may be modified with C1 -C6 hydroxyalkyl groups. Among the hydroxyalkyl groups that may be mentioned are hydroxymethyl, hydroxyethyl, hydroxypropyl and hy- droxybutyl groups.

These guar gums are well known in the prior art and may be prepared, for example, by reacting the corresponding alkene oxides, for instance propylene oxides, with the guar gum so as to obtain a guar gum modified with hydroxypropyl groups.

The degree of hydroxyalkylation preferably ranges from 0.4 to 1 .2, and corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functions present on the guar gum.

Such nonionic guar gums optionally modified with hydroxyalkyl groups are sold, for example, under the trade names Jaguar HP8, Jaguar HP60 and Jag- uar HP120 by the company Rhodia Chimie.

The guar gums modified with cationic groups that may be used more particularly according to the invention are guar gums comprising trialkylammonium cationic groups. Preferably, 2% to 30% by number of the hydroxyl functions of these guar gums bear trialkylammonium cationic groups. Even more preferentially, 5% to 20% by number of the hydroxyl functions of these guar gums are branched with trialkylammonium cationic groups. Mention may very particularly be made, among these trialkylammonium groups, of the trimethylammonium and triethylammonium groups. Even more preferentially, these groups represent from 5% to 20% by weight relative to the total weight of the modified guar gum. According to the invention, use may be made of guar gums modified with 2,3- epoxypropyltrimethylammonium chloride. These guar gums modified with cationic groups, are products already known per se and are, for example, described in patents US 3 589 578 and US 4 0131 307. Such products are moreover sold especially under the trade names Jaguar C13 S, Jaguar C 15 and Jaguar C 17 by the company Rhodia Chimie.

A modified locust bean gum that may be used is cationic locust bean gum containing hydroxypropyltrimonium groups, such as Catinal CLB 200 sold by the company Toho.

The starch molecules used in the present invention may originate from any plant source of starch, especially cereals and tubers; more particularly, they are starches from corn, rice, cassava, barley, potato, wheat, sorghum, pea, oat or tapioca. The starch hydrolysates mentioned above may also be used. The starch is preferably derived from potato. The starches may be chemically or physically modified especially by one or more of the following reactions: pregelatinization, oxidation, crosslinking, esteri- fication, etherification, amidation, heat treatments.

More particularly, these reactions may be performed in the following manner: - pregelatinization by splitting the starch granules (for example drying and cooking in a drying drum);

- oxidation with strong oxidizing agents, leading to the introduction of carboxyl groups into the starch molecule and to depolymerization of the starch molecule (for example by treating an aqueous starch solution with sodium hypochlorite); - crosslinking with functional agents capable of reacting with the hydroxyl groups of the starch molecules, which will thus bond together (for example with glyceryl and/or phosphate groups);

- esterification in alkaline medium for the grafting of functional groups, especially C1 -C6 acyl (acetyl), C1 -C6 hydroxyalkyl (hydroxyethyl or hydroxypropyl), carboxymethyl or octenylsuccinic.

Monostarch phosphates (of the type Am-O-PO-(OX)2), distarch phosphates (of the type Am-O-PO-(OX)-O-Am) or even tristarch phosphates (of the type Am-O- PO-(O-Am)₂) or mixtures thereof may especially be obtained by crosslinking with phosphorus compounds, Am meaning starch and X especially denoting alkali metals (for example sodium or potassium), alkaline-earth metals (for example calcium or magnesium), ammonium salts, amine salts, for instance those of monoethanolamine, diethanolamine, triethanolamine, 3-amino-1 ,2- propanediol, or ammonium salts derived from basic amino acids such as lysine, arginine, sarcosine, ornithine or citrulline.

The phosphorus compounds may be, for example, sodium tripolyphosphate, sodium orthophosphate, phosphorus oxychloride or sodium trimetaphosphate. Distarch phosphates or compounds rich in distarch phosphate will preferentially be used, for instance the product sold under the references Prejel VA-70-T AGGL (gelatinized hydroxypropyl cassava distarch phosphate), Prejel TK1 (gelatinized cassava distarch phosphate) and Prejel 200 (gelatinized acetyl cassava distarch phosphate) by the company Avebe, or Structure Zea from National Starch (gelatinized corn distarch phosphate).

A preferred starch is a starch that has undergone at least one chemical modifi- cation such as at least one esterification.

According to the invention, amphoteric starches comprising one or more anionic groups and one or more cationic groups may also be used. The anionic and cationic groups may be linked to the same reactive site of the starch molecule or to different reactive sites; they are preferably linked to the same reactive site. The anionic groups may be of carboxylic, phosphate or sulfate type, preferably carboxylic. The cationic groups may be of primary, secondary, tertiary or quaternary amine type.

The amphoteric starches are especially chosen from the compounds having the following formulae:

R' R

COOM R

HC C— COOM _mn _/ H HC C— COOM

St 0 - (CH₂)_n - N _{N H} |_| St - 0 - (CH₂) - N

C C— COOM \

(la) I I ^R" (Ma)

R' R

(Ilia) R' R' R' R' (IVa)

N N

St - O - C C — COOM St - O - C C COOM

H H

in which:

St-O represents a starch molecule,

R, which may be identical or different, represents a hydrogen atom or a methyl radical,

R', which may be identical or different, represents a hydrogen atom, a methyl radical or a -COOH group,

n is an integer equal to 2 or 3,

M, which may be identical or different, denotes a hydrogen atom, an alkali metal or alkaline-earth metal such as Na, K, Li or NH4, a quaternary ammonium or an organic amine,

R" represents a hydrogen atom or a C1 -C18 alkyl radical.

These compounds are especially described in US 5 455 340 and US 4 017 460.

Use is particularly made of the starches of formula (I la) or (Ilia); and preferen- tially starches modified with 2-chloroethylaminodipropionic acid, i.e. starches of formula (I la) or (Ilia) in which R, R', R" and M represent a hydrogen atom and n is equal to 2. The preferred amphoteric starch is a starch chloroethylami- dodipropionate. The celluloses and cellulose derivatives may be anionic, cationic, amphoteric or nonionic. Among these derivatives, cellulose ethers, cellulose esters and cellulose ester ethers are distinguished.

Among the cellulose esters, mention may be made of mineral cellulose esters (cellulose nitrates, sulfates and phosphates), organic cellulose esters (cellulose monoacetates, triacetates, amidopropionates, acetate butyrates, acetate propi- onates and acetate trimellitates), and mixed organic/mineral cellulose esters, such as cellulose acetate butyrate sulfates and cellulose acetate propionate sulfates.

Among the cellulose ester ethers, mention may be made of hydroxypropyl- methylcellulose phthalates and ethylcellulose sulfates.

Among the nonionic cellulose ethers that may be mentioned are alkylcelluloses such as methylcelluloses and ethylcelluloses (for example Ethocel Standard 100 Premium from Dow Chemical); hydroxyalkylcelluloses such as hydroxy- methylcelluloses and hydroxyethylcelluloses (for example Natrosol 250 HHR sold by Aqualon) and hydroxypropylcelluloses (for example Klucel EF from Aqualon); mixed hydroxyalkyl-alkylcelluloses such as hydroxypropylmethylcellu- loses (for example Methocel E4M from Dow Chemical), hydroxyethylmethylcel- luloses, hydroxyethylethylcelluloses (for example Bermocoll E 481 FQ from Akzo Nobel) and hydroxybutylmethylcelluloses.

Among the anionic cellulose ethers, mention may be made of carboxyalkylcellu- loses and salts thereof. Examples that may be mentioned include carboxy- methylcelluloses, carboxymethylmethylcelluloses (for example Blanose 7M from the company Aqualon) and carboxymethylhydroxyethylcelluloses, and also the sodium salts thereof.

Among the cationic cellulose ethers, mention may be made of crosslinked or non-crosslinked, quaternized hydroxyethylcelluloses. The quaternizing agent may especially be diallyldimethylammonium chloride (for example Celquat L200 from National Starch). Another cationic cellulose ether that may be mentioned is hydroxypropyltrimethylammonium hydroxyethyl cellulose (for example Ucare Polymer JR 400 from Amerchol).

The thickening polymers bearing sugar units may be associative. Among the associative thickening polymers bearing sugar units, mention may be made of celluloses or derivatives thereof, modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups or mixtures thereof in which the alkyl groups are of C8-C22; nonionic alkylhydroxyethylcelluloses such as the products Natrosol Plus Grade 330 CS and Polysurf 67 (C16 alkyl) sold by the company Aqualon; quaternized alkylhydroxyethylcelluloses (cationic), such as the products Quatrisoft LM 200, Quatrisoft LM-X 529-18-A, Quatrisoft LM-X 529-18-B (C12 alkyl) and Quatrisoft LM-X 529-8 (C18 alkyl) sold by the company Amerchol, the products Crodacel QM and Crodacel QL (C12 alkyl) and Crodacel QS (C18 alkyl) sold by the company Croda, and the product Soft- cat SL 100 sold by the company Amerchol; nonionic nonoxynylhydroxyethylcel- luloses such as the product Amercell HM-1500 sold by the company Amerchol; nonionic alkylcelluloses such as the product Bermocoll EHM 100 sold by the company Berol Nobel. As associative polymers bearing sugar units derived from guar, mention may be made of hydroxypropyl guars modified with a fatty chain, such as the product Esaflor HM 22 (modified with a C22 alkyl chain) sold by the company Lamberti; the product Miracare XC 95-3 (modified with a C14 alkyl chain) and the product RE 205-146 (modified with a C20 alkyl chain) sold by Rhodia Chimie.

Preferably, the polymers bearing sugar units according to the invention are non- ionic.

The polymer(s) bearing sugar units of the invention are preferably chosen from guar gums, locust bean gums, xanthan gums, starches and celluloses, in their modified form (derivatives) or unmodified.

Preferably, the composition comprises at least one thickening polymer chosen from thickening polymers bearing sugar units.

The composition according to the invention may comprise the thickening polymers) in an amount ranging from 0.01 % to 10% by weight, especially from 0.05% to 5% by weight and preferentially from 0.1 % to 3% by weight, relative to the total weight of the composition.

Other ingredients

The composition according to the invention is preferably aqueous and then comprises water at a concentration preferably ranging from 5% to 98% by weight, especially from 20% to 95% by weight and better still from 50% to 80% by weight, relative to the total weight of the composition.

The composition may also comprise one or more organic solvents that are liquid at 25°C and 1 atm., preferably chosen from polyols such as propylene glycol or glycerol, and C3-C7 polyol ethers. The composition according to the invention may also comprise at least one common cosmetic ingredient, other than the compounds of the invention, chosen especially from propellants; vegetable, mineral, animal or synthetic oils; solid fatty substances and especially waxes, C8-C40 esters, C8-C40 acids; C8- C40 alcohols; nonionic surfactants, cationic surfactants; anionic surfactants, amphoteric surfactants, zwitterionic surfactants; sunscreens; moisturizers; anti- dandruff agents; antioxidants; chelating agents; reducing agents; oxidation bases, couplers, oxidizing agents, direct dyes; hair-relaxing agents, such as thiols and alkaline hydroxides; nacreous agents and opacifiers; plasticizers or coalescers; hydroxy acids; pigments; fillers; silicones and in particular polydi- methylsiloxanes (PDMSs); conditioning or styling polymers; fragrances; basi- fying or acidifying agents; silanes; crosslinking agents, such as polyphenols, aldehydes or DHA. The composition can, of course, comprise several cosmetic ingredients appearing in the above list. Those skilled in the art will take care to choose the ingredients included in the composition and the amounts thereof so that they do not harm the properties of the compositions of the present inven- tion.

The pH of the composition, if it is aqueous, is preferably between 3 and 9 and especially between 3 and 6. The compositions according to the invention may be in any galenical form conventionally used and especially in the form of an aqueous, alcoholic or aqueous/alcoholic solution or suspension or oily solution or suspension; of a solution or a dispersion of the lotion or serum type; of an emulsion, in particular having a liquid or semi-liquid consistency, of the O/W, W/O or multiple type; of a suspen- sion or emulsion having a soft consistency of (O/W) or (W/O) cream type; of an aqueous or anhydrous gel, or of any other cosmetic form. These compositions can be packaged in pump-action sprays or in aerosol containers, in order to provide for application of the composition in the vaporized (lacquer) form or in the form of a mousse. In these cases, the composition preferably comprises at least one propellant.

The cosmetic composition may or may not be rinsed out after having been applied to the hair.

It is thus possible to apply the composition according to the invention to the hair between two shampoo washes, on wet hair or on dry hair, with or without a leave-in time, with or without heat, the said application optionally being followed by rinsing and drying, either at room temperature (25°C) or with a hair dryer or a straightening iron (250°C), for example.

Preferably, the composition according to the invention is a leave-in composition, i.e., preferably, the application step is not followed by a step of rinsing, for example with water, especially in the hour(s) following the application.

Specifically, it has been found that the process according to the invention could most particularly also give the hair conditioning, while at the same time avoiding regreasing of the hair and/or keeping the hair cleaner.

The cosmetic treatment process according to the invention is preferably a hair treatment process for caring for and/or cleansing the hair, and in particular a process for slowing down, or even preventing, the regreasing of the hair and thus lengthening the interval between shampoo washes (grease-removal treat- ment).

Preferentially, the grease-removal process is a leave-in process (leave-in grease-removal treatment). Most particularly, the process according to the invention comprises a step of applying the composition to the hair, the said application step not being followed by a rinsing step (leave-in application), for example with water, especially in the hour(s) (for example 1 to 24 hours) following the application.

The invention also relates to the use of a composition according to the invention for the grease-removal treatment of the hair, especially for slowing down, or even preventing, the regreasing of the hair, and/or for lengthening the interval between shampoo washes.

Preferably, the said use is leave-in use (use as a leave-in grease-removal treatment), i.e. not followed by a rinsing step, for example with water, especially in the hour(s) (for example 1 to 24 hours) following the application of the composition to the hair.

The application of compositions of this type to the hair makes it possible to significantly reduce the regreasing of the hair, and thus the greasy look and greasy feel of the hair, and thus makes it possible to reduce the washing frequency and to lengthen the interval between shampoo washes.

The invention is illustrated in greater detail in the examples that follow. Example 1

The following hair compositions are prepared (weight%):

The composition is applied easily to the hair and is left to dry in the open applies and spreads easily along the entire length of the keratin fibre.

In a test performed on 15 consumers identifying themselves as having greasy hair, several leave-in applications of composition A above were performed in alternation with shampoo washes. The results show that the consumers perceive a marked grease-removal effect with less rapid regreasing of their hair, which remains light, disentangled and clean. Another test was performed on volunteers; composition B above was applied between two shampoo washes on dirty (unwashed) hair, and left on. Before the treatment, the hair is flattened onto the scalp, is in clumps and is difficult to shape. After the treatment, ease of shaping of the hairstyle, lifting of the roots and disentangling of the hair are regained. The hair looks cleaner.

Example 2

The following hair compositions are prepared (weight%):

4 g of composition are applied per half-head, to 25 volunteers. The composition is massaged in so as to homogenize its distribution, and a panel of experts then makes an evaluation, 24 hours after application of the composition.

It is found that, for all four of the following criteria: greasy hair, shiny hair, flattened hair and hair in clumps, the experts' evaluation is always markedly in favour of the composition according to the invention.

The composition according to the invention thus makes it possible to limit the regreasing of the hair, when compared with a comparative composition, 24 hours after application.

Example 3

The following hair compositions are prepared (weight%):

Particles tested: Example INCI Name Commercial reference

A Acrylates copolymer Expancel 461 DE 20 D70

B Acrylonitrile/methyl methacry- Expancel 551 DE 40D42

(Ex. 2) late/vinylidene chloride copolymer

C Acrylates/ethylhexyl acrylate cross- Techpolymer ACP-8C

polymer

D Methyl methacrylate crosspolymer SUNPMMA H

E Polymethyl methacrylate Sepimat H 10

The compositions are applied to a lock of natural Caucasian hair (0.5 g of composition per g of hair); the composition is spread over the entire length of the lock. The locks are suspended and an excess of sebum is applied locally. The rate of migration of the sebum over the locks after 24 hours of application is observed.

It is found that all the compositions according to the invention allow a reduction in the rate of migration of the sebum over natural locks, when compared with the comparative composition.

Claims

1 . Cosmetic hair treatment process comprising the application to the hair of a cosmetic composition comprising:

- hollow and/or porous particles with a mean particle size of from 10 to 300 microns (μιτι);

- one or more thickening polymers; and

the said application step preferably not being followed by a rinsing step.

2. Process according to Claim 1 , for hair treatment, for caring for and/or cleansing the hair, which makes it possible to slow down or even prevent the re- greasing of the hair; and/or to lengthen the interval between shampoo washes.

3. Process according to either of the preceding claims, in which the said parti- cles have a mean particle size of from 10 to 200 μιτι, preferably from 10 to 100 μιτι and better still from 15 to 40 m.

4. Process according to one of the preceding claims, in which the hollow and/or porous particles are chosen from silica (micro)particles, crosslinked or non- crosslinked (meth)acrylic polymer particles; polyamide particles; glass particles; polymer particles, especially of crosslinked or non-crosslinked, optionally thermoplastic, optionally expanded vinyl or (meth)acrylic polymer; and mixtures thereof.

5. Process according to one of the preceding claims, in which the hollow and/or porous particles are chosen from polyamide particles, in particular of Nylon 6, Nylon 6-6, Nylon 12 or Nylon 6-12; particles, especially spherical particles, of polymethyl methacrylate (PMMA); porous particles of crosslinked acrylic polymer; particles of a copolymer of ethylene glycol dimethacrylate and methyl methacrylate; particles of polyallyl methacrylate and of ethylene glycol dimethacrylate; silica particles, which are especially spherical; hollow glass beads; hollow particles of crosslinked polymethyl methacrylate; hollow particles of one or more expanded thermoplastic polymers.

6. Process according to one of the preceding claims, in which the hollow and/or porous particles are hollow particles of an expanded thermoplastic copolymer of acrylonitrile, vinylidene chloride, vinyl chloride and/or a (meth)acrylic or styrene monomer; preferably of vinylidene chloride and acrylonitrile, or of vinylidene chloride, acrylonitrile and a C1 -C4 alkyl (meth)acrylate, or of styrene monomer.

7. Process according to one of the preceding claims, in which the hollow and/or porous particles are hollow particles of an expanded polymer of vinylidene chloride and acrylonitrile or of vinylidene chloride, acrylonitrile and methyl methacry- late; with a mean particle size of from 10 to 300 μιτι, for example from 10 to 200 μιτι, preferably from 10 to 100 m and better still from 15 to 40 μιτι; the particles being optionally filled with a gas, chosen especially from air, nitrogen, isobutane and isopentane, preferentially isobutane.

8. Process according to one of the preceding claims, in which the said hollow and/or porous particles are present in the composition in an amount ranging from 0.01 % to 20% by weight, especially ranging from 0.05% to 10% by weight and better still from 0.1 % to 5% by weight, relative to the total weight of the composition.

9. Process according to one of the preceding claims, in which the monoalcohols are chosen from ethanol and isopropanol, and mixtures thereof; and most particularly ethanol.

10. Process according to one of the preceding claims, in which the monoalco- hol(s) are present in the composition in an amount ranging from 5% to 35% by weight and better still from 5% to 30% by weight relative to the total weight of the composition.

1 1 . Process according to one of the preceding claims, in which the thickening polymer is chosen from acrylic thickening polymers, thickening polymers bear- ing a sugar unit, and mixtures thereof; more particularly from:

- (meth)acrylic associative thickeners;

- crosslinked acrylic acid homopolymers;

- crosslinked copolymers of (meth)acrylic acid and of (C1 -C6)alkyl acrylate;

- nonionic homopolymers and copolymers containing ethylenically unsaturated monomers of ester and/or amide type;

- ammonium acrylate homopolymers or copolymers of ammonium acrylate and of acrylamide;

- (meth)acrylamido(C1 -C4)alkylsulfonic acid homopolymers and copolymers;

- crosslinked methacryloyloxy(C1 -C4)alkyltri(C1 -C4)alkylammonium homopoly- mers and copolymers;

- tree or shrub exudates, and derivatives thereof; - gums derived from algae, and derivatives thereof;

- gums derived from seeds or tubers, and derivatives thereof;

- microbial gums, and derivatives thereof;

- plant extracts, including cellulose, starch and inulin, and derivatives thereof.

12. Process according to one of the preceding claims, in which the thickening polymer is chosen from crosslinked acrylic acid homopolymers, and/or thickening polymers bearing a sugar unit, and especially from guar gums, locust bean gums, xanthan gums, starches and celluloses, in their modified form (deriva- tives) or unmodified form.

13. Process according to one of the preceding claims, in which the thickening polymer(s) are present in the composition in an amount ranging from 0.01 % to 10% by weight, especially ranging from 0.05% to 5% by weight and preferen- tially from 0.1 % to 3% by weight, relative to the total weight of the composition.

14. Process according to any one of the preceding claims, in which the composition comprises water at a concentration ranging from 5% to 98% by weight, especially from 20% to 95% by weight and better still from 50% to 80% by weight, relative to the total weight of the composition.

15. Use of a cosmetic composition comprising:

- one or more thickening polymers;