WO2008006898A2

WO2008006898A2 - Mascara comprising a thermogelling polymer

Info

Publication number: WO2008006898A2
Application number: PCT/EP2007/057233
Authority: WO
Inventors: Stéphane Arditty
Original assignee: L'oreal
Priority date: 2006-07-13
Filing date: 2007-07-13
Publication date: 2008-01-17
Also published as: WO2008006898A3

Abstract

The subject of the invention is a cosmetic composition intended to be applied to keratin fibres and more particularly the eyelashes and the eyebrows and comprising at least one thermogelling polymer. This type of polymer makes it possible to obtain stable emulsions and to offer mascara consistencies suitable for making up keratin fibres. The composition may be in a solid, semi-solid or liquid form, optionally with overrun. The invention also relates to a method for making up and/or caring for keratin fibres, especially the eyelashes or eyebrows, the said method consisting in applying to the said keratin fibres a composition containing at least one thermogelling polymer.

Description

Mascara comprising a thermogelling polymer

The subject of the invention is a cosmetic composition intended to be applied to keratin fibres and more particularly the eyelashes and the eyebrows and comprising at least one thermogelling polymer. This type of polymer makes it possible to obtain stable emulsions and to offer mascara consistencies suitable for making up keratin fibres.

The composition may be in a solid, semi-solid or liquid form, optionally with overrun.

The invention also relates to a method for making up and/or care of keratin fibres, especially the eyelashes or eyebrows, the said method consisting in applying to the said keratin fibres a composition containing at least one thermogelling polymer.

Mascaras are in particular prepared according to two types of formulation: aqueous mascaras termed cream mascaras, in the form of a dispersion of waxes in water; anhydrous mascaras or mascaras with a low water content termed waterproof mascaras in the form of dispersions of waxes in organic solvents.

The present application relates more specifically to aqueous mascaras.

The application of mascara makes it possible to increase the volume of the eyelashes and consequently to increase the intensity of the look. For that, numerous thickening or volumizing mascaras exist whose principle consists in depositing the maximum material on the eyelashes so as to obtain a volumizing (or charging) effect.

It is in particular through the quantity of solid particles (in particular waxes, which make it possible to structure the composition) that the desired application specificities for the compositions, such as for example their fluidity or consistency, as well as their thickening power (also called charging or makeup power), are adjusted.

These solid particles are dispersed in the cream mascara with the aid of a surfactant system. Among the conventional emulsifiers or emulsifier systems are in particular the emulsifier systems based on triethanolamine stearate.

The problem posed in the present application is to provide a mascara in which not only the waxes but also the pigments are homogeneously dispersed, the said mascara having a sufficiently thick texture to obtain a charging, volumizing deposit on the eyelashes, and having a satisfactory consistency allowing easy application to the eyelashes and a smooth and homogeneous deposit.

Surprisingly and unexpectedly, the applicant has observed that the use of at least one thermogelling polymer in a mascara makes it possible to obtain a composition having, alone or in combination, the above properties.

More specifically, and according to a first aspect, the subject of the invention is a cosmetic composition for making up and/or caring for keratin fibres, and more particularly the eyelashes and the eyebrows, comprising an aqueous phase and at least one thermogelling polymer, the said polymer constituting the main surfactant system of the composition.

The expression "main surfactant system" is understood to mean a system which, in its absence, does not lead to the formation of a stable composition.

The expression "stable" is understood to mean a composition which, after having been placed in an oven at 45°C for two months, does not have, after returning to room temperature, grains perceptible to the touch when a fine layer of the composition is sheared between the fingers.

Advantageously, the thermogelling polymer constitutes the sole surfactant system of the composition.

The expression "sole" is understood to mean that any optional additional surfactant system is present in an amount not exceeding 1%, and preferably not exceeding 0.5%. Preferably still, the expression "sole" denotes a complete absence of any other surfactant system.

According to a second aspect, the subject of the invention is also a cosmetic composition for making up and/or caring for keratin fibres, and more particularly the eyelashes and the eyebrows, the said composition comprising less than 1 % by weight of triethanolamine relative to the total weight of the composition. Advantageously, the composition according to one embodiment of the invention comprises less than 0.5% by weight of triethanolamine relative to the total weight of the composition, preferably less than 0.1% by weight, and even better is free of triethanolamine.

Preferably, the composition comprises less than 1% by weight of triethanolamine stearate relative to the total weight of the composition, preferably less than 0.5% by weight, and even better is free of triethanolamine stearate.

Accordingly to a third aspect, the subject of the invention is also a cosmetic composition for making up and/or caring for keratin fibres, in particular the eyelashes or the eyebrows, comprising an aqueous phase and at least one thermogelling polymer, the said composition additionally comprising at least one associative polymer.

According to an advantageous embodiment, the thermogelling polymer is a polymer of the polyurethane or sodium polyacrylate type with POE (polyethylene oxide) and POP (polypropylene oxide) groups, containing or not containing urea units.

According to another aspect, the present invention relates to a method for making up and/or caring for keratin fibres, consisting in applying to the said fibres a composition according to the invention, the said method additionally comprising a step consisting in heating the composition prior to, simultaneously with or following the application of the said composition.

The heating of the composition may be carried out by any appropriate means. In the case in particular of heating of the composition prior to its application, the composition may be heated in a microwave or in a water bath.

When the heating of the composition is carried out during its application or following its application, the heating may be carried out by means of a heating device, typically a heating element, provided directly on the applicator of the composition, or on a tool distinct from the applicator.

Advantageously, the composition is heated to a temperature greater than or equal to the specific gelling temperature of the thermogelling polymer or of at least one of the thermogelling polymers of the composition. According to another aspect, the present invention relates to a method for making up and/or caring for keratin fibres consisting in forming on the said fibres a first deposit of a first composition containing a physiologically acceptable medium, and then in forming on all or part of the first deposit a second deposit of a second composition containing a physiologically acceptable medium, at least one of the first and second compositions containing at least one thermogelling polymer.

The present application relates to compositions incorporating the aspects mentioned above, whether they are taken alone or in combination.

The compositions in accordance with the invention may have a viscoelastic behaviour.

In general, a material is said to be viscoelastic when, under the effect of shearing, it has both the characteristics of an elastic material, that is to say capable of storing energy, and the characteristics of a viscose material, that is to say capable of dissipating energy.

The viscoelastic behaviour of the compositions in accordance with the invention may be more particularly characterized by the rigidity modulus G. This parameter is in particular defined in the book "Initiation a Ia rheologie", G. Couarraze and J. L. Grossiord, 2nd edition, 1991 , Edition Lavoisier-Tec 1 Doc.

The measurements are performed on a controlled stress rheometer, RS 600 from the company ThermoRheo, equipped with a thermostatted bath and a stainless steel rotor having a cone/flat geometry, with a diameter of 35 mm and an angle of 2°. The 2 surfaces are "sanded" in order to limit the phenomena of sliding on the walls. The measurements are performed at 25°C ± 1 °C.

The dynamic measurements are performed by applying a harmonic variation of the stress. In these experiments, the amplitudes of the shear stress (noted t) and of the shear deformation (noted g) are small so as to remain within the limits of the linear viscoelastic domain of the composition (conditions making it possible to evaluate the rheological characteristics of the composition at rest).

The linear viscoelastic domain is generally defined by the fact that the response of the material (i.e. the deformation) is at any moment directly proportional to the value of the force applied (i.e. the stress). In this domain, the applied stresses are low and the material is subjected to deformations without modifying its microscopic structure. Under these conditions, the material is studied "at rest" and in a non-destructive manner.

The composition is subjected to a harmonic shear according to a stress τ(t) varying sinusoidally according to a pulse ω (ω = 2FIv), v being the frequency of the shear applied. The composition thus sheared is subjected to a stress τ(t) and responds according to a deformation g(t) corresponding to microdeformations for which the rigidity modulus varies little as a function of the stress applied.

The stress τ(t) and the deformation g(t) are defined respectively by the following relationships: τ(0 = T₀ cos(ft) • t) γ(t) = γ₀ cos(&) - t - δ) To being the maximum amplitude of the stress and go being the maximum amplitude of the deformation. The elasticity δ is the phase shift angle between the stress and the deformation.

The measurements are performed at a frequency of 1 Hz (v= 1 Hz).

Increasing stresses are applied to the sample starting with an initial stress equal to 0.01 Pa up to a final stress of 1000 Pa, the stresses being applied only once.

The variation of the rigidity modulus G (corresponding to the ratio of τo to γo) and of the elasticity δ (corresponding to the phase shift angle of the stress applied relative to the deformation measured) as a function of the stress τ(t) applied is thus measured.

The deformation of the composition is measured in particular for the stress zone in which the variation of the rigidity modulus G and of the elasticity δ is less than 7% (zone of microdeformations) and the so-called "plateau" parameters Gp and δp are thus determined.

The composition has for example a plateau rigidity modulus Gp greater than or equal to 10 Pa, preferably greater than or equal to 50 Pa, possibly ranging up to 106 Pa and preferably up to 5 x 10⁵ Pa.

The thermogelling polymer may additionally be combined with surfactants or cosurfactants in order to adjust the cosmetic properties of the formula.

Thermogelling polymer

Preferably, the thermogelling polymers according to the invention are water-soluble and comprise water-soluble units and units having, in water, a lower critical solution temperature (LCST), the solution temperature upon heating in aqueous solution of the said units at LCST being from 5 to 40⁰C for a concentration by mass in water of 1% of the said units and the concentration of the said polymer in the said composition being such that its gelling temperature is in the region from 5 to 40⁰C.

The expression "water-soluble polymer" is generally understood to mean a polymer that is soluble in water, at a temperature of 5 to 80⁰C, in an amount of at least 10 g/l, preferably at least 20 g/l. However, the expression "water-soluble polymer" is also understood to mean a polymer which does not necessarily have the solubility mentioned above, but which in aqueous solution at 1% by weight, from 5 to 80°C, makes it possible to obtain a macroscopically homogeneous and transparent solution, that is to say having a maximum light transmittance value, regardless of the wavelength between 400 and 800 nm, through a sample 1 cm thick, of at least 85%, preferably of at least 90%.

The expression "water-soluble units" is generally understood to mean that these units are units which are soluble in water, at a temperature of 5 to 80⁰C, in an amount of at least 10 g/l, preferably of at least 20 g/l. However, the expression "water-soluble units" is also understood to mean units which do not necessarily have the solubility mentioned above, but which in aqueous solution at 1% by weight, from 5 to 80°C, make it possible to obtain a macroscopically homogeneous and transparent solution, that is to say having a maximum light transmittance value, regardless of the wavelength between 400 and 800 nm, through a sample 1 cm thick, of at least 85%, preferably of at least 90%. These water-soluble units do not have a solution temperature upon heating of the LCST type. To this end, it is useful to recall that the expression "units at LCST" is preferably understood to mean units whose solubility in water is modified above a certain temperature. They are units having a solution temperature upon heating (or cloud point) defining their zone of solubility in water. The minimum solution temperature obtained as a function of the concentration of polymer consisting solely of units at LCST is called "LCST" (Lower Critical Solution Temperature). For each polymer concentration at LCST, a solution temperature upon heating is observed. It is greater than the LCST which is the minimum point on the curve. Below this temperature, the polymer is soluble in water, above this temperature, the polymer loses its solubility in water.

These units at LCST of the polymer preferably have, according to the invention, a solution temperature upon heating of 5 to 40⁰C for a concentration by mass in water of 1% by weight of the said units at LCST.

More preferably, the solution temperature upon heating in aqueous solution of the units at LCST of the polymer is from 10 to 35°C for a concentration by mass in water of 1% of the said units at LCST.

More preferably, the polymer concentration is such that the gelling temperature is in the region from 10 to 35°C.

The polymer having the structure described above with water-soluble and specific units at LCST defined above has, in aqueous solution, gelling properties above a critical temperature, or thermogelling properties.

These gelling properties upon heating observed above the solution temperature of the chains at LCST are described in particular in the following documents:

[1] D. HOURDET et al., Polymer, 1994, vol. 35, No. 12, pages 2624-2630.

[2] F. L'ALLORET et al., Coll. Polym. Sci., 1995, vol. 273, No. 12, pages 1163-1 173. [3] F. L'ALLORET, Revue de I'lnstitut Frangais du Petrole, 1997, vol. 52, No. 2, pages 117-128.

They are due to the association of the chains at LCST within the hydrophobic microdomains above their solution temperature, thus forming crosslinking nodes between the main chains. These gelling properties are observed when the polymer concentration is sufficient to allow interactions between grafts at LCST carried by various macromolecules. The minimum concentration necessary, called "critical aggregation concentration or CAC" is evaluated by measurements of rheology: it is the concentration above which the viscosity of an aqueous solution of the polymers of the invention becomes higher than the viscosity of a solution of the equivalent polymer not containing chains at LCST.

Above the CAC, the polymers of the invention preferably have gelling properties when the temperature becomes higher than a critical value called "gelling temperature or

Tgel". According to the literature data, there is good agreement between the Tgel and the solution temperature of the chains at LCST, under the same concentration conditions. The gelling temperature of an aqueous solution of a polymer of the invention is determined by measurements of rheology: it is the temperature above which the viscosity of the solution of a polymer of the invention becomes higher than the viscosity of a solution of the equivalent polymer not containing chains at LCST.

The polymers of the invention are preferably characterized by a specific gelling temperature generally of 5 to 40⁰C, preferably of 10 to 35°C, for a concentration by mass in water, for example equal to 2% by weight.

The polymers used in the invention may be block polymers or graft polymers which comprise, on the one hand, water-soluble units and, on the other hand, units at LCST as defined above.

It should be specified that, in the present context, the water-soluble units or the units at LCST of the polymers used according to the invention are defined as not including the groups linking to one another, on the one hand, the said water-soluble units and, on the other hand, the said units at LCST.

The said linkage groups are derived from the reaction, during the preparation of the polymer, of the reactive sites carried, on the one hand, by the precursors of the said water-soluble units and, on the other hand, by the precursors of the said units at LCST.

The polymers used in the context of the invention may therefore be block polymers, comprising for example blocks consisting of water-soluble units alternating with blocks at LCST.

These polymers may also be provided in the form of graft polymers whose backbone consists of water-soluble units, the said backbone bearing grafts consisting of units at LCST.

The said polymers may be partially crosslinked.

These water-soluble units are totally or partially capable of being obtained by polymerization, in particular free-radical polymerization, or by polycondensation, or alternatively consist totally or partially of existing natural or modified natural polymers.

By way of example, the water-soluble units are totally or partially capable of being obtained by polymerization, in particular free-radical polymerization, of at least one monomer chosen from the following monomers:

- (meth)acrylic acid;

- vinyl monomers of the following formula (I):

H₂C=CR

(I) CO X

in which:

- R is chosen from H, -CH₃, -C₂H₅ or -C₃H₇; and

- X is chosen from : - alkyl oxides of the -OR' type where R' is a saturated or unsaturated, linear or branched, hydrocarbon radical having from 1 to 6 carbon atoms, optionally substituted with at least one halogen atom (iodine, bromine, chlorine, fluorine); a sulphonic (-SO₃-) group, sulphate (-SO₄-), phosphate (-PO₄H₂); hydroxyl (-OH); primary amine (-NH2); secondary amine (-NHR₁), tertiary amine (-NR₁R₂) or quaternary amine (^+R₁R₂R₃) group with R₁, R₂ and R₃ being, independently of each other, a saturated or unsaturated, linear or branched hydrocarbon radical having 1 to 6 carbon atoms, provided that the sum of the carbon atoms of R' + R₁ + R₂ + R₃ does not exceed 7; and

- groups -NH₂, -NHR₄ and -NR₄R₅ in which R₄ and R₅ are, independently of each other, saturated or unsaturated, linear or branched, hydrocarbon radicals having 1 to 6 carbon atoms, provided that the total number of carbon atoms of R4 + R5 does not exceed 7, the said R₄ and R₅ being optionally substituted with a halogen atom (iodine, bromine, chlorine, fluorine); a hydroxyl (-OH); sulphonic (-SO₃-); sulphate (-SO₄-); phosphate (-PO₄H₂); primary amine (-NH₂); secondary amine (-NHR₁), tertiary amine (-NR₁R₂) and/or quaternary amine (-N+R-|R₂R₃) group, with R1 , R2 and R3 being, independently of each other, a saturated or unsaturated, linear or branched hydrocarbon radical having 1 to 6 carbon atoms, provided that the sum of the carbon atoms of R₄ + R₅ + R₁ + R₂ + R₃ does not exceed 7; - maleic anhydride;

- itaconic acid;

- vinyl alcohol of formula CH₂=CHOH;

- vinyl acetate of formula CH₂=CH-OCOCH₃;

- N-vinyllactams such as N-vinylpyrrolidone, N-vinylcaprolactam and N-butyrolactam; - vinyl ethers of formula CH₂=CHORe in which R₆ is a saturated or unsaturated, linear or branched hydrocarbon radical having from 1 to 6 carbons;

- water-soluble derivatives of styrene, in particular styrene sulphonate;

- dimethyldiallylammonium chloride; and

- vinylacetamide.

The water-soluble units of the thermogelling polymer may consist entirely or partly of one or more of the components, such as the polycondensates and the natural or modified natural polymers, it being possible for the said component to be chosen from:

- water-soluble polyurethanes, - xanthan gum, in particular that marketed under the names Keltrol T and Keltrol SF by Kelco; or Rhodigel SM and Rhodigel 200 from Rhodia;

- alginates (Kelcosol from Monsanto) and their derivatives such as propylene glycol alginate (Kelcoloid LVF from Kelco);

- cellulose derivatives and in particular carboxymethylcellulose (Aquasorb A500, Hercules), hydroxypropylcellulose, hydroxyethylcellulose and quaternized hydroxyethylcellulose;

- galactomannans and their derivatives, such as Konjac gum, guar gum, hydroxypropylguar, hydroxypropylguar modified with sodium methylcarboxylate groups (Jaguar XC97-1 , Rhodia), guar hydroxypropyltrimethylammonium chloride. Polyethyleneimine may also be mentioned.

Preferably, the water-soluble units have a molar mass ranging from 1000 g/mol to 5 000 000 g/mol when they constitute the water-soluble backbone of a graft polymer.

These water-soluble units preferably have a molar mass ranging from 500 g/mol to 100 000 g/mol when they constitute a block of a multiblock polymer.

The units at LCST of the polymers used in the invention may be defined as being units whose solubility in water is modified above a certain temperature. They are units having a solution temperature upon heating (or cloud point) defining their zone of solubility in water. The minimum solution temperature obtained as a function of the polymer concentration is called "LCST" (Lower Critical Solution Temperature). For each polymer concentration, a solution temperature upon heating is observed; it is greater than the LCST which is the minimum point of the curve. Below this temperature, the polymer constituting the unit at LCST is soluble in water; above this temperature, the polymer constituting the unit at LCST loses its solubility in water.

Some of these polymers at LCST are in particular described in the following articles: - TAYLOR et al, Journal of Polymer Science, part A : Polymer Chemistry, 1975, 13, 2551 ;

- J. BAILEY et al, Journal of Applied Polymer Science, 1959, 1 ,56; - HESKINS et al, Journal of Macromolecular Science, Chemistry A2, 1968, vol. 8, 1441.

The expression "soluble in water at the temperature T" is understood to mean that the units have a solubility at T of at least 1 g/l, preferably of at least 2 g/l.

The measurement of the LCST may be carried out visually: the temperature at which the cloud point of the aqueous solution appears is determined; this cloud point results in the opacification of the solution, or loss of transparency.

In general, a transparent composition will have a maximum light transmittance value, regardless of the wavelength between 400 and 800 nm, through a sample with a thickness of 1 cm, of at least 85%, preferably of at least 90%. The transmittance may be measured by placing a sample with a thickness of 1 cm in the light ray of a spectrophotometer working in the wavelengths of the light spectrum.

The units at LCST of the polymers used in the invention may consist of one or more polymers chosen from the following polymers:

- polyethers such as polypropylene oxide (POP), random copolymers of ethylene oxide (EO) and of propylene oxide (PO),

- polyvinyl methyl ethers,

- N-substituted polymeric and copolymeric derivatives of acrylamide having an LCST such as poly-N-isopropylacrylamide (NIPAM) and poly-N-ethylacrylamide, and

- polyvinylcaprolactam and copolymers of vinylcaprolacatam.

Preferably, the units at LCST consist of polypropylene oxide (POP)n where n is an integer from 10 to 70, or random copolymers of ethylene oxide (EO) and propylene oxide (PO), represented by the formula:

(E0)m (PO)n in which m is an integer ranging from 1 to 40, preferably from 2 to 20, and n is an integer ranging from 10 to 60, preferably from 20 to 50.

Preferably, the molar mass of these units at LCST is from 500 to 5300 g/mol, more preferably from 1500 to 4000 g/mol.

It is observed that the random distribution of the EO and PO units results in the existence of a lower critical solution temperature above which a macroscopic phase separation is observed. This behaviour is different from that of the block copolymers (EO)(PO) which micellize above a so-called critical miscellization temperature (aggregation on a microscopic scale).

The units at LCST may therefore be in particular polypropylene oxides such as Polyglycols P3000 and P4000 from Dow Chemical, random copolymers of ethylene oxide and propylene oxide which are aminated, in particular monoaminated, diaminated or triaminated. These polymers, before reaction, carry reactive sites; in this case, amino groups react with the reactive sites of the water-soluble polymers, for example carboxyl groups, to give the final polymer used in the invention. In the final polymer, the water-soluble units are linked to the units at LCST by linkage groups derived from the reaction of the reactive groups or sites carried by the units at LCST and the precursors of the water-soluble units, respectively. These linkage groups will be, for example, amide, ester, ether or urethane groups.

Among these polymers at LCST that are commercially available, there may be mentioned the copolymers sold under the name Jeffamine by HUNTSMAN, and in particular Jeffamine XTJ-507 (M-2005), Jeffamine D-2000 and Jeffamine XTJ-509 (or T-3000).

The units at LCST may also be derived from random EO/PO copolymers with OH ends, such as those sold under the name Polyglycols P41 and B1 1 by Clariant.

It is also possible to use, in the invention as units at LCST, the N-substituted polymer and copolymer derivatives of acrylamide having an LCST, and polyvinylcaprolactam and copolymers of vinylcaprolactam.

By way of examples of N-substituted polymer and copolymer derivatives of acrylamide having an LCST, there may be mentioned poly-N-isopropylacrylamide, poly- N-ethylacrylamide and copolymers of N-isopropylacrylamide (or of N-ethylacrylamide) and of a vinyl monomer chosen from monomers having the formula (I) given above, maleic anhydride, itaconic acid, vinylpyrrolidone, styrene and its derivatives, dimethyldiallylammonium chloride, vinylacetamide, vinyl ethers and derivatives of vinyl acetate.

The molar mass of these polymers is preferably from 1000 g/mol to 500 000 g/mol, preferably from 2000 to 50 000 g/mol.

The synthesis of these polymers may be carried out by free-radical polymerization with the aid of a pair of initiators such as aminoethanethiol hydrochloride, in the presence of potassium persulphate, in order to obtain precursor oligomers having an aminated reactive end.

By way of examples of copolymers of vinylcaprolactam, there may be mentioned copolymers of vinylcaprolactam and of a vinyl monomer having the formula (I) given above, or of a monomer chosen from maleic anhydride, itaconic acid, vinylpyrrolidone, styrene and its derivatives, dimethyldiallylammonium chloride, vinylacetamide, vinyl alcohol, vinyl acetate, vinyl ethers and derivatives of vinyl acetate. The molar mass of these polymers and copolymers of vinylcaprolactam is generally from 1000 g/mol to 500 000 g/mol, preferably from 2000 to 50 000 g/mol.

The synthesis of these compounds may be carried out by free-radical polymerization with the aid of a pair of initiators such as aminoethanethiol hydrochloride, in the presence of potassium persulphate, in order to obtain units at LCST having an aminated reactive end.

The proportion by mass of these units at LCST in the final polymer is preferably from 5% to 70%, in particular from 10% to 60%, and particularly from 20% to 50% by weight, relative to the final polymer.

It was seen above that the solution temperature upon heating of the said units at LCST of the polymer used in the invention is from 5 to 40⁰C, preferably from 10 to 35°C, for a concentration by mass in water of 1% by weight of the said units at LCST.

The polymers used in the context of the invention may be easily prepared by persons skilled in the art on the basis of their general knowledge, using processes for grafting, copolymerization or coupling reaction.

When the final polymer is in the form of a graft polymer, in particular having a water- soluble backbone with side chains or grafts at LCST, it is possible to prepare by grafting units at LCST having at least one reactive end or reactive site, which is in particular aminated, on a water-soluble polymer forming the backbone, bearing a minimum of 10 mol% of reactive groups such as carboxylic acid functional groups. This reaction may be carried out in the presence of a carbodiimide such as dicyclohexylcarbodiimide or 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, in a solvent such as N-methylpyrrolidone or water.

Another possibility is to prepare graft polymers consisting in copolymerizing for example a macromonomer at LCST (chain at LCST previously described with a vinyl end) and a water-soluble vinyl monomer such as acrylic acid or vinyl monomers having the formula (I). When the final polymer is in the form of a block polymer, it is possible to prepare it by coupling between water-soluble units and units at LCST, these units having at each end complementary reactive sites.

In the case of the grafting processes and coupling processes, the reactive sites of the units at LCST may be amine, in particular monoamine, diamine or triamine, functional groups and OH functional groups. In this case, the reactive sites of the water-soluble units may be carboxylic acid functional groups. The groups linking the water-soluble units and the units at LCST will therefore be, for example, amide groups or ester groups.

The thermogelling polymers in accordance with the invention may be chosen from those described in the following patents and patent applications: the patent applications EP1307501 , EP1355990, EP1355625, FR2856923, EP1493774 and WO04/006872, the patents US6,878,754 and US6,689,856; the patent applications EP1407791 , EP1416044, FR 2788008, WO 03/008462, FR2694939, EP0629649, US6645476, WO97/00275, WO98/06438, WO98/29487, WO98/48768, WO98/50005, WO00/07603, WO02/076392, FR2820976, WO00/35961 , WO02/032560, EP0692506, US6870012, WO03/106536, WO00/38651 , WO00/00222, WO01/41735, US2003/0099709, GB2408510.

Particularly advantageous thermogelling water-soluble polymers may be chosen from:

(1 ) polyurethanes comprising polyethylene oxide/polyoxypropylene/polyethylene oxide (or POE-POP-POE) groups such as those described in applications EP-1407791 (example 1 describes a polyurethane derived from the polycondensation of Pluronic F- 127 with hexamethylene diisocyanate), EP-A-692506, FR-A-2840907, WO 03/106536, US-A-2005175573, US-A-5702717.

Such polyurethanes are obtained in a known manner by polycondensation of diisocyanates and heat-sensitive diol triblocks POE-POP-POE and in particular described in the applications cited above.

As diisocyanates, there may be mentioned aliphatic diisocyanates such as ethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, and also 4,4'- methylene-bis-dicyclohexyl diisocyanate, 4,4'- diphenylmethane diisocyanate, xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, dimethyldiphenylene diisocyanate.

Triblock diols POE-POP-POE used may correspond to the following formula (I):

HO-(CH₂-CH₂-O)_X-(CH₂-CH(CH_S)-OV(CH₂-CH₂-O)_X-H

with 20<x<120 and 20<y<120 such as Pluronics, in particular Pluronic F-127.

The polyurethane may comprise urea and/or allophanate groups, as described in applications WO 03/106536 and US-A-5702717.

The polycondensation may also be carried out in the presence of other reactive compounds such as diols comprising one or more carboxylic acid groups or a tertiary amine (in particular amino methyl) group or alternatively such as monohydroxylated polyethylene oxides. In particular, the polycondensation may be carried out in the presence of water.

The polyurethane may be linear or branched.

(2) multiblock copolymers comprising a poly block of N-isopropylamide and n-butyl acrylate randomly distributed and a polyethylene glycol block such as those described in application EP-A-1407791.

It is possible in particular to use the product sold under the trade name TGP-20 by the company MEBIOL.

(3) copolymers of acrylamidomethylpropanesulphonic acid (or AMPS) such as those described in patents US6645476 and US6689856, and their salts (in particular sodium or ammonium salts) and of a macromonomer of an ester of (meth)acrylic acid and of alkoxylated C2-C4 alkyl (in particular ethylene oxide (EO) and/or propylene oxide (PO) (in particular at 1 to 500 units of alkoxylated alkyl, more preferably from 3 to 50, and better still 7 to 30 units). Such macromonomers are chosen in particular from esters of (meth)acrylic acid with an ether of polyethylene and propylene glycol or alternatively an ether of polyglycol (8 to 25 EO) and of a C10 to C22 fatty alcohol) in particular chosen from Genapol C-080 or UD-080, or LA-070 or LA-110 or T-080 or T-150 or T-110 or T-200 or T-250 from Clariant.

Such macromonomers may also be derived from aminated, in particular mono-, di- or triaminated EO/PO random copolymers of the Jeffamine type from HUNTSMAN, and in particular Jeffamine XTJ-507 (M-2005), Jeffamine D-2000 and Jeffamine XTJ-509 (or T-3000).

Such macromonomers may also be derived from EO/PO random copolymers with OH ends, such as those sold under the name Polyglycols P41 and B1 1 by Clariant,

Use will be made more particularly of the copolymer of polyacrylamido-2- methylpropanesulphonic acid (AMPS) neutralized with aqueous ammonia (40% by weight relative to the total weight of the polymer) and of a macromonomer of polyether methacrylate (60% by weight) in which the polyether is a POE/POP random copolymer comprising 5.5 mol of ethylene oxide (EO) units and 31 propylene oxide units.

(4) copolymers as described in patent application EP1307501 consisting of a polyacrylic acid (PAA) backbone bearing side chains or grafts consisting of units at LCST chosen from (i) those of the ethylene oxide (EO) and propylene oxide (PO) random copolymer type, represented by the formula:

(EO)_1n (PO)_n

in which m is an integer ranging from 1 to 40, preferably from 2 to 20, and n is an integer ranging from 10 to 60, preferably from 20 to 50; the molar mass of these units at LCST being preferably from 500 to 5300 g/mol, more preferably from 1500 to 4000 g/mol.

(ii) poly-N-isopropylacrylamide polymers whose molar mass is preferably from 1000 g/mol to 500 000 g/mol, more preferably from 2000 to 50 000 g/mol. The thermogelling polymer level in the compositions according to the invention may range from 0.01 to 20%, by weight, preferably from 0.1 to 15% by weight, even better from 0.1% to 10% by weight, better still from 0.5 to 10% by weight, and preferably from 1 to 10% by weight relative to the total weight of the composition.

According to an advantageous embodiment, the thermogelling polymer is present in an amount greater than or equal to 0.5%, preferably greater than or equal to 1% by weight relative to the total weight of the composition.

The compositions used according to the invention may contain all the compounds customarily entering into the formulation of the products to be applied to the eyelashes/eyebrows. In general, it comprises a physiologically acceptable medium.

The expression "physiologically acceptable medium" denotes a medium which is nontoxic and capable of being applied to the superficial body growths of human beings. The physiologically acceptable medium is in particular adapted to the form in which the composition is intended to be packaged, for example semi-solid or fluid at room temperature and under atmospheric pressure.

The physiologically acceptable medium of the composition may comprise at least one aqueous phase and/or at least one fatty phase.

The physiologically acceptable medium of the composition may comprise at least one volatile solvent.

The volatile solvent(s) may in particular be chosen from water, volatile organic solvents, volatile oils, and mixtures thereof.

The volatile organic solvent(s) and the volatile oils which may be contained in a composition according to the invention are organic solvents and volatile cosmetic oils, which are liquid at room temperature, having a non-zero vapour pressure, at room temperature and atmospheric pressure, ranging for example from 0.13 Pa to 40 000 Pa (10-3 to 300 mmHg), in particular from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg). The composition according to certain embodiments of the invention comprises an aqueous phase which may form the continuous phase of the composition.

The expression composition with an aqueous continuous phase is understood to mean that the composition has a conductivity, measured a 25°C, greater than or equal to 23 μS/cm (microSiemens/cm), the conductivity being measured for example with the aid of a Mettler Toledo MPC227 conductimeter and a conductivity measuring cell lnlab730. The measuring cell is immersed in the composition so as to remove the air bubbles which may form between the 2 electrodes of the cell. The reading of the conductivity is carried out as soon as the conductimeter value is stabilized. A mean is determined over at least 3 successive measurements.

The aqueous phase contains water and/or at least one water-soluble solvent.

The expression "water-soluble solvent" denotes in the present invention a compound which is liquid at room temperature and miscible with water (miscibility in water greater than 50% by weight at 25°C and atmospheric pressure).

The water-soluble solvents which can be used in the compositions according to the invention may additionally be volatile.

Among the water-soluble solvents which can be used in the compositions in accordance with the invention, there may be mentioned in particular lower monoalcohols having from 1 to 5 carbon atoms such as ethanol and isopropanol, glycols having from 2 to 8 carbon atoms such as ethylene glycol, propylene glycol, 1 ,3- butylene glycol and dipropylene glycol, C₃-C₄ ketones and C₂-C₄ aldehydes.

The aqueous phase (water and optionally the water-miscible solvent) is generally present in the composition according to the present application in an amount ranging from 1% to 95% by weight, relative to the total weight of the composition, preferably ranging from 3% to 80% by weight, and preferably ranging from 5% to 60% by weight.

The composition according to the invention may also comprise a liquid fatty phase. The expression liquid fatty phase, for the purposes of the application, is understood to mean a fatty phase which is liquid at room temperature (25°C) and atmospheric pressure (760 mmHg), composed of one or more non-aqueous fatty substances which are liquid at room temperature, also called oils, which are compatible with each other.

The oil(s) may be present in the composition according to the invention, for example, in an amount ranging from 1% to 50% by weight, preferably from 5% to 30% by weight relative to the total weight of the composition.

The oil(s) contained in the composition may be hydrocarbon oils, silicone oils, fluorinated oils, or mixtures thereof.

The expression "hydrocarbon oil" is understood to mean an oil containing mainly hydrogen and carbon atoms and optionally oxygen, nitrogen, sulphur and phosphorus atoms.

The oil may be chosen from volatile oils and/or non-volatile oils, and mixtures thereof.

The expression "volatile oil" is understood to mean, for the purposes of the invention, an oil capable of evaporating in contact with the skin or the keratin fibre in less than one hour, at room temperature and atmospheric pressure.

The expression "non-volatile oil" is understood to mean an oil remaining on the skin or the keratin fibre at room temperature and atmospheric pressure for at least several hours and having in particular a vapour pressure of less than 10-3 mmHg (0.13 Pa).

The volatile hydrocarbon oils may be chosen from hydrocarbon oils having from 8 to 16 carbon atoms.

As volatile oils, it is also possible to use volatile silicones.

It is also possible to use fluorinated volatile solvents such as nonafluoromethoxybutane or perfluoromethylcyclopentane.

As mentioned above, the composition may also comprise at least one non-volatile oil, and in particular chosen from non-volatile hydrocarbon and/or silicone and/or fluorinated oils.

The liquid fatty phase may represent from 5 to 60% by weight relative to the total weight of the composition, preferably from 10 to 50% and more preferably still from 15 to 40% by weight.

According to one embodiment, the composition according to the invention comprises, in addition to the thermogelling polymer, at least one associative polymer.

The expression "associative polymer" for the purposes of the present invention is understood to mean any amphiphilic polymer comprising in its structure at least one fatty chain and at least one hydrophilic portion.

The associative polymers may be anionic, cationic, non-ionic or amphoteric.

Among the associative anionic polymers, there may be mentioned those comprising at least one hydrophilic unit, and at least one allyl ether unit with a fatty chain, more particularly from those whose hydrophilic unit consists of an ethylenic unsaturated anionic monomer, more particularly of a vinylcarboxylic acid and most particularly of an acrylic acid, a methacrylic acid or mixtures thereof, and those whose allyl ether unit having a fatty chain corresponds to the monomer of the following formula (I):

CH₂ = C(R')CH₂ O B_n R (I)

in which R' denotes H or CH₃, B denotes an 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 still from 12 to 18 carbon atoms.

Anionic amphiphilic polymers of this type are described and prepared, according to an emulsion polymerization process, in patent EP-O 216 479.

As associative anionic polymers, there may also be mentioned the anionic polymers comprising at least one hydrophilic unit of the olefinic unsaturated carboxylic acid type, and at least one hydrophobic unit exclusively of the (Ci_O-C_3O)alkyl ester of unsaturated carboxylic acid type.

There may be mentioned, by way of example, the anionic polymers described and prepared according to patents US-3 915 921 and 4 509 949.

As cationic associative polymers, there may be mentioned quaternized cellulose derivatives and polyacrylates having amino side groups.

The non-ionic associative polymers may be chosen from: - celluloses modified by groups comprising at least one fatty chain such as for example hydroxyethylcelluloses modified by groups comprosing at least one fatty chain such as alkyl, in particular as C₈-C₂₂, arylalkyl or alkylaryl groups, such as NATROSOL PLUS GRADE 330 CS (C₁₆ alkyls) sold by the company AQUALON, - celluloses modified by polyalkylene glycol ether of alkylphenol groups, guars such as hydroxypropyl guar, which are modified by groups comprising at least one fatty chain such as an alkyl chain, copolymers of vinylpyrrolidone and hydrophobic monomers having a fatty chain; copolymers of CrC₆ alkyl methacrylates or acrylates and amphiphilic monomers comprising at least one fatty chain, copolymers of hydrophilic methacrylates or acrylates and hydrophobic monomers comprising at least one fatty chain such as for example the polyethylene glycol methacrylate/lauryl methacrylate copolymer, associative polyurethanes - mixtures thereof.

Preferably, the associative polymer is chosen from associative polyurethanes.

Associative polyurethanes are non-ionic block copolymers comprising in the chain both hydrophilic blocks most often of a polyoxyethylenated nature and hydrophobic blocks which may be aliphatic linkages alone and/or cycloaliphatic and/or aromatic linkages.

In particular, these polymers comprise at least two lipophilic hydrocarbon chains, having from C₆ to C₃o carbon atoms, separated by a hydrophilic block, the hydrocarbon chains may be pendant chains or chains at the end of the hydrophilic block. In particular, it is possible to provide for one or more pendant chains. In addition, the polymer may comprise a hydrocarbon chain at one end or at both ends of a hydrophilic block.

The associative polyurethanes may be blocks in triblock or multiblock form. The hydrophobic blocks may therefore be at each end of the chain (for example: triblock copolymer having a hydrophilic central block) or distributed both at the ends and in the chain (multiblock copolymer for example). These polymers may also be grafts or star- shaped.

Preferably, the associative polyurethanes are triblock copolymers whose hydrophilic block is a polyoxyethylenated chain comprising from 50 to 1000 oxyethylenated groups. In general, the associative polyurethanes comprise a urethane bond between the hydrophilic blocks, hence the origin of the name.

By way of example of the associative polymers which can be used in the invention, there may be mentioned the polymer Ci6-OE₁₂o-Ci6 from the company SERVO DELDEN (under the name SER AD FX1100, a molecule having a urethane functional group and a weight-average molecular weight of 1300), EO being an oxyethylenated unit. As associative polymer, it is also possible to use Rheolate 205 having a urea functional group, sold by the company RHEOX or alternatively Rheolate 208 or 204. These associative polyurethanes are sold in pure form.

The product DW 1206B from RHOM & HAAS having a C₂₀ alkyl chain and having a urethane bond, sold at 20% dry matter content in water, may also be used.

It is also possible to use solutions or dispersions of these polymers, in particular in water or in an aqueous-alcoholic medium. By way of example of such polymers, there may be mentioned SER AD FX1010, SER AD FX1035 and SER AD 1070 from the company SERVO DELDEN, Rheolate 255, Rheolate 278 and Rheolate 244 sold by the company RHEOX. It is also possible to use the product DW 1206F and DW 1206J, as well as Acrysol RM 184 or Acrysol 44 from the company RHOM & HAAS, or alternatively Borchigel LW 44 from the company BORCHERS.

The polymers which can be used in 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).

There may be mentioned by way of example of associative polymers Aristoflex SNC, LNC or HMS (Clariant), Arlacel P 135 (Uniquema), associative PUR such as Nuvis FX 1 100 (Elementis), modified celluloses such as Natrosol Plus Grade 330 CS or Polysurf 67 CS (Hercules-Aqualon), modified starches, Pemulen TR-1 and Pemulen TR-2 (Noveon), Aculyn 22 Polymer and Aculyn 28 Polymer (Rhom and Haas), Viscophobe DB1000 (Amerchol - Dow Chemical), this list not being limiting.

The associative polymer may be present in an amount ranging from 0.1 to 10% by weight, even better from 0.2 to 7% by weight and better still 0.3 to 5% by weight relative to the total weight of the composition.

The compositions according to the invention may comprise at least one agent structuring the liquid fatty phase described above, chosen from semi-crystalline polymers, lipophilic gelling agents and mixtures thereof.

The structuring agent may represent from 5 to 80% by weight relative to the total weight of the composition, preferably from 7 to 75%, and more preferably still from 10 to 55% by weight.

The quantity of oily structuring agent may be adjusted by persons skilled in the art as a function of the structuring properties of the said agent(s).

By way of particular example of structuring semicrystalline polymer which can be used in the composition according to the invention, there may be mentioned the products Intelimer^® from the company Landec which are described in the brochure "Intelimer^® polymers", Landec IP22 (Rev. 4-97). These polymers are in a solid form at room temperature (25°C). They carry crystallizable side chains and have the preceding formula X.

According to one embodiment, the compositions according to the invention may comprise at least one wax. The wax content may range from 5 to 70% by weight relative to the total weight of the composition, in particular it may contain from 7 to 50%, more particularly from 10 to 45%.

By way of illustration of the waxes suitable for the invention, there may be mentioned in particular hydrocarbon waxes such as beeswax, lanolin wax, Chinese wax; rice bran wax, Carnauba wax, Candelilla wax, Ouricury wax, esparto wax, berry wax, shellac wax, Japan wax and sumac wax; montan wax, orange and lemon waxes, microcrystalline waxes, paraffins and ozokerite; polyethylene waxes, the waxes obtained by Fisher-Tropsch synthesis and waxy copolymers and their esters.

There may also be mentioned waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched C₈-C₃₂ fatty chains. Among these, there may be mentioned in particular isomerized jojoba oil such as trans-isomerized partially hydrogenated jojoba oil manufactured or marketed by the company DESERT WHALE under the trade reference lso-Jojoba-50^®, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated copra oil, hydrogenated lanolin oil and di-(1 ,1 ,1- trimethylolpropane) tetrastearate sold under the name Hest 2T-4S^® by the company HETERENE.

Silicone waxes and fluorinated waxes may also be mentioned.

It is also possible to use waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol, which are sold under the names Phytowax ricin 16L64^® and 22L73^® by the company SOPHIM. Such waxes are described in application FR-A- 2792190.

According to a particular embodiment, the compositions according to the invention may comprise at least one wax termed sticky wax. As sticky wax, there may be used a C₂o- C₄₀ alkyl (hydroxystearyloxy)stearate (the alkyl group comprising from 20 to 40 carbon atoms), alone or as a mixture.

Such a wax is sold in particular under the names "Kester Wax K 82 P^®", Ηydroxypolyester K 82 P^®" and "Kester Wax K 80 P^®" by the company KOSTER KEUNEN. In the present invention, it is also possible to use waxes designated later by the expression "microwaxes". As microwaxes which can be used in the compositions according to the invention, there may be mentioned in particular carnauba microwaxes such as that marketed under the name MicroCare 350^® by the company MICRO POWDERS, synthetic wax microwaxes such as that marketed under the name MicroEase 114S^® by the company MICRO POWDERS, microwaxes consisting of a mixture of carnauba wax and polyethylene wax such as those marketed under the names Micro Care 300^® and 310^® by the company MICRO POWDERS, microwaxes consisting of a mixture of carnauba wax and synthetic wax such as that marketed under the name Micro Care 325^® by the company MICRO POWDERS, polyethylene microwaxes such as those marketed under the names Micropoly 200^®, 220^®, 220L^® and 250S^® by the company MICRO POWDERS and polytetrafluoroethylene microwaxes such as those marketed under the names Microslip 519^® and 519 L^® by the company MICRO POWDERS.

The compositions according to the invention may contain emulsifying surfactants other than the surfactant system formed by the thermogelling polymer(s).

These additional surfactants may be chosen from non-ionic, anionic, cationic or amphoteric surfactants or alternatively from surfactant emulsifiers. Reference may be made to the document "Encyclopedia of Chemical Technology, KIRK-OTHMER", volume 22, p. 333-432, 3rd edition, 1979, WILEY, for the definition of the properties and functions (emulsifier) of surfactants, in particular p. 347-377 of this reference, for the anionic, amphoteric or non-ionic surfactants.

The additional surfactants may be present in an amount ranging from 0,01 to 10 % by weight relative to the total weight of the composition, preferably from 0,05% to 10% by weight.

The compositions according to the invention may comprise, according to a particular embodiment, at least one film-forming polymer.

The film-forming polymer may be present in the composition according to the invention in a dry matter (or active material) content ranging from 0.1 % to 30% by weight relative to the total weight of the composition, preferably from 0.5% to 20% by weight, and even better from 1% to 15% by weight.

In the present invention, the expression "film-forming polymer" is understood to mean a polymer capable of forming, on its own or in the presence of a film-forming aid, a film which is macroscopically continuous and adherent to the eyelashes, and preferably a cohesive film, and better still a film whose cohesion and mechanical properties are such that the said film can be isolated and handled separately, for example when the film is made by casting over an antiadherent surface such as a surface coated with TEFLON® or siliconized.

Among the film-forming polymers which can be used in the composition of the present invention, there may be mentioned synthetic polymers of the free-radical type or of the polycondensate type, polymers of natural origin, and mixtures thereof.

The compositions of the invention may comprise a particulate phase comprising particles which may be present for example in an amount of 0.01 to 40%, in particular 0.01 to 30%, and even better 0.05 to 20% by weight, relative to the total weight of the composition.

These particles may comprise at least one pigment and/or at least one pearlescent agent and/or at least glitter and/or at least one filler used in the cosmetic compositions.

As inorganic pigments which may enter into the formulation of the composition, there may be mentioned titanium, zirconium or cerium oxides and zinc, iron or chromium oxides, ferric blue, manganese violet, ultramarine blue and chromium hydrate. Among the organic pigments which can be used in the invention, there may be mentioned carbon black, D & C type pigments, and carmine, barium, strontium, calcium or aluminium lacquers or diketopyrrolopyrrole (DPP) which are described in the documents EP-A-542669, EP-A-787730, EP-A-787731 and WO-A- 96/08537.

The pearlescent agents may be present in the composition in an amount of 0.01 to 25% by weight, in particular from 0.01 to 15% by weight, and even better from 0.02 to 5% by weight relative to the total weight of the composition.

The pearlescent pigments may be chosen from white pearlescent pigments such as mica coated with titanium or with bismuth oxychloride, coloured pearlescent pigments such as mica-titanium with iron oxides, mica-titanium with in particular ferric blue or chromium oxide, mica-titanium with an organic pigment of the abovementioned type, and pearlescent pigments based on bismuth oxychloride.

The fillers may be present in an amount of 0.01 to 40% by weight, in particular 0.01 to 30% by weight, and even better 0.02 to 20% by weight relative to the total weight of the composition. There may be mentioned in particular talc, zinc stearate, mica, kaolin, polyamide powders (Nylon^®) (Orgasol^® from Atochem), polyethylene powders, powders of tetrafluoroethylene polymers (Teflon^®), starch, boron nitride, polymeric microspheres such as those of polyvinylidene chloride/acrylonitrile such as Expancel^® (Nobel Industrie), acrylic acid copolymers (Polytrap^® from the company Dow Corning) and microbeads of silicone resin (Tospearls^® from Toshiba, for example), elastomeric organopolysiloxanes.

The compositions according to the invention may also comprise water-soluble or fat- soluble colorants in an amount ranging from 0.01 to 6% by weight, in particular from 0.01 to 3% by weight relative to the total weight of the composition. The fat-soluble colorants are for example Sudan red, DC Red 17, DC Green 6, β-carotene, soybean oil, Sudan brown, DC Yellow 1 1 , DC Violet 2, DC orange 5, quinoline yellow. The water- soluble colorants are for example beat juice, methylene blue.

The compositions according to the invention may furthermore comprise all the ingredients conventionally used in the relevant fields and more especially in the cosmetic and dermatological fields specific to the making up and/or the care of the eyelashes. These ingredients are chosen in particular from vitamins, antioxidants, trace elements, demulcents, sequestrants, alkalinizing or acidifying agents, UV-screening agents, preservatives, thickeners, hydrophilic or lipophilic active agents, such as emollients, moisturizers, perfumes and mixtures thereof. The quantities of these various ingredients are those conventionally used in the field considered and are for example from 0.01 to 20% by weight relative to the total weight of the composition.

According to a particular embodiment, the composition according to the invention is a composition with overrun. The expression "overrun" is understood to mean a composition whose density is less than 0.95.

The density is measured according to the following protocol: a container whose volume Vo (cm³) is known with a precision of ± 0.005 cm³ (Vo being of the order of 10 cm³), is weighed by means of a balance with a precision of ± 0.00005 g. Its mass is noted Mo

(g). This container is delicately filled with the foam until the container overflows. The surface of the container is then made level with a straight blade in order to obtain a perfectly level foam surface. The mass M (g) of the container filled with foam is then measured.

The density corresponds to the ratio between the mass density of the composition calculated as follows:

over the mass density of water (1 g/cm³).

A composition with overrun preferably has a density of less than or equal to 0.95, even better of less than or equal to 0.8. Preferably, the density of the composition is greater than or equal to 0.1 , and even better greater than or equal to 0.2 .

Packaging and application of the compositions according to the invention:

The compositions according to the invention may be packaged in a container delimiting at least one compartment which comprises the composition, the said container being closed by a closing component.

The container is preferably linked to an applicator, in particular in the form of a brush comprising an arrangement of bristles maintained by a twisted wire. Such a twisted brush is described in particular in patent US 4 887 622. It may also be in the form of a comb comprising a plurality of application components obtained in particular from moulding. Such combs are described for example in patent FR 2 796 529. The applicator may be integrally attached to the container as patent FR 2 761 959 describes for example. Advantageously, the applicator is integrally attached to a wand, which is itself integrally attached to a closing component.

The closing component may be coupled to the container by screwing on. Alternatively, the coupling between the closing element and the container is made other than by screwing on, in particular through a bayonet mechanism, by snap fastening or by tightening. The expression "snap fastening" is understood to mean any system involving passing over a flange or a collar of a material by elastic deformation of a portion, in particular of the closing component, and then by returning to an elastically unstressed position of the said portion after passing over the flange or the collar.

The container may be at least partially made of a thermoplastic material. By way of examples of thermoplastic materials, there may be mentioned polypropylene or polyethylene. Advantageously, the container is made of a non-thermoplastic material, in particular of glass or metal (or alloy).

The container is preferably equipped with a draining device placed close to the opening of the container. Such a draining device makes it possible to wipe the applicator and optionally the wand to which it may be integrally attached. Such a draining device is described for example in patent FR 2 792 618.

EXAMPLES

Example 1 : Mascara

Beeswax 30% Thermogelling polymer of the polyurethane type with POE and POP groups 5% Hydroxyethylcellulose 0.89%

Antifoam (simethicone) 0.4%

Preservatives qs

Water qs 100 The fatty phase (wax) is heated to 98°C and then the aqueous phase (thermogelling polymer, hydroxyethylcellulose and water) heated beforehand to 93°C is added, with vigorous stirring.

Example 2: Mascara

Paraffin wax 30% Thermogelling polymer of the polyurethane type with POE and POP groups 5% Hydroxyethylcellulose 0.94%

Antifoam (simethicone) 0.4%

Preservatives qs

Water qs 100

Example 3: Mascara

Candelilla wax 30% Thermogelling polymer of the polyurethane type with POE and POP groups 5% Hydroxyethylcellulose 0.94%

Antifoam (simethicone) 0.4%

Preservatives qs

Water qs 100

Example 4: Mascara

Fatty phase

Beeswax 4.07%

Paraffin wax 12.86% Candelilla wax 3.21 %

Aqueous phase

AMPS/ethoxylated C16/C18 alcohol methacrylate (8 mol EO) copolymer 80/20 (Aristoflex SNC from Clariant) 0.46% Thermogelling polymer of the polyurethane type with POE and POP groups 3%

Pigments (black iron oxide) 7.14%

Hydroxyethylcellulose 0.89%

Gum arabic 3.39% Antifoam (simethicone) 0.13%

Preservatives qs

Water qs 100

The fatty phase is heated to 98°C and then the aqueous phase heated beforehand to 93°C is added, with vigorous stirring.

Example 5: Mascara

Beeswax 4.07%

Paraffin wax 12.86%

Carnauba wax 3.21 %

Polyether graft sodium polyacrylate thermogelling polymer 5%

Pigments (black iron oxide) 7.14%

Hydroxyethylcellulose 0.89%

Gum arabic 3.39%

Antifoam (simethicone) 0.13%

Preservatives qs

Water qs 100

Example 6: Mascara

Beeswax 4.07%

Paraffin wax 12.86% Candelilla wax 3.21 %

PS/PAA copolymer in the form of an aqueous alcoholic gel (18% active material) 0.5%

Thermogelling polymer of the polyurethane type with POE and POP groups 3% Pigments (black iron oxide) 7.14% Hydroxyethylcellulose 0.89%

Gum arabic 3.39%

Antifoam (simethicone) 0.13%

Preservatives qs

Water qs 100

The parameter Gp of each composition is measured according to the protocol indicated above.

Example 7: Mascara

Fatty phase Beeswax 5.7%

Paraffin wax 5.7%

Candelilla wax 5.7%

Aqueous phase Oxyethylenated stearyl alcohol (100 EOypolyethylene glycol (136 EO) hexamethylene diisocyanate copolymer (RHEOLATE FX 1 100 from the company SERVO DELDEN) 2%

Thermogelling polymer of the polyurethane type having POE and POP groups 2.80%

Propylene glycol 5%

Pigment (black iron oxide) 7%

Sodium polymethacrylate 1 % Polyquaternium 0.1%

Hydroxyethylcellulose 0.76%

Gum arabic 2.87%

Antifoam (simethicone) 0.13%

Preservatives qs

Water qs 100

Claims

1. Cosmetic composition for making up and/or caring for keratin fibres, in particular the eyelashes or the eyebrows, comprising an aqueous phase and at least one thermogelling polymer, the said polymer constituting the main surfactant system of the composition.

2. Cosmetic composition for making up and/or caring for keratin fibres, in particular the eyelashes or the eyebrows, comprising an aqueous phase and at least one thermogelling polymer, the said composition comprising less than 1% by weight of triethanolamine relative to the total weight of the composition.

3. Composition according to one of the preceding claims, characterized in that it comprises less than 0.5% by weight of triethanolamine relative to the total weight of the composition, preferably less than 0.1% by weight, and even better is free of triethanolamine.

4. Composition according to one of the preceding claims, characterized in that the thermogelling polymer comprises water-soluble units and units at LCST, the said units at LCST having in water a solution temperature of 5 to 40⁰C at a concentration by mass of 1%.

5. Composition according to one of the preceding claims, in which the thermogelling polymer has a gelling temperature of 5 to 50⁰C for a concentration by mass in water of 2%.

6. Composition according to one of the preceding claims, in which the thermogelling polymer is in the form of a block polymer comprising water-soluble units and alternating units at LCST or in the form of a graft polymer consisting of a backbone formed of water-soluble units and bearing grafts consisting of units at LCST.

7. Composition according to one of Claims 4 to 6, characterized in that the water- soluble units of the thermogelling polymer, as a whole or in part, are obtained by polymerization of at least one water-soluble monomer or its salt chosen from: - (meth)acrylic acid; - vinyl monomers of the following formula (I):

H₂C=CR

(I) CO X

in which:

- R is chosen from H, -CH₃, -C₂H₅ or -C₃H₇; and

- X is chosen from :

- alkyl oxides of the -OR' type where R' is a saturated or unsaturated, linear or branched, hydrocarbon radical having from 1 to 6 carbon atoms, optionally substituted with at least one halogen atom (iodine, bromine, chlorine, fluorine); a sulphonic (-SO₃-), sulphate (-SO₄-), phosphate (-PO₄H₂); hydroxyl (-OH); primary amine (-NH2); secondary amine (-NHR₁), tertiary amine (-NR₁R₂) or quaternary amine (-N+R-i R₂R₃) group with R₁, R₂ and R₃ being, independently of each other, a saturated or unsaturated, linear or branched hydrocarbon radical having 1 to 6 carbon atoms, provided that the sum of the carbon atoms of

R' + R₁ + R₂ + R₃ does not exceed 7; and

- groups -NH₂, -NHR₄ and -NR₄R₅ in which R₄ and R₅ are, independently of each other, saturated or unsaturated, linear or branched, hydrocarbon radicals having 1 to 6 carbon atoms, provided that the total number of carbon atoms of R4 + R5 does not exceed 7, the said R₄ and R₅ being optionally substituted with a halogen atom (iodine, bromine, chlorine, fluorine); a hydroxyl (-OH); sulphonic (-SO₃-); sulphate (-SO₄-); phosphate (-PO₄H₂); primary amine (-NH₂); secondary amine (-NHR₁), tertiary amine (-NR₁R₂) and/or quaternary amine (^+R₁R₂R₃) group, with R1 , R2 and R3 being, independently of each other, a saturated or unsaturated, linear or branched hydrocarbon radical having 1 to 6 carbon atoms, provided that the sum of the carbon atoms of R₄ + R₅ + R₁ + R₂ + R₃ does not exceed 7;

- maleic anhydride;

- itaconic acid; - vinyl alcohol of formula CH₂=CHOH;

- vinyl acetate of formula CH₂=CH-OCOCH₃;

- N-vinyllactams such as N-vinylpyrrolidone, N-vinylcaprolactam and N-butyrolactam; - vinyl ethers of formula CH₂=CHOR₆ in which R₆ is a saturated or unsaturated, linear or branched hydrocarbon radical having from 1 to 6 carbons;

- water-soluble derivatives of styrene, in particular styrene sulphonate;

- dimethyldiallylammonium chloride; and - vinylacetamide.

8. Composition according to any one of Claims 4 to 7, in which the water-soluble units of the thermogelling polymer consist entirely or in part of one or more of the components chosen from: - water-soluble polyurethanes,

- xanthan gum;

- alginates and their derivatives such as propylene glycol alginate ;

- cellulose derivatives and in particular carboxymethylcellulose, hydroxypropylcellulose, hydroxyethylcellulose and quaternized hydroxyethylcellulose;

- galactomannans and their derivatives, such as Konjac gum, guar gum, hydroxypropylguar, hydroxypropylguar modified with sodium methylcarboxylate groups, guar hydroxypropyltrimethylammonium chloride, polyethyleneimine.

9. Composition according to any one of Claims 4 to 8, in which the units at LCST of the thermogelling polymer consist entirely or in part of one or more polymers chosen from the following polymers:

- polyvinyl methyl ethers,

- N-substituted polymeric and copolymeric derivatives of acrylamide having an LCST such as poly-N-isopropylacrylamide (NIPAM) and poly-N-ethylacrylamide, and - polyvinylcaprolactam and copolymers of vinylcaprolacatam.

10. Composition according to any one of Claims 4 to 9, in which the units at LCST of the thermogelling polymer consist of polypropylene oxide (POP)n where n is an integer from 10 to 70, or random copolymers of ethylene oxide (EO) and propylene oxide (PO), represented by the formula: (EO)m (PO)n

in which m is an integer ranging from 1 to 40, preferably from 2 to 20, and n is an integer ranging from 10 to 60, preferably from 20 to 50.

11. Composition according to Claim 10, in which the molar mass of the LCST units is from 500 to 5300 g/mol, preferably from 1500 to 4000 g/mol.

12. Composition according to any one of Claims 4 to 1 1 , in which the proportion by mass of the units at LCST of the polymer is from 5 to 70%, preferably from 10 to 60% and better still from 20 to 50% relative to the polymer.

13. Composition according to one of the preceding claims, characterized in that the thermogelling polymer is a polymer of the polyurethane or sodium polyacrylate type with POE (polyethylene oxide) and POP (polypropylene oxide) groups, in particular containing urea groups.

14. Composition according to one of the preceding claims, characterized in that the thermogelling polymer is present in an amount ranging from 0.01 to 20% by weight, preferably from 0.1 to 15% by weight, even better from 0.1% to 10% by weight, better still from 0.5 to 10% by weight, and preferably from 1 to 10% by weight relative to the total weight of the composition.

15. Composition according to one of the preceding claims, characterized in that the aqueous phase is present in an amount ranging from 1 % to 95% by weight, relative to the total weight of the composition, preferably ranging from 3% to 80% by weight, and preferentially ranging from 5% to 60% by weight.

16. Composition according to one of the claims, characterized in that it comprises less than 1% by weight of triethanolamine stearate relative to the total weight of the composition, preferably less than 0.5% by weight.

17. Composition according to one of the preceding claims, characterized in that it is free of triethanolamine stearate.

18. Cosmetic composition for making up and/or caring for keratin fibres, in particular the eyelashes or the eyebrows, comprising an aqueous phase and at least one thermogelling polymer, the said composition additionally comprising at least one associative polymer.

19. Composition according to the preceding claim, characterized in that the associative polymer is present in an amount ranging from 0.1 to 10% by weight, even better from 0.2 to 7% by weight and better still 0.3 to 5% by weight relative to the total weight of the composition.

20. Composition according to one of the preceding claims, characterized in that it comprises at least one wax.

21. Composition according to the preceding claim, characterized in that the wax is present in an amount ranging from 5 to 70% by weight relative to the total weight of the composition, in particular it may contain from 7 to 50% by weight, more particularly from 10 to 45% by weight.

22. Composition according to one of the preceding claims, characterized in that it has overrun.

23. Method for making up and/or caring for keratin fibres, in particular the eyelashes or the eyebrows, consisting in applying to the said fibres a composition according to any one of the preceding claims.

24. Method for making up and/or caring for keratin fibres, in particular the eyelashes or the eyebrows, consisting in applying to the said fibres a composition according to any one of the preceding claims, the said method additionally comprising a step consisting in heating the composition prior to, simultaneously with or following the application of the said composition.

25. Method according to the preceding claim, characterized in that the composition is heated to a temperature of greater than or equal to the specific gelling temperature of the thermogelling polymer or of at least one of the thermogelling polymers of the composition.

26. Method for making up and/or caring for keratin fibres, in particular the eyelashes or the eyebrows, consisting in forming on the said fibres a first deposit of a first composition containing a physiologically acceptable medium, and then in forming on all or part of the first deposit a second deposit of a second composition containing a physiologically acceptable medium, at least one of the first and second compositions containing at least one thermogelling polymer.