WO2016116492A1

WO2016116492A1 - Oil/oil emulsion comprising solid microparticles, at least a first oily phase, at least a second oily phase and at least a third oily phase that are mutually immiscible

Info

Publication number: WO2016116492A1
Application number: PCT/EP2016/051102
Authority: WO
Inventors: Virginie Perez Nowak; Annabelle SERVAIS-DEALET; Marion FRAICHE
Original assignee: L'oreal
Priority date: 2015-01-21
Filing date: 2016-01-20
Publication date: 2016-07-28

Abstract

The invention relates to a composition in the form of an oil/oil (O/O) emulsion, which is more particularly intended for making up and/or caring for the lips, comprising at least: solid microparticles having at least one curved part and at least one break in the curvature of said curved part, at least a first oily phase comprising at least one oil chosen from silicone oils and fluoro oils, preferably silicone oils, at least a second oily phase comprising at least one oil chosen from silicone oils and fluoro oils, preferably silicone oils, and at least a third oily phase comprising at least one volatile or non-volatile oil, preferably non-volatile oil. According to the invention, the first oily phase, the second oily phase and the third oily phase are immiscible at room temperature. The invention also relates to a process for making up and/or caring for the lips, in which the composition according to the invention is applied.

Description

OIL/OIL EMULSION COMPRISING SOLID MICROPARTICLES, AT LEAST A FIRST OILY PHASE, AT LEAST A SECOND OILY PHASE AND AT LEAST A

THIRD OILY PHASE THAT ARE MUTUALLY IMMISCIBLE The present invention relates to a composition in the form of an oil/oil (O/O) emulsion, which is more particularly intended for making up and/or caring for the lips.

The development of fluid compositions for making up and/or caring for the lips, such as glosses (liquid lipstick), which are stable and endowed with satisfactory properties in terms of application (glidance on application, ease of spreading and fineness of the deposit) and also in terms of the makeup effect of the deposit on the lips, for instance the gloss and/or the gloss persistence, preferably without becoming tacky, is an ongoing objective.

Thus, there is still a need for novel architectures leading to cosmetic compositions more particularly intended for making up and/or caring for the lips, which are stable and which have the comfort properties required by users.

The authors of the present invention have directed their research towards O/O emulsions, which are particularly used in lipcare and/or lip makeup products. These emulsions are relatively uncommon, but nevertheless have the advantage of having novel properties.

The main problem posed by this type of emulsion is associated with its stability: O/O emulsions are generally stabilized with gelling agents or even emulsifying surfactants and/or (co)polymers.

For example, patent application WO 2009/150 852 is directed towards an oil-in-oil cosmetic composition comprising a non-volatile hydrocarbon-based oil, a non- volatile silicone oil and a fatty acid ester of dextrin; said application does not describe O/O emulsions of Pickering type, i.e. emulsions stabilized with solid particles.

Surprisingly and advantageously, the authors of the present invention have used O/O emulsions of Pickering type stabilized with solid particles. Once positioned at the interface, the solid particles "block" the dispersed phase, which leads to stabilization of the dispersed phase in the form of droplets.

Surprisingly, the authors of the present invention have also noted that, in the field more particularly of making up and/or caring for the lips, this type of Pickering emulsion in combination with particular starting materials makes it possible to obtain a glossy deposit with good persistence of the gloss and colour on the lips and also a low level of tack. The object of the present invention is thus to provide a composition in the form of an oil/oil (O/O) emulsion, which is more particularly intended for making up and/or caring for the lips, having a low level of tack and also good persistence of the colour on the lips over time.

Thus, the present invention relates to a composition in the form of an oil/oil (0/0) emulsion, which is more particularly intended for making up and/or caring for the lips, comprising at least:

- solid microparticles having at least one curved part and at least one break in the curvature of said curved part,

at least a first oily phase comprising at least one oil chosen from silicone oils and fluoro oils, preferably silicone oils,

at least a second oily phase comprising at least one oil chosen from silicone oils and fluoro oils, preferably silicone oils, and

at least a third oily phase comprising at least one volatile or non-volatile oil, preferably non-volatile oil,

in which the first oily phase, the second oily phase and the third oily phase are immiscible at room temperature.

Moreover, the present invention relates to a composition in the form of an oil/oil (0/0) emulsion, which is more particularly intended for making up and/or caring for the lips, comprising at least:

solid microparticles having at least one curved part and at least one break in the curvature of said curved part,

at least a second oily phase comprising at least one oil chosen from silicone oils and fluoro oils, preferably silicone oils,

- at least a third oily phase comprising at least one volatile or non-volatile oil, preferably non-volatile oil,

at least one hydrocarbon-based resin having a number-average molecular weight of less than or equal to 10 000 g/mol, and at least one pasty fatty substance, in which the first oily phase, the second oily phase and the third oily phase are immiscible at room temperature.

The invention also relates to a process for making up and/or caring for the lips, in which the composition according to the invention is applied.

The composition according to the invention thus makes it possible to obtain a makeup result, in particular on the lips, which is sparingly tacky, less pasty and has good colour persistence.

The emulsion according to the invention also makes it possible to dispense with the use, as stabilizers, of compounds of surfactant type, especially synthetic surfactants, and/or of gelling agents, since some of these agents may present toxicity risks to the environment depending on the amounts used.

The term "room temperature" is intended to denote a temperature of about 25°C. It is set at atmospheric pressure (i.e. a pressure of 1.013 x 10⁵ Pa).

The compositions according to the invention comprise a physiologically acceptable medium, i.e. a non-toxic medium that can be applied to human lips, which is of pleasant appearance, odour and feel.

According to a preferred embodiment, the composition according to the invention is a liquid or pasty composition, preferably a liquid composition.

Solid particles:

The composition according to the invention comprises solid microparticles having at least one curved part and at least one break in the curvature of said curved part.

For the purposes of the present invention, the term "microparticles" is intended to denote a particle whose largest dimension ranges from 0.1 to 100 μηη, preferably from 0.1 to 50 μηη and more preferably from 0.5 to 20 μηη.

The solid microparticles that may be used for stabilizing the O/O emulsion according to the invention have a particular form; they thus have at least one curved part and at least one break in the curvature of said curved part, the microparticles preferably having at least two curved parts.

According to a preferred variant, the solid microparticles that may be used in the present invention comprise several curvatures.

The term "several curvatures" means curvatures of different radius. For the purposes of the present invention, the term "radius of curvature" does not cover the "infinity" value "∞"; thus, the microparticles used according to the invention are not in the form of platelets or leaflets.

In particular, the solid microparticles that may be used in the present invention comprise at least one concave part and at least one convex part.

More particularly, the microparticles in accordance with this variant have a form chosen from forms of "bowl", "golf ball" and "polytope" type.

According to a second preferred variant, the solid microparticles that may be used in the present invention comprise only one curvature.

For the purposes of the invention, the term "only one curvature" means that when the microparticle comprises several curves, these curves have curvatures of the same radius.

They are chosen especially from hemispherical, fusiform microparticles, for example of "rugby ball" type.

The solid microparticles that may be used in the present invention may be mineral or organic.

In general, the microparticles that may be used in the present invention are such that their largest dimension ranges from 0.1 to 100 μηη, preferably from 0.1 to 50 μηη and more preferably from 0.5 to 20 μηη.

Advantageously, the microparticles that may be used in the present invention have a density ranging from 0.5 to 2.8 and preferably from 0.8 to 1 .5.

The microparticles according to the invention are generally obtained by radical polymerization or by polycondensation.

The term "radical polymerization" means polymerization of at least one ethylenic monomer.

In this case, preferably, the microparticles according to the invention contain, or even are formed from, a polymer chosen from polyacrylates, polymethyl methacrylate (PMMA) and polystyrenes.

The term "polycondensation" means polymerization between two monomers with elimination of a small molecule.

In this case, preferably, the microparticles according to the invention contain, or even are formed from, a polymer chosen from polysilicones, polyurethanes and polyesters.

Bowls According to the first variant of the invention, the microparticles comprise at least one concave part and at least one convex part, and the microparticles more particularly have a hollow hemispherical shape, i.e. of "bowl" type.

The "bowl"-shaped microparticles may comprise or be formed from a silicone material, and preferably comprise or are formed from a silicone material.

The latter preferred embodiment is described in detail below under the name "concave particles of silicone material".

Concave particles of silicone material

The concave particles present in the composition according to the invention are silicone particles, in particular hollow sphere portions formed from a silicone material.

Said particles preferably have a mean diameter ranging from 0.1 μηη to 20 μηη and preferentially from 0.5 to 15 μηη. The term "mean diameter" means the largest dimension of the particle.

The hollow sphere portions used in the composition according to the invention have the form of truncated hollow spheres, having only one orifice communicating with their central cavity, and having a horseshoe-shaped or bowl- shaped cross section.

The silicone material is a crosslinked polysiloxane of three-dimensional structure; it preferably comprises, or even is formed from, units of formula (I) Si0₂ and of formula (II) R¹SiOi_.5, in which R¹ denotes an organic group bearing a carbon atom directly linked to the silicon atom.

Advantageously, the solid microparticles are in the form of bowls and comprise, or even are formed from, units of formula (I) Si0₂ and of formula (II) R¹SiOi_.5, in which R¹ denotes an organic group bearing a carbon atom directly linked to the silicon atom.

The organic group R¹ may be a reactive organic group; R¹ may more particularly be an epoxy group, a (meth)acryloxy group, an alkenyl group, a mercaptoalkyi, aminoalkyi or haloalkyl group, a glyceroxy group, a ureido group, a cyano group and, preferably, an epoxy group, a (meth)acryloxy group, an alkenyl group or a mercaptoalkyi or aminoalkyi group. These groups generally contain from 2 to 6 carbon atoms and especially from 2 to 4 carbon atoms. The organic group R¹ may also be an unreactive organic group; Ri may then more particularly be a C1-C4 alkyl group, especially a methyl, ethyl, propyl or butyl group, or a phenyl group, and preferably a methyl group.

Epoxy groups that may be mentioned include a 2-glycidoxyethyl group, a 3- glycidoxypropyl group and a 2-(3,4-epoxycyclohexyl)propyl group.

(Meth)acryloxy groups that may be mentioned include a 3- methacryloxypropyl group and a 3-acryloxypropyl group.

Alkenyl groups that may be mentioned include vinyl, allyl and isopropenyl groups.

Mercaptoalkyl groups that may be mentioned include mercaptopropyl and mercaptoethyl groups.

Aminoalkyl groups that may be mentioned include a 3-(2- aminoethyl)aminopropyl group, a 3-aminopropyl group and an N,N- dimethylaminopropyl group.

Haloalkyl groups that may be mentioned include a 3-chloropropyl group and a trifluoropropyl group.

Glyceroxy groups that may be mentioned include a 3-glyceroxypropyl group and a 2-glyceroxyethyl group.

A ureido group that may be mentioned is a 2-ureidoethyl group. Cyano groups that may be mentioned include cyanopropyl and cyanoethyl groups.

Preferably, in the unit of formula (II), Ri denotes a methyl group. Advantageously, the silicone material comprises the units (I) and (II) in a unit (l)/unit (II) mole ratio ranging from 30/70 to 50/50 and preferably ranging from 35/65 to 45/55.

The silicone material particles may especially be obtained according to a process comprising:

(a) the introduction into an aqueous medium, in the presence of at least one hydrolysis catalyst, and optionally of at least one surfactant, of a compound (III) of formula SiX₄ and of a compound (IV) of formula RSiY₃, in which X and Y denote, independently of each other, a C1-C4 alkoxy group, an alkoxyethoxy group containing a C1-C4 alkoxy group, a C₂-C₄ acyloxy group, an Ν,Ν-dialkylamino group containing d- C₄ alkyl groups, a hydroxyl group, a halogen atom or a hydrogen atom, and R denotes an organic group comprising a carbon atom directly bonded to the silicon atom; and (b) the placing in contact of the mixture resulting from step (a) with an aqueous solution containing at least one polymerization catalyst and optionally at least one surfactant, at a temperature of between 30 and 85°C, for at least two hours.

Step (a) corresponds to a hydrolysis reaction and step (b) corresponds to a condensation reaction.

In step (a), the mole ratio of compound (III) to compound (IV) usually ranges from 30/70 to 50/50, advantageously from 35/65 to 45/45 and is preferentially 40/60. The weight ratio of water to the total of compounds (III) and (IV) preferably ranges from 10/90 to 70/30. The order of introduction of compounds (III) and (IV) generally depends on their rate of hydrolysis. The temperature of the hydrolysis reaction generally ranges from 0 to 40°C and usually does not exceed 30°C to avoid premature condensation of the compounds.

For the groups X and Y of compounds (III) and (IV):

C1-C4 alkoxy groups that may be mentioned include methoxy and ethoxy groups;

As alkoxyethoxy groups containing a C1-C4 alkoxy group, mention may be made of methoxyethoxy and butoxyethoxy groups;

C2-C4 alkoxy groups that may be mentioned include acetoxy and propioxy groups;

As Ν,Ν-dialkylamino groups containing C1-C4 alkyl groups, mention may be made of dimethylamino and diethylamino groups;

Halogen atoms that may be mentioned include chlorine and bromine atoms. Compounds of formula (III) that may be mentioned include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, trimethoxyethoxysilane, tributoxyethoxysilane, tetraacetoxysilane, tetrapropioxysilane, tetraacetoxysilane, tetra(dimethylamino)silane, tetra(diethylamino)silane, silane tetraol, chlorosilane triol, dichlorodisilanol, tetrachlorosilane and chlorotrihydrogenosilane. Preferably, the compound of formula (III) is chosen from tetramethoxysilane, tetraethoxysilane and tetrabutoxysilane, and mixtures thereof.

The compound of formula (III) leads, after the polymerization reaction, to the formation of the units of formula (I).

The compound of formula (IV) leads, after the polymerization reaction, to the formation of the units of formula (II).

The group R in the compound of formula (IV) has the meaning as described for the group R¹ for the compound of formula (II). As examples of compounds of formula (IV) comprising an unreactive organic group R, mention may be made of methyltrimethoxysilane, ethyltriethoxysilane, propyltributoxysilane, butyltributoxysilane, phenyltrimethoxyethoxysilane, methyltributoxyethoxysilane, methyltriacetoxysilane, methyltripropioxysilane, methyltriacetoxysilane, methyltri(dimethylamino)silane, methyltri(diethylamino)silane, methylsilanetriol, methylchlorodisilanol, methyltrichlorosilane and methyltrihydrogenosilane.

As examples of compounds of formula (IV) comprising a reactive organic group R, mention may be made of:

- silanes containing an epoxy group, for instance 3- glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4- epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3- glycidoxypropylmethyldimethoxysilane, 2-glycidoxyethylmethyldimethoxysilane, 3- glycidoxypropyldimethylmethoxysilane and 2-glycidoxyethyldimethylmethoxysilane;

- silanes containing a (meth)acryloxy group, for instance 3- methacryloxypropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane;

- silanes containing an alkenyl group, for instance vinyltrimethoxysilane, allyltrimethoxysilane and isopropenyltrimethoxysilane;

- silanes containing a mercapto group, for instance mercaptopropyltrimethoxysilane and mercaptoethyltrimethoxysilane;

- silanes containing an aminoalkyl group, for instance 3- aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, N,N- dimethylaminopropyltrimethoxysilane and N,N-dimethylaminoethyltrimethoxysilane;

- silanes containing a haloalkyl group, for instance 3- chloropropyltrimethoxysilane and trifluoropropyltrimethoxysilane;

- silanes containing a glyceroxy group, for instance 3- glyceroxypropyltrimethoxysilane and bis(3-glyceroxypropyl)dimethoxysilane;

- silanes containing a ureido group, for instance 3- ureidopropyltrimethoxysilane, 3-ureidopropylmethyldimethoxysilane and 3- ureidopropyldimethylmethoxysilane;

- silanes containing a cyano group, for instance cyanopropyltrimethoxysilane, cyanopropylmethyldimethoxysilane and cyanopropyldimethylmethoxysilane.

Preferably, the compound of formula (IV) comprising a reactive organic group R is chosen from silanes containing an epoxy group, silanes containing a (meth)acryloxy group, silanes containing an alkenyl group, silanes containing a mercapto group and silanes containing an aminoalkyl group.

Examples of compounds (III) and (IV) that are preferred for the implementation of this invention are, respectively, tetraethoxysilane and methyltrimethoxysilane.

Hydrolysis and polymerization catalysts that may be used, independently, include basic catalysts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate and aqueous ammonia, or amines such as trimethylamine, triethylamine or tetramethylammonium hydroxide, or acidic catalysts such as organic acids, for instance, citric acid, acetic acid, methanesulfonic acid, p- toluenesulfonic acid, dodecylbenzenesulfonic acid or dodecylsulfonic acid, or mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid.

When it is present, the surfactant used is preferably a nonionic or anionic surfactant or a mixture thereof. Sodium dodecylbenzenesulfonate may be used as anionic surfactant. The end of the hydrolysis is marked by the disappearance of the water-insoluble products (III) and (IV) and the production of a homogeneous liquid layer.

The condensation step (b) may use the same catalyst as the hydrolysis step or another catalyst chosen from those mentioned above.

After this process, a suspension in water of fine organosilicone particles is obtained, which may then optionally be separated from their medium. The process described above may thus comprise an additional filtration step, for example on a membrane filter, of the product resulting from step (b), optionally followed by a step of centrifugation of the filtrate intended to separate the particles from the liquid medium, and then a step of drying the particles. Other separation methods may obviously be used.

The form of the hollow sphere portions obtained according to the above process, and the sizes thereof, will depend especially on the mode of contact of the products of step (b).

A rather basic pH and cold introduction of the polymerization catalyst into the mixture obtained from step (a) will lead to "bowl"-shaped hollow sphere portions with a rounded bottom, whereas a rather acidic pH and dropwise introduction of the mixture obtained from step (a) into the hot polymerization catalyst will lead to hollow sphere portions with a "horseshoe' -shaped cross section. According to one preferred embodiment of the invention, "bowl"-shaped hollow sphere portions are used. These may be obtained as described in patent application JP-A-2003-128 788 or FR 2 902 654. The parts of these patent applications devoted to "bowl"-shaped particles and to processes for preparing them are incorporated by reference into the present text.

Horseshoe-shaped hollow sphere portions are described in patent application JP-A-2000-191 789.

Figure 1 of FR 2 902 654 illustrates a concave particle in the form of sphere portions with a bowl-shaped cross section. The width W2 corresponds to the diameter of the particles.

As emerges from this figure, these concave portions are formed (in a section perpendicular to a plane of the aperture delimited by the hollow sphere portion) of a small inner arc (1 1 ), a large outer arc (21 ) and segments (31 ) that connect the ends of the respective arcs, the width (W1 ) between the two ends of the small inner arc (1 1 ) ranging from 0.01 to 8 μηη and preferably from 0.02 to 6 μηη on average, the width (W2) between the two ends of the large outer arc (21 ) ranging from 0.05 to 10 μηη and preferably from 0.06 to 8 μηη on average and the height (H) of the large outer arc (21 ) ranging from 0.015 to 8 μηη and preferably from 0.03 to 6 μηη on average.

The sizes mentioned above are obtained by calculating the mean of the sizes of one hundred particles chosen from an image obtained using a scanning electron microscope.

As concave particles in the form of sphere portions that may be used according to the invention, examples that may be mentioned include:

- bowl-shaped particles formed from the crosslinked organosilicone Tak-1 10 (methylsilanol/silicate crosslinked polymer) from the company Takemoto Oil & Fat, of width 2.5 μηη, height 1.2 μηη and thickness 150 nm (particles sold under the name NLK- 506 by the company Takemoto Oil & Fat);

- bowl-shaped particles formed from the crosslinked organosilicone Tak-1 10 (methylsilanol/silicate crosslinked polymer) from the company Takemoto Oil & Fat, of width 0.8 μηη, height 0.4 μηη and thickness 130 nm (particles sold under the name NLK- 515 by the company Takemoto Oil & Fat);

- bowl-shaped particles formed from the crosslinked organosilicone Tak-1 10 (methylsilanol/silicate crosslinked polymer) from the company Takemoto Oil & Fat, of width 7 μηη, height 3.5 μηη and thickness 200 nm (particles sold under the name NLK- 510 by the company Takemoto Oil & Fat). Preferably, the solid microparticles according to the invention are formed from methylsilanol/silicate crosslinked polymer (INCI name: methylsilanol/silicate crosspolymer).

Advantageously, the concave silicone particles, in particular the bowls, have a mean diameter of less than or equal to 5 μηη, especially ranging from 0.1 μηη to 5 μηη, preferentially ranging from 0.2 to 5 μηη, more preferentially ranging from 0.5 to 4 μηη and even more preferably ranging from 0.5 to 3 μηη.

Polytopes

According to another variant, the microparticles that may be used according to the invention are non-spherical fine particles in the form of polygons having at least six concave faces. These particles are characterized by a mean value of the maximum outside diameters of said individual non-spherical fine particles ranging from 0.1 to 20 μηη; a mean value of the ratio between the minimum outside diameters and the maximum outside diameters of said individual non-spherical fine particles ranging from 0.60 to 0.97; and a mean number of concave surfaces, whose ratio of the relative maximum diameter to the maximum outside diameter ranges from 0.50 to 0.90, ranging from 6 to 14 per non-spherical fine particle.

These particles are described in greater detail in patent application EP 2 476 719 A1 , and the parts of that patent application that are devoted to the definition of the non-spherical fine particles and to the process for preparing them are incorporated by reference into the present text.

The non-spherical fine particles in the form of polygons having at least six concave faces that may be used according to the invention are also known as "polytopes" or "ossicles", and the largest dimension of these particles preferably ranges from 1 to 10 μηι).

Rugby balls

According to another variant, the microparticles that may be used according to the invention are particles of non-(hemi)spherical shape, in particular fusiform shape, also known as a "rugby ball" shape.

The fusiform microparticles and processes for obtaining them are described especially in Japanese patent application 2003-171 465 or European patent application EP 2 433 979 filed by Takemoto Oil & Fat. Golf balls

As golf balls that may be used, mention may be made most particularly of organic silicone microparticles comprising a polysiloxane crosslinked structure, of spherical overall shape and having a multitude of dimples at their surface.

The microparticles of this type and processes for obtaining them are described especially in Japanese patent JP 38 46667 filed by Takemoto Oil & Fat.

Preferably, the total amount of solid microparticles comprising at least one curved part and at least one break in the curvature of said curved part ranges from 0.01 % to 5%, preferably from 0.1 % to 4% by weight and even more preferentially from 0.1 % to 3% by weight relative to the total weight of the emulsion.

Preferably, the solid microparticles according to the invention comprise one or more curvatures, preferably several curvatures.

Preferably, the solid microparticles according to the invention have a hollow hemispherical shape, i.e. of "bowl" type.

Oils:

The composition according to the invention comprises at least three oily phases; i.e. at least a first oily phase comprising at least one oil chosen from silicone oils and fluoro oils, at least a second oily phase comprising at least one oil chosen from silicone oils and fluoro oils and at least a third oily phase comprising at least one nonvolatile or volatile oil.

According to the invention, the first oily phase, the second oily phase and the third oily phase are immiscible at room temperature, and at atmospheric pressure (760 mmHg/1.013x10⁵ Pa).

For the purposes of the present invention, the term "immiscible oily phases" means that the mixing of the oily phases, in pairs, does not lead to a homogeneous one-phase solution. Said mixing is performed with the same weight amount of each oil.

For the purposes of the invention, the term "oil" means a compound whose viscosity is not more than 200 000 cPs (200 Pa.s) at 25°C. Also, for the purposes of the invention, an "oil" is immiscible with water (mixing performed with the same weight amount of water).

It should be noted that the viscosities are measured according to the following protocol: The viscosity is measured at 25°C ± 0.5°C using a Haake RS600 controlled- stress rheometer from the company Thermo Rheo equipped with a spindle of cone/plate geometry with a diameter of between 2 cm and 6 cm and an angle of between 1 ° and 2°, the choice of the spindle depending on the viscosity to be measured (the more fluid the formulation, the greater the diameter of the chosen cone and the smaller the angle).

The measurement is performed by applying on the oil sample a logarithmic ramp of shear gradient ε' ranging from 10^"3 s^"1 to 1000 s^"1 for a duration of 5 minutes.

The rheogram representing the change in viscosity as a function of the shear gradient ε' is then plotted. The value under consideration is that of the viscosity at 500 s^"1.whether it is measured at this gradient or extrapolated by the plot if no experimental point corresponds to this value.

More particularly, the oils are said to be "immiscible" when mixing them leads to a separation of phases according to the following protocols:

For oils whose viscosity is less than 10 000 cPs (10 Pa.s) at 25°C, the two oils to be evaluated are introduced (5 g/5 g) at room temperature into a conical-tipped plastic centrifuge tube (ref. Corning® 15ml_ PET Centrifuge Tubes, Rack Packed with Plug Seal Cap, Sterile (Product #430055), which is placed in a Vortex Genie 2 machine. Stirring is performed at speed 10 for 10 seconds, followed by manual inversion of the tube before replacing it in the Vortex machine. This cycle is repeated three times in succession. The mixture is then left to stand at room temperature for 48 hours.

If at least one of the oils has a viscosity of greater than or equal to 10 000 cPs (10 Pa.s) at 25°C, then the mixture of the two oils (5 g/5 g) is placed in an oven at 50°C for 30 minutes before performing the three stirring cycles described previously.

The mixture is then observed.

When the mixture is separated into two phases and the separation of the two phases is sharply delimited at the interface, the phases are said to be "separated" and the oily phases are consequently immiscible.

In the contrary case, the mixture is observed using a phase-contrast microscope, at room temperature (about 25°C). If a continuous phase and a dispersed phase in the form of drops are observed, the phases are said to be "separated" and the oily phases are considered as immiscible.

If the observation of the mixture reveals only a single phase, then the phases are said to be "non-separated" and the oily phases are considered as miscible. This same protocol is used to check the miscibility of the oil with water.

More particularly, the composition according to the invention comprises at least a first oily phase containing at least one non-volatile oil, at least a second oily phase containing at least one non-volatile oil and at least a third oily phase containing at least one volatile or non-volatile oil.

Preferably, the first, second and third oily phases each contain at least one non-volatile oil.

The term "non-volatile" refers to an oil whose vapour pressure at room temperature (25°C) and atmospheric pressure is non-zero and is less than 10^"3 mmHg (0.13 Pa).

The term "volatile" refers to an oil that can evaporate on contact with the skin in less than one hour, at room temperature and atmospheric pressure.

More particularly, the term "volatile oil" means an oil which has a non-zero vapour pressure, at room temperature (25°C) and atmospheric pressure, in particular having a vapour pressure ranging from 0.13 Pa to 40 000 Pa, preferably ranging from 1 .3 Pa to 13 000 Pa and preferentially ranging from 1.3 Pa to 1300 Pa.

First oily phase and second oily phase

The first oily phase comprises at least one oil chosen from silicone oils and fluoro oils and the second oily phase comprises at least one oil chosen from silicone oils and fluoro oils.

Preferably, the oils constituting the first oily phase are chosen from silicone oils and fluoro oils or mixtures thereof, and more particularly from non-volatile non- phenyl silicone oils; non-volatile phenyl silicone oils, optionally bearing at least one dimethicone fragment; fluoro oils; or mixtures thereof.

Preferably, the oils constituting the second oily phase are chosen from silicone oils and fluoro oils or mixtures thereof, and more particularly from non-volatile non-phenyl silicone oils; non-volatile phenyl silicone oils, optionally bearing at least one dimethicone fragment; fluoro oils; or mixtures thereof.

Preferably, the first oily phase comprises at least one oil that is immiscible with at least one oil of the second oily phase.

This first oily phase may be the continuous phase or the dispersed phase.

This second oily phase may be the continuous phase or the dispersed phase. The term "silicone oil" means an oil containing at least one silicon atom, and especially containing Si-0 groups.

The term "fluoro oil" means an oil containing at least one fluorine atom. 1 . Silicone oils

Non-volatile non-phenyl silicone oils

The term "non-phenyl silicone oil" denotes a silicone oil not bearing any phenyl substituents.

Representative examples of these non-volatile non-phenyl silicone oils which may be mentioned include polydimethylsiloxanes; alkyl dimethicones; vinylmethyl methicones; and also silicones modified with aliphatic groups and/or with functional groups such as hydroxyl, thiol and/or amine groups.

It should be noted that "dimethicone" (INCI name) corresponds to a polydimethylsiloxane (chemical name).

In particular, these oils may be chosen from the following non-volatile non- phenyl silicone oils:

- polydimethylsiloxanes (PDMS) as sold by the company Dow Corning;

- PDMSs comprising aliphatic groups, in particular alkyl or alkoxy groups, which are pendent and/or at the end of the silicone chain, these groups each comprising from 2 to 24 carbon atoms. An example that may be mentioned is cetyl dimethicone sold under the commercial reference Abil Wax 9801 from Evonik Goldschmidt.

- PDMSs comprising at least one aliphatic group and/or at least one functional group such as hydroxyl, thiol and/or amine groups,

- polysiloxanes modified with fatty acids, fatty alcohols or polyoxyalkylenes, and mixtures thereof,

The non-volatile non-phenyl silicone oil is preferably chosen from nonvolatile dimethicone oils.

Preferably, these non-volatile non-phenyl silicone oils are chosen from polydimethylsiloxanes; alkyl dimethicones and also PDMSs comprising at least one aliphatic group, in particular C₂-C₂4 alkyl groups and/or at least one functional group such as hydroxyl, thiol and/or amine groups.

The non-phenyl silicone oil may be chosen in particular from silicones of formula (Γ):

(Ι')

in which:

Ri _> 2, R5 and R₆ are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms,

R₃ and R₄ are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms, a vinyl radical, an amine radical or a hydroxyl radical,

X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxyl radical or an amine radical,

n and p are integers chosen so as to have a fluid compound, in particular whose viscosity at 25°C is between 9 centistokes (cSt) (9 x 10^"6 m²/s) and 800 000 cSt (i.e. between 8 mPa.s and 720 000 mPa.s).

As non-volatile non-phenyl silicone oils that may be used according to the invention, mention may be made of those for which:

- the substituents Ri to R₆ and X represent a methyl group, and p and n are such that the viscosity is 500 000 cSt (i.e. 450 000 mPa.s), for example the product sold under the name SE30 by the company General Electric, the product sold under the name AK 500000 by the company Wacker, the product sold under the name Mirasil DM 500 000 by the company Bluestar, and the product sold under the name Dow Corning 200 Fluid 500 000 cSt (i.e. 450 000 mPa.s) by the company Dow Corning,

- the substituents Ri to R₆ and X represent a methyl group, and p and n are such that the viscosity is 60 000 cSt (54 000 mPa.s), for example the product sold under the name Dow Corning 200 Fluid 60 000 CS by the company Dow Corning, and the product sold under the name Wacker Belsil DM 60 000 by the company Wacker,

- the substituents Ri to R₆ and X represent a methyl group, and p and n are such that the viscosity is 100 cSt (i.e. 90 mPa.s) or 350 cSt (i.e. 315 mPa.s), for example the products sold respectively under the names Belsil DM100 Dimethicone from Wacker, Dow Corning 200 Fluid 350 CS and Dow Corning® SH 200 Fluid 100 CS by the company Dow Corning,

- the substituents Ri to R₆ represent a methyl group, the group X represents a hydroxyl group, and n and p are such that the viscosity is 700 cSt (630 mPa.s), for example the product sold under the name Baysilone Fluid TO.7 by the company Momentive.

Non-volatile phenyl silicone oils

The expression "phenylated silicone oil" or "phenyl silicone oil" denotes a silicone oil bearing at least one phenyl substituent.

These phenyl silicone oils may be chosen from those which also bear at least one dimethicone fragment, or from those which do not bear any.

The term "dimethicone fragment" denotes a divalent siloxane group in which the silicon atom bears two methyl radicals, this group not being located at the ends of the molecule. According to the invention, a dimethicone fragment corresponds to the following unit: -Si(CH3)2-0-.

The non-volatile phenyl silicone oil may thus be chosen from:

a) phenyl silicone oils optionally bearing a dimethicone fragment corresponding to the following formula (I):

R

I R R

R— Si 0

R— Si 0— Si-

R R

R

R— Si 0

R (I)

in which the groups R, which are monovalent or divalent, represent, independently of each other, a methyl or a phenyl, with the proviso that at least one group R represents a phenyl.

Preferably, in this formula, the phenyl silicone oil comprises at least three, for example at least four, at least five or at least six, phenyl groups.

b phenyl silicone oils optionally bearing a dimethicone fragment corresponding to formula (II) below:

R R R

R— Si 0 Si 0 Si R R R R (II) in which the groups R represent, independently of each other, a methyl or a phenyl, with the proviso that at least one group R represents a phenyl.

Preferably, in this formula, the compound of formula (II) comprises at least three, for example at least four or at least five, phenyl groups.

Mixtures of different phenylorganopolysiloxane compounds described above can be used.

Examples that may be mentioned include mixtures of triphenyl-, tetraphenyl- or pentaphenyl-organopolysiloxanes. Among the compounds of formula (II), mention may more particularly be made of phenyl silicone oils which do not bear a dimethicone fragment, corresponding to formula (II) in which at least 4 or at least 5 radicals R represent a phenyl radical, the remaining radicals representing methyls.

Such non-volatile phenyl silicone oils are preferably trimethylpentaphenyltrisiloxane or tetramethyltetraphenyltrisiloxane. They are in particular sold by Dow Corning under the reference PH-1555 HRI or Dow Corning 555 Cosmetic Fluid (chemical name: 1 ,3,5-trimethyl-1 ,1 ,3,5,5-pentaphenyltrisiloxane; INCI name: trimethylpentaphenyltrisiloxane), or the tetramethyltetraphenyltrisiloxane sold under the reference Dow Corning 554 Cosmetic Fluid by Dow Corning may also be used.

They correspond especially to formulae (III) and (ΙΙΓ) below:

Ph Ph Ph Me Ph Me

I I I I I I

Me-Si-O-Si-O— Si-Me Ph-Si-O-Si-O— Si-Ph

\ \ \ \ \ \

Ph Me Ph ^ Me Ph Me

in which Me represents methyl, and Ph represents phenyl. c) phenyl silicone oils bearing at least one dimethicone fragment corresponding to formula (IV) below:

in which Me represents methyl, y is between 1 and 1000 and X represents -CH2-CH(CH3)(Ph). d) phenyl silicone oils corresponding to formula (V) below, and mixtures thereof:

in which:

- to Rio, independently of each other, are saturated or unsaturated, linear, cyclic or branched, preferably saturated or unsaturated, linear or branched, C C₃o hydrocarbon-based radicals,

- m, n, p and q are, independently of each other, integers between 0 and 900, with the proviso that the sum m+n+q is other than 0.

Preferably, the sum m+n+q is between 1 and 100. Preferably, the sum m+n+p+q is between 1 and 900 and preferably between 1 and 800. Preferably, q is equal to 0.

Preferably, Ri to Rio, independently of each other, represent a linear or branched C1-C30 alkyl radical, preferably Ci-C₂o and more particularly C Ci₆ alkyl, or a monocyclic or polycyclic C₆-Ci₄ and in particular C10-C13 aryl radical, or an aralkyl radical, the alkyl part of which is preferably C1-C3 alkyl.

Preferably, Ri to R10 may each represent a methyl, ethyl, propyl, butyl, isopropyl, decyl, dodecyl or octadecyl radical, or alternatively a phenyl, tolyl, benzyl or phenethyl radical. Ri to R10 may in particular be identical, and in addition may be a methyl radical.

According to a first more particular embodiment of formula (V), mention may be made of:

i) phenyl silicone oils optionally bearing at least one dimethicone fragment corresponding to formula (VI) below, and mixtures thereof:

in which:

- R-i to R₆, independently of each other, are saturated or unsaturated, linear, cyclic or branched, preferably saturated or unsaturated, linear or branched, C1-C30 hydrocarbon-based radicals, a preferably C₆-Ci₄ aryl radical or an aralkyl radical, the alkyl part of which is CrC₃ alkyl,

- m, n and p are, independently of each other, integers between 0 and 100, with the proviso that the sum n+m is between 1 and 100.

Preferably, Ri to R₆, independently of each other, represent a C1-C30, preferably Ci-C₂o and in particular Ci-Ci₆, alkyl radical, or a C₆-Ci₄ aryl radical which is monocyclic (preferably C₆) or polycyclic and in particular C1₀-C13, or an aralkyl radical (preferably the aryl part is C₆ aryl; the alkyl part is C1-C3 alkyl).

Preferably, Ri to R₆ may each represent a methyl, ethyl, propyl, butyl, isopropyl, decyl, dodecyl or octadecyl radical, or alternatively a phenyl, tolyl, benzyl or phenethyl radical.

Ri to R₆ may in particular be identical, and in addition may be a methyl radical. Preferably, m = 1 or 2 or 3, and/or n = 0 and/or p = 0 or 1 may be applied, in formula (VI). According to a particular embodiment, the non-volatile phenyl silicone oil is chosen from phenyl silicone oils bearing at least one dimethicone fragment.

Preferably, such oils correspond to compounds of formula (VI) in which: A) m=0 and n and p are, independently of each other, integers between 1 and 100.

Preferably, Ri to R₆ are methyl radicals.

According to this embodiment, the silicone oil is preferably chosen from a diphenyl dimethicone such as KF-54 from Shin-Etsu, KF54HV from Shin-Etsu, KF-50- 300CS from Shin-Etsu, KF-53 from Shin-Etsu or KF-50-100CS from Shin-Etsu. B) p is between 1 and 100, the sum n+m is between 1 and 100, and n=0. These phenyl silicone oils optionally bearing at least one dimethicone fragment correspond more particularly to formula (VII) below:

Me Me OR' Me

Me— Si- -O-Si- -o- -Si- 0- -Si-Me

I m I

Me Me Ph Me

(VII)

in which Me is methyl and Ph is phenyl, OR' represents a group -OSiMe₃ and p is 0 or is between 1 and 1000, and m is between 1 and 1000. In particular, m and p are such that compound (VII) is a non-volatile oil.

According to a first embodiment of non-volatile phenyl silicone bearing at least one dimethicone fragment, p is between 1 and 1000 and m is more particularly such that compound (VII) is a non-volatile oil. Use may be made, for example, of polyphenyltrimethylsiloxydimethylsiloxane, sold in particular under the reference Belsil PDM 1000 by the company Wacker.

According to a second embodiment of non-volatile phenyl silicone not bearing a dimethicone fragment, p is equal to 0 and m is between 1 and 1000, and in particular is such that compound (VII) is a non-volatile oil.

Phenyltrimethylsiloxytrisiloxane, sold in particular under the reference Dow Corning 556 Cosmetic Grade Fluid (DC556), may, for example, be used. ii) non-volatile phenyl silicone oils not bearing a dimethicone fragment corresponding to formula (VIII) below, and mixtures thereof:

in which:

- R, independently of each other, represent a saturated or unsaturated, cyclic or branched, preferably saturated or unsaturated, linear or branched, d- C₃o hydrocarbon-based radical; more particularly, R represent a C1-C30 alkyl radical, an aryl radical, preferably a C₆-Ci₄ aryl radical, or an aralkyl radical, the alkyl part of which is C1-C3 alkyl,

- m and n are, independently of each other, integers between 0 and 100, with the proviso that the sum n+m is between 1 and 100.

Preferably, R, independently of each other, represent a linear or branched C1-C30 and in particular a C1-C20, in particular Ci-Ci₆ alkyl radical, a monocyclic or polycyclic C₆-Ci₄, and in particular C10-C13, aryl radical, or an aralkyl radical of which preferably the aryl part is C₆ aryl and the alkyl part is C1-C3 alkyl.

Preferably, the groups R may each represent a methyl, ethyl, propyl, butyl, isopropyl, decyl, dodecyl or octadecyl radical, or alternatively a phenyl, tolyl, benzyl or phenethyl radical.

The groups R may in particular be identical, and in addition may be a methyl radical.

Preferably, m = 1 or 2 or 3, and/or n = 0 and/or p = 0 or 1 may be applied, in formula (VIII).

According to a preferred embodiment, n is an integer between 0 and 100 and m is an integer between 1 and 100, with the proviso that the sum n+m is between 1 and 100, in formula (VIII). Preferably, R is a methyl radical.

According to one embodiment, a phenyl silicone oil of formula (VIII) with a viscosity at 25°C of between 5 and 1500 mm²/s (i.e. 5 to 1500 cSt), and preferably with a viscosity of between 5 and 1000 mm²/s (i.e. 5 to 1000 cSt), may be used.

According to this embodiment, the non-volatile phenyl silicone oil is preferably chosen from phenyl trimethicones (when n=0) such as DC556 from Dow Corning (22.5 cSt), or else from diphenylsiloxyphenyl trimethicone oil (when m and n are between 1 and 100) such as KF56 A from Shin Etsu, or the Silbione 70663V30 oil from Rhone-Poulenc (28 cSt). The values in parentheses represent the viscosities at 25°C.

e) phenyl silicone oils optionally bearing at least one dimethicone fragment corresponding to the following formula, and mixtures thereof:

(IX)

in which:

Ri , R2, R5 and R₆, which may be identical or different, are an alkyl radical containing 1 to 6 carbon atoms,

R₃ and R₄, which may be identical or different, are an alkyl radical containing from 1 to 6 carbon atoms or an aryl radical (preferably C₆-Ci₄), with the proviso that at least one of R₃ and R₄ is a phenyl radical,

X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxyl radical or a vinyl radical,

n and p being an integer greater than or equal to 1 , chosen so as to give the oil a weight-average molecular weight of less than 200 000 g/mol, preferably less than 150 000 g/mol and more preferably less than 100 000 g/mol. f) and a mixture thereof.

2. Fluoro oils

According to another embodiment, the oil(s) constituting the first oily phase and/or the second oily phase are chosen from fluoro oils. The fluoro oils that may be used according to the invention may be chosen from fluorosilicone oils, fluoro polyethers and fluorosilicones especially as described in document EP-A-847 752, and perfluoro compounds.

According to the invention, the term "perfluoro compounds" means compounds in which all the hydrogen atoms have been replaced with fluorine atoms.

According to a preferred embodiment, the fluoro oil according to the invention is chosen from perfluoro oils.

As examples of perfluoro oils that may be used in the invention, mention may be made of perfluorodecalins and perfluoroperhydrophenanthrenes.

According to a preferred embodiment, the fluoro oil is chosen from perfluoroperhydrophenanthrenes, and especially the Fiflow® products sold by the company Creations Couleurs. In particular, use may be made of the fluoro oil whose I NCI name is perfluoroperhydrophenanthrene, sold under the reference Fiflow 220 by the company F2 Chemicals.

Preferably, the first oily phase comprises at least one oil chosen from non- volatile phenyl silicone oils optionally bearing a dimethicone fragment, and more preferentially the first oily phase comprises at least one oil not bearing any dimethicone fragments.

Preferably, the oil constituting the first oily phase is 1 ,3,5-trimethyl-1 ,1 ,3,5,5- pentaphenyltrisiloxane.

Preferably, the second oily phase comprises at least one oil chosen from non-volatile phenyl silicone oils optionally bearing at least one dimethicone fragment, and more preferentially the second oily phase comprises at least one oil bearing at least one dimethicone fragment.

Preferably, the oil constituting the second oily phase is polyphenyltrimethylsiloxydimethylsiloxane.

Preferably, the first oily phase comprises at least one oil chosen from nonvolatile phenyl silicone oils not bearing any dimethicone fragments that are immiscible with the second oily phase comprising at least one oil chosen from non-volatile phenyl silicone oils bearing at least one dimethicone fragment.

The composition according to the invention more particularly comprises a content of first oily phase and second oily phase of between 5% and 60% by weight, preferably between 10% and 50% by weight and even more preferentially between 20% and 50% by weight relative to the total weight of the composition.

The composition according to the invention more particularly comprises a content of first oily phase of between 2% and 40% by weight, preferably between 5% and 35% by weight and even more preferentially between 10% and 35% by weight relative to the total weight of the composition.

The composition according to the invention more particularly comprises a content of second oily phase of between 2% and 40% by weight, preferably between 5% and 35% by weight and even more preferentially between 10% and 35% by weight relative to the total weight of the composition.

Third oily phase

The third oily phase comprises at least one volatile or non-volatile oil.

Preferably, the third oily phase comprises at least one non-volatile oil. Preferably, the third oily phase comprising at least one volatile or nonvolatile oil is immiscible with the first oily phase and with the second oily phase at room temperature and at atmospheric pressure (760 mmHg/1.013x10⁵ Pa).

This third oily phase may be the continuous phase or the dispersed phase. Preferably, the third oily phase is the continuous phase.

The oil(s) constituting the third oily phase may advantageously be chosen from polar hydrocarbon-based non-volatile oils, in particular chosen from non-volatile oils comprising not more than one free hydroxyl group or not comprising any, or from non-volatile oils comprising at least two free hydroxyl groups, or from apolar hydrocarbon-based non-volatile oils, or mixtures thereof.

According to a second possibility, the oil(s) constituting the third oily phase are chosen from silicone oils that are immiscible with the oil(s) of the first oily phase and of the second oily phase. That which has been described previously regarding the first oily phase and the second oily phase is applicable in the present case. Reference may thus be made thereto.

1 . Polar non-volatile hydrocarbon-based oils

The term "polar hydrocarbon-based oil" means an oil formed essentially from, or even constituted by, carbon and hydrogen atoms, and also heteroatoms such as oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms.

It may thus contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.

In particular, the hydrocarbon-based non-volatile polar oil may be chosen from the list of oils below, and mixtures thereof: a) non-volatile oils comprising not more than one free hydroxyl group or not comprising any

The oil(s) constituting the third oily phase may be chosen from non-volatile hydrocarbon-based oils comprising not more than one free hydroxyl group, or not comprising any. As examples of oils of this type, mention may be made of: i) Ester oils

^* Hydrocarbon-based plant oils such as liquid triglycerides of fatty acids containing from 4 to 40 carbon atoms and more particularly from 4 to 24 carbon atoms. Examples that may be mentioned include heptanoic or octanoic acid triglycerides, jojoba oil, sesame oil and ximenia seed oil, or mixtures thereof.

^* Synthetic glycerides such as those of capric/caprylic acids, C18-36 acid triglyceride (Dub TGI 24 from Stearineries Dubois).

* Monoesters or diesters obtained from a saturated or unsaturated, aromatic or non-aromatic monocarboxylic or dicarboxylic fatty acid, in particular comprising from 4 to 40 and in particular from 4 to 24 carbon atoms, optionally comprising a free hydroxyl, on the one hand, and from a saturated or unsaturated, aromatic or non- aromatic monoalcohol or polyol, comprising from 2 to 40 and in particular from 3 to 24 carbon atoms, on the other hand; the number of carbon atoms (excluding the carbonyl group) being at least 12 and preferably at least 16, the ester comprising at most one free hydroxyl, if it contains any.

- As examples of monoesters or diesters, mention may be made of purcellin oil (cetostearyl octanoate), isononyl isononanoate, C12 to C18 alkyl benzoate such as 2-octyldodecyl benzoate, 2-ethylhexyl palmitate, octyldodecyl neopentanoate, 2- octyldodecyl stearate, 2-octyldodecyl erucate, oleyl erucate, isostearyl isostearate, alcohol or polyalcohol, preferably diol, octanoates, decanoates or ricinoleates, isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, 2-ethylhexyl palmitate, 2-hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl myristate and 2- diethylhexyl succinate; or mixtures thereof.

- Fatty acid monoesters and diesters, in particular of C4-C22 and preferably C6-C22, and especially of octanoic acid, heptanoic acid, lanolic acid, oleic acid, lauric acid or stearic acid, and of C3-C6 glycol, for instance propylene glycol dioctanoate, propylene glycol monoisostearate or neopentyl glycol diheptanoate, are also suitable for use.

- Hydroxylated monoesters and diesters, preferably with a total carbon number ranging from 20 to 70, for instance isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate or diisostearyl malate.

^* Pentaerythritol esters of C6-C22 fatty monoacids or diacids, for instance the mixture of esters of pentaerythritol and of isostearic, capric, caprylic and adipic acids (Supermol-L from Croda).

^* Polyesters comprising at least three ester functions, of saturated, unsaturated or aromatic, linear, branched or cyclic, optionally hydroxylated, C₄-C₄o monocarboxylic or polycarboxylic acids and, respectively, of C₂-C ₀ and preferably C₃- C₄o polyols or monoalcohols; said polyester optionally comprising at least one free hydroxyl.

Examples that may be mentioned include oils comprising three ester functions, of a monohydroxylated acid comprising three carboxylic functions, and of a C2-C4 monoalcohol, in particular triethyl citrate.

By way of example, mention may be made of linear fatty acid esters with a total carbon number ranging from 35 to 70, for instance pentaerythrityl tetrapelargonate (MW = 697 g/mol).

Esters of branched fatty alcohols or of branched fatty acids, for instance, especially, triisoarachidyl citrate (MW = 1033.76 g/mol), pentaerythrityl tetraisononanoate (MW = 697 g/mol), glyceryl triisostearate (MM = 891 g/mol), pentaerythrityl tetraisostearate (MW = 1202 g/mol), poly(2-glyceryl) tetraisostearate (MW = 1232 g/mol), and also those described in patent application EP-A-0 955 039, for instance glyceryl tris(2-decyl)tetradecanoate (MW = 1 143 g/mol) or pentaerythrityl tetrakis(2-decyl)tetradecanoate (MW = 1538 g/mol), are also suitable for use.

Mention may also be made of esters of aromatic acids and of alcohols comprising 4 to 22 atoms, such as tridecyl trimellitate (MW = 757 g/mol).

Use may also be made of polyesters resulting from the esterification of at least one hydroxylated carboxylic acid triglyceride with an aliphatic monocarboxylic acid and with an aliphatic dicarboxylic acid, which is optionally unsaturated, for instance the succinic acid and isostearic acid castor oil sold under the reference Zenigloss by Zenitech. ii) saturated or unsaturated, linear or branched monohydroxylated fatty alcohols containing from 8 to 30 carbon atoms and more advantageously from 12 to 26 carbon atoms, for instance octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2- undecylpentadecanol or oleyl alcohol;

Hi) saturated or unsaturated Ci₂-C₂₆ and preferably C12-C22 fatty acids, such as oleic acid, linoleic acid and linolenic acid, and mixtures thereof; iv) dialkyl carbonates, the two alkyl chains possibly being identical or different, such as dicaprylyl carbonate sold under the name Cetiol CC® by Cognis; and v) vinylpyrrolidone copolymers such as the vinylpyrrolidone/1 -hexadecene copolymer, Antaron V-216 sold or manufactured by the company ISP (MW = 7300 g/mol). 2. Non-volatile oils comprising at least two free hydroxyl groups:

The oil(s) constituting the third oily phase may be chosen from non-volatile hydrocarbon-based oils comprising at least two free hydroxyl groups and preferably at least three free hydroxyl groups.

According to an advantageous variant of the invention, the second oil(s) also comprise at least one ester function.

Examples of suitable oils that may be mentioned include:

^* hydrocarbon-based plant oils such as liquid triglycerides of fatty acids containing from 4 to 40 carbon atoms and comprising at least two free hydroxyl groups and advantageously at least three free hydroxyl groups, for instance castor oil;

^* hydroxylated esters, preferably with a total carbon number ranging from 35 to 70, for instance poly(2-glyceryl) triisostearate (MW = 965 g/mol), poly(2-glyceryl) isostearate; poly(2-glyceryl) diisostearate; poly(3-glyceryl) diisostearate, glyceryl stearate; glyceryl isostearate; or mixtures thereof;

* esters of a diol dimer and of a diacid dimer of general formula

HO-R¹-(-OCO-R²-COO-R¹-)_h-OH, in which:

R¹ represents a diol dimer residue obtained by hydrogenation of dilinoleic diacid,

R² represents a hydrogenated dilinoleic diacid residue, and

h represents an integer ranging from 1 to 9,

especially the esters of dilinoleic diacids and of dilinoleyl diol dimers sold by the company Nippon Fine Chemical under the trade names Lusplan DD-DA5® and DD-DA7®, and

^* polyesters obtained by condensation of an unsaturated fatty acid dimer and/or trimer and of diol, in particular such as of dilinoleic acid and of 1 ,4-butanediol.

Mention may especially be made in this respect of the polymer sold by Biosynthis under the name Viscoplast 14436H (INCI name: dilinoleic acid/butanediol copolymer), or else copolymers of polyols and of dimer diacids, and esters thereof, such as Hailucent ISDA. 3. Apolar non-volatile hydrocarbon-based oils

The composition according to the invention may also comprise, as oil(s) present in the third oily phase, at least one apolar non-volatile hydrocarbon-based oil.

These oils may be of plant, mineral or synthetic origin.

For the purposes of the present invention, the term "apolar oil" means an oil formed essentially from, or even constituted by, carbon and hydrogen atoms, and not containing any oxygen, nitrogen, silicon or fluorine atoms.

Preferably, the non-volatile apolar hydrocarbon-based oil may be chosen from linear or branched hydrocarbons of mineral or synthetic origin, such as:

- liquid paraffin or derivatives thereof,

- squalane,

- isoeicosane,

- naphthalene oil,

- polybutenes, for instance Indopol H-100 (molar mass or MW = 965 g/mol),

Indopol H-300 (MW = 1340 g/mol) and Indopol H-1500 (MW = 2160 g/mol) sold or manufactured by the company Amoco,

- polyisobutenes, hydrogenated polyisobutenes, for instance Parleam® sold by the company Nippon Oil & Fats, Panalane H-300 E sold or manufactured by the company Amoco (MW = 1340 g/mol), Viseal 20000 sold or manufactured by the company Synteal (MW = 6000 g/mol) and Rewopal PIB 1000 sold or manufactured by the company Witco (MW = 1000 g/mol), or alternatively Parleam Lite sold by NOF Corporation,

- decene/butene copolymers, polybutene/polyisobutene copolymers, especially Indopol L-14,

- polydecenes and hydrogenated polydecenes, for instance: Puresyn 10 (MW = 723 g/mol) and Puresyn 150 (MW = 9200 g/mol) sold or manufactured by the company Mobil Chemicals, or alternatively Puresyn 6 sold by ExxonMobil Chemical),

- and mixtures thereof.

4. Volatile silicone or hydrocarbon-based oils

The composition according to the invention may also comprise, as oil(s) present in the third oily phase, at least one volatile silicone or hydrocarbon-based oil.

According to the invention, these volatile oils especially facilitate the application of the composition to the skin, the lips or the integuments. These oils may be hydrocarbon-based oils or silicone oils optionally comprising alkyl or alkoxy groups that are pendent or at the end of the silicone chain, or a mixture of these oils.

As volatile silicone oils that may be used in the invention, mention may be made of linear or cyclic silicone oils with a viscosity at room temperature of less than 8 cSt and especially containing from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oils that may be used in the invention, mention may be made especially of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane and cyclohexadimethylsiloxane (sold under the reference Xiameter PMX-0246 Cyclohexasiloxane by the company Dow Corning), and mixtures thereof.

As volatile hydrocarbon-based oils that may be used in the invention, mention may be made of volatile hydrocarbon-based oils containing from 8 to 16 carbon atoms, and mixtures thereof, especially branched C₈-Ci₆ alkanes such as Cede isoalkanes (also known as isoparaffins), isododecane, isodecane, isohexadecane (sold under the name Isohexadecane by the company Ineos) and, for example, the oils sold under the trade names Isopar or Permethyl, and mixtures thereof.

Use is preferably made of isododecane (Permethyl 99 A), C₈-Ci₆ isoparaffins such as Isopar L, E, G or H, or mixtures thereof, optionally combined with decamethyltetrasiloxane or with cyclopentasiloxane.

Use may also be made of volatile fluoro oils.

The term "oily phase" means a phase composed solely of oil and free, for example, if they are present, of pasty fatty substances or of hydrocarbon-based resin with a number-average molecular weight of less than or equal to 10 000 g/mol.

In accordance with an advantageous embodiment of the invention, the volatile oil(s), when they are used, are present in a content such that the three oily phases are immiscible within the meaning of the invention.

The composition according to the invention comprises a content of third oily phase of between 5% and 60% preferably between 10% and 55% and even more preferentially between 15% and 55% by weight relative to the total weight of the composition. Preferably, the third oily phase comprises at least one polar non-volatile hydrocarbon-based oil and at least one apolar non-volatile hydrocarbon-based oil and mixtures thereof, in particular a mixture of one or more polar non-volatile hydrocarbon- based oils and one or more apolar non-volatile hydrocarbon-based oils.

Preferably, the polar non-volatile oil is an oil comprising not more than one free hydroxyl group or not comprising any, more preferentially a polyester comprising at least three ester functions, of saturated, unsaturated or aromatic, linear, branched or cyclic, optionally hydroxylated, C₄-C₄o monocarboxylic or polycarboxylic acids and, respectively, of C₂-C ₀ and preferably C₃-C ₀ polyols or monoalcohols; said polyester optionally comprising at least one free hydroxyl, even more preferentially pentaerythrityl tetraisostearate.

Preferably, the apolar non-volatile oil is chosen from linear or branched hydrocarbons of mineral or synthetic origin, such as polybutenes.

The composition may comprise at least one volatile oil. More particularly, the first oily phase and/or the second oily phase and/or the third oily phase may comprise at least one volatile oil. Reference may be made to that which has been detailed previously regarding the nature of these oils. These volatile oils represent less than 10% by weight, relative to the weight of the composition.

Resin:

The composition according to the invention may comprise at least one hydrocarbon-based resin (thus not comprising any silicon or fluorine atoms) with a number-average molecular weight of less than or equal to 10 000 g/mol.

Advantageously, the softening point of the resin ranges from 70 to 130°C, more particularly from 80 to 120°C and preferably from 90 to 1 10°C (standard ASTM E 28).

Advantageously, this number-average molecular weight ranges from 250 g/mol to 10 000 g/mol, preferably from 250 g/mol to 5000 g/mol, more preferentially from 250 g/mol to 2000 g/mol, or even from 250 g/mol to 1000 g/mol.

The number-average molecular weights (Mn) are determined by gel permeation liquid chromatography (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector). Aliphatic hydrocarbon-based resins that may especially be mentioned include:

- hydrogenated indene/methylstyrene/styrene copolymers sold under the name Regalite by the company Eastman Chemical, in particular Regalite R1090, Regalite R1 100, Regalite S1 100 and Regalite S5100, or under the name Arkon P-90, Arkon P-100, and Arkon P-1 15 by the company Arakawa;

- aliphatic pentanediene resins such as those derived from the majority polymerization of the 1 ,3-pentanediene (trans- or cis-piperylene) monomer and of minor monomers chosen from isoprene, butene, 2-methyl-2-butene, pentene and 1 ,4- pentanediene, and mixtures thereof. These resins may have a molecular weight ranging from 1000 to 2500 g/mol. Such 1 ,3-pentanediene resins are sold, for example, under the references Piccotac 95 by the company Eastman Chemical, Escorez 1 102, Escorez 1304, Escorez 1310LC and Escorez 1315 by the company Exxon Chemicals, or Wingtack 95 by the company Cray Valley;

- diene resins of cyclopentanediene dimers such as those derived from the polymerization of dicyclopentanediene, methyldicyclopentanediene, other pentanediene dimers, and mixtures thereof. These resins generally have a molecular weight ranging from 500 to 800 g/mol, for instance those sold under the reference Escorez 5380, Escorez 5300, Escorez 5400, Escorez 5415 or Escorez 5490 by the company ExxonMobil Chem., and the resins Sukorez SU-90, Sukorez SU-100, Sukorez SU-1 10, Sukorez SU-100S, Sukorez SU-200, Sukorez SU-210, Sukorez SU- 490 and Sukorez SU-400, by the company Kolon;

- hydrogenated resins derived from the polymerization of pentanediene, for instance those sold under the name Eastotac H-100E, Eastotac H-1 15E, Eastotac C-100L, Eastotac C-1 15L, Eastotac H-100L, Eastotac H-1 15L, Eastotac C-100R, Eastotac C-1 15R, Eastotac H-100R, Eastotac H-1 15R, Eastotac C-100W, Eastotac C-1 15W, Eastotac H-100W, Eastotac H-1 15W, by the company Eastman Chemical Co.;

- and mixtures thereof.

The resin may be, for example, the hydrogenated indene/methylstyrene/styrene copolymer sold under the name Regalite R1 1 10 by the company Eastman Chemical, or the aliphatic 1 ,3-pentanediene resin sold under the name Piccotac 1095 by the company Eastman Chemical.

Preferably, the resin(s) according to the invention are chosen from aliphatic hydrocarbon-based resins. Preferably, the resin(s) according to the invention are chosen from hydrogenated indene/methylstyrene/styrene copolymers.

Preferably, the content of resin according to the invention is from 0.5% to 30% preferably from 1 % to 25% and even more preferentially from 1.5% to 20% by weight relative to the total weight of the composition.

The composition according to the invention advantageously comprises a resin content of greater than or equal to 0.5%, or even greater than or equal to 1 % and more particularly greater than or equal to 1 .5% by weight relative to the total weight of the composition.

Pasty fatty substances:

The composition according to the invention may also comprise at least one pasty fatty substance.

It should be noted that this pasty fatty substance is water-immiscible.

For the purposes of the present invention, the term "pasty" refers to a compound that undergoes a reversible solid/liquid change of state, having anisotropic crystalline organization in the solid state, and comprising, at a temperature of 23°C, a liquid fraction and a solid fraction.

In other words, the starting melting point of the pasty fatty substance may be less than 23°C. The liquid fraction of the pasty fatty substance measured at 23°C may represent 9% to 97% by weight of the pasty compound. This liquid fraction at 23°C preferably represents between 15% and 85% and more preferably between 40% and 85% by weight.

Within the context of the invention, the melting point corresponds to the temperature of the most endothermic peak observed in thermal analysis (DSC) as described in the standard ISO 1 1357-3; 1999. The melting point of a pasty fatty substance may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name MDSC 2920 by the company TA Instruments.

The measuring protocol is as follows:

A sample of 5 mg of pasty fatty substance placed in a crucible is subjected to a first temperature rise ranging from -20°C to 100°C, at a heating rate of 10°C/minute, is then cooled from 100°C to -20°C at a cooling rate of 10°C/minute and is finally subjected to a second temperature rise ranging from -20°C to 100°C at a heating rate of 5°C/minute. During the second temperature rise, the variation in the difference in power absorbed by the empty crucible and by the crucible containing the sample of pasty fatty substance is measured as a function of the temperature. The melting point of the pasty compound is the temperature value corresponding to the top of the peak of the curve representing the variation in the difference in power absorbed as a function of the temperature.

The liquid fraction by weight of the pasty compound at 23°C is equal to the ratio of the heat of fusion consumed at 23°C to the heat of fusion of the pasty fatty substance.

The heat of fusion of the pasty fatty substance is the heat consumed by the substance in order to pass from the solid state to the liquid state. The pasty fatty substance is said to be in the solid state when all of its mass is in crystalline solid form. The pasty fatty substance is said to be in the liquid state when all of its mass is in liquid form.

The heat of fusion of the pasty fatty substance is equal to the area under the curve of the thermogram obtained using a differential scanning calorimeter (DSC), such as the calorimeter sold under the name MDSC 2920 by the company TA Instrument, with a temperature rise of 5°C or 10°C per minute, according to the standard ISO 1 1357-3; 1999.

The heat of fusion of the pasty fatty substance is the amount of energy required to make the pasty fatty substance change from the solid state to the liquid state. It is expressed in J/g.

The heat of fusion consumed at 23°C is the amount of energy absorbed by the sample to change from the solid state to the state that it has at 2°C, formed from a liquid fraction and a solid fraction.

The liquid fraction of the pasty fatty substance measured at 32°C preferably represents from 30% to 100% by weight of the pasty fatty substance, preferably from 50% to 100%, more preferably from 60% to 100% by weight of the pasty fatty substance. When the liquid fraction of the pasty compound measured at 32°C is equal to 100%, the temperature of the end of the melting range of the pasty fatty substance is less than or equal to 32°C.

The liquid fraction of the pasty fatty substance measured at 32°C is equal to the ratio of the heat of fusion consumed at 32°C to the heat of fusion of the pasty fatty substance. The heat of fusion consumed at 32°C is calculated in the same way as the heat of fusion consumed at 23°C. The pasty fatty substance may in particular be chosen from synthetic pasty compounds and fatty substances of plant origin.

The pasty fatty substance(s) may be chosen in particular from:

- lanolin and derivatives thereof, such as lanolin alcohol, oxyethylenated lanolins, acetylated lanolin, lanolin esters such as isopropyl lanolate, and oxypropylenated lanolins,

- petroleum jelly (also known as petrolatum),

- polyol ethers chosen from C2-C4 polyalkylene glycol pentaerythrityl ethers, fatty alcohol ethers of sugars, and mixtures thereof. For example, mention may be made of polyethylene glycol pentaerythrityl ether comprising 5 oxyethylene units (5 OE) (CTFA name: PEG-5 Pentaerythrityl Ether), polypropylene glycol pentaerythrityl ether comprising 5 oxypropylene (5 OP) units (CTFA name: PPG-5 Pentaerythrityl Ether) and mixtures thereof, and more especially the mixture PEG-5 Pentaerythrityl Ether, PPG-5 Pentaerythrityl Ether and soybean oil, sold under the name Lanolide by the company Vevy, which is a mixture in which the constituents are in a 46/46/8 weight ratio: 46% PEG-5 pentaerythrityl ether, 46% PPG-5 pentaerythrityl ether and 8% soybean oil,

polymeric or non-polymeric silicone compounds,

- polymeric or non-polymeric fluoro compounds,

- vinyl polymers, especially,

- olefin homopolymers and copolymers,

- hydrogenated diene homopolymers and copolymers,

- linear or branched oligomers, homopolymers or copolymers of alkyl (meth)acrylates preferably containing a C₈-C₃o alkyl group,

- oligomers, which are homopolymers and copolymers of vinyl esters containing C8-C30 alkyl groups, and

- oligomers, which are homopolymers and copolymers of vinyl ethers containing C8-C30 alkyl groups,

- liposoluble polyethers resulting from polyetherification between one or more C2-C100 and preferably C2-C50 diols.

Among the liposoluble polyethers that are particularly considered are copolymers of ethylene oxide and/or of propylene oxide with C₆-C₃₀ long-chain alkylene oxides, more preferably such that the weight ratio of the ethylene oxide and/or of the propylene oxide to the alkylene oxides in the copolymer is from 5:95 to 70:30. In this family, mention will be made especially of copolymers such as long-chain alkylene oxides arranged in blocks with an average molecular weight from 1000 to 10 000, for example a polyoxyethylene/polydodecyl glycol block copolymer such as the ethers of dodecanediol (22 mol) and of polyethylene glycol (45 OE) sold under the brand name Elfacos ST9 by Akzo Nobel.

- esters and polyesters.

Among the esters, the following are especially considered:

- esters of a glycerol oligomer, especially diglycerol esters, in particular condensates of adipic acid and of diglycerol, for which some of the hydroxyl groups of the glycerols have reacted with a mixture of fatty acids such as stearic acid, capric acid, isostearic acid and 12-hydroxystearic acid, for instance the glyceryl ester of caprylic, capric, isostearic, stearic, hydroxystearic and adipic acids (INCI name: bis- diglyceryl polyacyladipate-2) sold under the reference Softisan® 649 by the company Sasol,

- vinyl ester homopolymers bearing C8-C30 alkyl groups, such as polyvinyl laurate (sold especially under the reference Mexomer PP by the company Chimex),

- the arachidyl propionate sold under the brand name Waxenol 801 by

Alzo,

- phytosterol esters,

- fatty acid triglycerides and derivatives thereof,

- pentaerythritol esters,

- esters of a diol dimer and of a diacid dimer, where appropriate esterified on their free alcohol or acid function(s) with acid or alcohol radicals, especially dimer dilinoleate esters; such esters may be chosen especially from the esters having the following INCI nomenclature: bis-behenyl/isostearyl/phytosteryl dimer dilinoleyl dimer dilinoleate (Plandool G), phytosteryl/isosteryl/cetyl/stearyl/behenyl dimer dilinoleate (Plandool H or Plandool S), and mixtures thereof,

- butters of plant origin, such as mango butter, such as the product sold under the reference Lipex 203 by the company Aarhuskarlshamn, shea butter, in particular the product whose INCI name is Butyrospermum Parkii Butter, such as the product sold under the reference Sheasoft® by the company Aarhuskarlshamn, cupuacu butter (Rain Forest RF3410 from the company Beraca Sabara), murumuru butter (Rain Forest RF3710 from the company Beraca Sabara), cocoa butter; and also orange wax, for instance the product sold under the reference Orange Peel Wax by the company Koster Keunen,

- totally or partially hydrogenated plant oils, for instance hydrogenated soybean oil, hydrogenated coconut oil, hydrogenated rapeseed oil, mixtures of hydrogenated plant oils such as the mixture of hydrogenated soybean, coconut, palm and rapeseed plant oil, for example the mixture sold under the reference Akogel® by the company Aarhuskarlshamn (INCI name: Hydrogenated Vegetable Oil), the product sold under the reference Cegesoft® HF 52 from BASF (INCI name Hydrogenated Vegetable Oil), the trans-isomerized partially hydrogenated jojoba oil manufactured or sold by the company Desert Whale under the commercial reference lso-Jojoba-50®, partially hydrogenated olive oil, for instance the compound sold under the reference Beurrolive by the company Soliance,

- hydrogenated castor oil esters, such as hydrogenated castor oil dimer dilinoleate, for example Risocast DA-L sold by Kokyu Alcohol Kogyo, and hydrogenated castor oil isostearate, for example Salacos HCIS (V-L) sold by Nisshin Oil,

- and mixtures thereof.

Preferably, the pasty fatty substances that are suitable for use in the invention are chosen from hydrocarbon-based compounds and comprise, besides carbon and hydrogen atoms, at least oxygen atoms. The pasty fatty substances therefore do not comprise any silicon atoms or any fluorine atoms.

According to a preferred embodiment, the binder phase comprises at least one pasty fatty substance, advantageously chosen from lanolin and derivatives thereof, esters, or mixtures thereof.

Preferably, the pasty fatty substance(s) are chosen from lanolin and derivatives thereof, esters of glycerol oligomers, butters of plant origin, totally or partially hydrogenated plant oils, and hydrogenated castor oil esters, or mixtures thereof.

Preferably, the pasty fatty substance(s) are chosen in particular from esters of glycerol oligomers, esters of hydrogenated castor oils, totally or partially hydrogenated plant oils, and mixtures thereof, in particular a mixture of esters of glycerol oligomers, esters of hydrogenated castor oils and totally or partially hydrogenated plant oils. Preferably, the pasty fatty substance(s) are chosen in particular from esters of glycerol oligomers, especially diglycerol esters, in particular condensates of adipic acid and of diglycerol.

If the composition according to the invention comprises any, the content of fatty substance that is pasty at room temperature and atmospheric pressure advantageously represents from 2% to 20% by weight and preferably from 5% to 15% by weight relative to the total weight of the composition.

Waxes:

The composition according to the invention may also comprise at least one wax.

For the purposes of the present invention, the term "wax" means a lipophilic compound, which is solid at room temperature (25°C), with a reversible solid/liquid change of state, which has a melting point of greater than or equal to 30°C that may be up to 120°C.

The melting point of the wax may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name DSC 30 by the company Mettler.

Preferably, the measuring protocol is as follows:

A sample of 5 mg of wax placed in a crucible is subjected to a first temperature rise ranging from -20°C to 100°C, at a heating rate of 10°C/minute, it is then cooled from 100°C to -20°C at a cooling rate of 10°C/minute and is finally subjected to a second temperature rise ranging from -20°C to 100°C at a heating rate of 5°C/minute. During the second temperature rise, the variation in the difference in power absorbed by the empty crucible and by the crucible containing the sample of wax is measured as a function of the temperature. The melting point of the compound is the temperature value corresponding to the top of the peak of the curve representing the variation in the difference in power absorbed as a function of the temperature.

The wax may especially have a hardness ranging from 0.05 MPa to 15 MPa and preferably ranging from 6 MPa to 15 MPa. The hardness is determined by measuring the compression force, measured at 20°C using the texturometer sold under the name TA-TX2i by the company Rheo, equipped with a stainless-steel cylinder 2 mm in diameter travelling at a measuring speed of 0.1 mm/s, and penetrating the wax to a penetration depth of 0.3 mm. Preferably, the wax(es) are chosen from waxes whose melting point is greater than or equal to 60°C, preferably greater than or equal to 65°C.

According to a preferred embodiment, the wax content is between 0.1 % and 10% by weight, more particularly between 0.5% and 7% by weight and even more preferably between 0.5% and 5% by weight, relative to the total weight of the composition.

Advantageously, the total wax content is less than 12% by weight, preferably less than 10% by weight and even more advantageously less than 6% by weight, relative to the total weight of the composition.

The waxes that may be used in the compositions according to the invention are chosen from waxes that are solid at room temperature, of animal, plant, mineral or synthetic origin, and mixtures thereof.

The composition according to the invention may comprise at least one polar or apolar wax, or mixtures thereof.

Polar waxes:

According to a first embodiment of the invention, the wax is a polar wax. For the purposes of the present invention, the term "polar wax" means a wax whose solubility parameter at 25°C, a, is other than 0 (J/cm³)^½. In addition, said polar waxes have a reversible solid/liquid change of state, and also the melting point characteristics mentioned previously.

In particular, the term "polar wax" means a wax whose chemical structure is formed essentially from, or even constituted by, carbon and hydrogen atoms, and comprising at least one highly electronegative heteroatom such as an oxygen, nitrogen, silicon or phosphorus atom.

The definition and calculation of the solubility parameters in the Hansen three-dimensional solubility space are described in the article by CM. Hansen: "The three dimensional solubility parameters", J. Paint Technol. 39, 105 (1967).

According to this Hansen space:

- δ₀ characterizes the London dispersion forces derived from the formation of dipoles induced during molecular impacts;

- δ_ρ characterizes the Debye interaction forces between permanent dipoles and also the Keesom interaction forces between induced dipoles and permanent dipoles; - 8_h characterizes the specific interaction forces (such as hydrogen bonding, acid/base, donor/acceptor, etc.); and

- 8_a is determined by the equation: 8_a = (δ_ρ ² + 8_h ²)^½

The parameters δ_ρ, 8_h, 5_D and 8_a are expressed in (J/cm³)^½.

The polar waxes may in particular be hydrocarbon-based, fluoro or silicone waxes.

The term "silicone wax" means an oil comprising at least one silicon atom, especially comprising Si-0 groups.

The term "hydrocarbon-based wax" means a wax formed essentially from, or even constituted by, carbon and hydrogen atoms, and optionally oxygen and nitrogen atoms, and that does not contain any silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.

According to a first preferred embodiment, the polar wax is a hydrocarbon- based wax. As a hydrocarbon-based polar wax, a wax chosen from ester waxes and alcohol waxes is in particular preferred.

According to the invention, the term "ester wax" means a wax comprising at least one ester function.

According to the invention, the term "alcohol wax" means a wax comprising at least one alcohol function, i.e. comprising at least one free hydroxyl (OH) group.

According to a first embodiment, the polar wax is chosen from ester waxes, alcohol waxes and silicone waxes.

Preferably, the ester wax is chosen from:

i) waxes of formula RiCOOR₂ in which R-i and R₂ represent linear, branched or cyclic aliphatic chains, the number of atoms of which varies from 10 to 50, which may contain a heteroatom such as O, N or P. In particular, use may be made, as an ester wax, of a C₂o-C₄o alkyl (hydroxystearyloxy)stearate (the alkyl group comprising from 20 to 40 carbon atoms), alone or as a mixture, or a C₂o-C₄₀ alkyl stearate. Such waxes are especially sold under the names Kester Wax K 82 P®, Hydroxypolyester K 82 P®, Kester Wax K 80 P® and Kester Wax K82H by the company Koster Keunen.

Use may also be made of a glycol and butylene glycol montanate (octacosanoate) such as the wax Licowax KPS Flakes (INCI name: glycol montanate) sold by the company Clariant.

ii) Bis(1 ,1 , 1 -trimethylolpropane) tetrastearate, sold under the name Hest 2T- 4S® by the company Heterene, iii) diester waxes of a dicarboxylic acid of general formula R³-(-OCO-R⁴- COO-R⁵), in which R³ and R⁵ are identical or different, preferably identical, and represent a C₄-C₃o alkyl group and R⁴ represents a linear or branched C₄-C₃o aliphatic group which may or may not comprise one or more unsaturations and which is preferably linear and unsaturated,

iv) waxes corresponding to the partial or total esters, preferably total esters, of a saturated, optionally hydroxylated Ci₆-C₃₀ carboxylic acid with glycerol. The term "total esters" means that all the hydroxyl functions of glycerol are esterified.

Examples that may be mentioned include trihydroxystearine (or glyceryl trihydroxystearate) sold under the name Thixcin R by the company Elementis, tristearine (or glyceryl tristearate) and tribehenine (or glyceryl tribehenate), alone or as a mixture.

v) Mention may also be made of the waxes obtained by catalytic hydrogenation of animal or plant oils having linear or branched C₈-C₃₂ fatty chains, for example such as hydrogenated jojoba oil, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil, and also the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol, such as those sold under the names Phytowax Ricin 16L64® and 22L73® by the company Sophim. Such waxes are described in patent application FR-A-2792190 and the waxes obtained by hydrogenation of olive oil esterified with stearyl alcohol such as that sold under the name Phytowax Olive 18L57, or else;

vi) beeswax, synthetic beeswax, polyglycerolated beeswax, carnauba wax, candelilla wax, oxypropylenated lanolin wax, rice bran wax, ouricury wax, esparto grass wax, cork fibre wax, sugar cane wax, Japan wax, sumac wax, montan wax, orange wax, laurel wax and hydrogenated jojoba wax;

vii) mixtures thereof.

According to another embodiment, the polar wax may be an alcohol wax. More particularly, these waxes are Ci₆-C₅o and advantageously Ci₆-C₄₀ fatty alcohols, which are preferably linear, preferably saturated and optionally comprising at least one free hydroxyl. Said waxes may also be polyoxyethylenated. Examples of alcohol waxes that may be mentioned include the wax Performacol 550-L Alcohol from New Phase Technologies, stearyl alcohol, cetyl alcohol, myristyl alcohol, palmityl alcohol, behenyl alcohol, erucyl alcohol or arachidyl alcohol, or mixtures thereof. According to a second embodiment, the polar wax may be a silicone wax, for instance siliconized beeswax.

Preferably, the wax is a polar wax chosen from the waxes corresponding to the total esters of a saturated, optionally hydroxylated Ci₆-C₃o carboxylic acid with glycerol, such as trihydroxystearine; beeswax, synthetic beeswax, polyglycerolated beeswax, carnauba wax, candelilla wax, oxypropylenated lanolin wax, rice bran wax, ouricury wax, esparto grass wax, cork fibre wax, sugar cane wax, Japan wax, sumac wax, montan wax, orange wax, laurel wax and hydrogenated jojoba wax, alone or as a mixture.

Apolar waxes:

According to another embodiment, the wax is an apolar wax.

For the purposes of the present invention, the term "apolar wax" means a wax whose solubility parameter at 25°C as defined below, a, is equal to 0 (J/cm³)^½. In addition, said apolar waxes have a reversible solid/liquid change of state, and also the melting point characteristics mentioned previously.

The apolar waxes are in particular hydrocarbon-based waxes formed solely from carbon and hydrogen atoms, and free of heteroatoms such as N, O, Si and P.

In particular, the term "apolar wax" means a wax that is formed solely from apolar wax, rather than a mixture also comprising other types of waxes that are not apolar waxes.

As illustrations of apolar waxes that are suitable for use in the invention, mention may be made especially of hydrocarbon-based waxes, for instance microcrystalline waxes, paraffin waxes, ozokerite, polymethylene waxes, polyethylene waxes and microwaxes, especially polyethylene waxes.

Polyethylene waxes that may be mentioned include Performalene 500-L Polyethylene and Performalene 400 Polyethylene sold by New Phase Technologies, and Asensa SC 21 1 sold by Honeywell.

A polymethylene wax that may be mentioned is Cirebelle 108 sold by

Cirebelle.

An ozokerite that may be mentioned is Ozokerite Wax SP 1020 P. As microcrystalline waxes that may be used, mention may be made of Multiwax W 445® sold by the company Sonneborn, and Microwax HW® and Base Wax 30540® sold by the company Paramelt. As microwaxes that may be used in the compositions according to the invention as apolar wax, mention may be made especially of polyethylene microwaxes such as those sold under the names Micropoly 200®, 220®, 220L® and 250S® by the company Micro Powders.

Preferably, the composition according to the invention comprises at least one wax chosen from apolar waxes.

Preferably, the apolar wax(es) are chosen from polyethylene waxes, ozokerite, microcrystalline waxes and polymethylene waxes, alone or as mixtures. Preferably, the composition comprises at least one polar wax in particular of the type such as waxes corresponding to the total esters of a saturated, optionally hydroxylated Ci₆-C₃₀ carboxylic acid with glycerol, and at least one apolar wax in particular of the type such as polyethylene waxes and a mixture thereof, in particular a mixture of a polar wax of the type such as waxes corresponding to the total esters of a saturated, optionally hydroxylated Ci₆-C₃o carboxylic acid with glycerol and of an apolar wax of the type such as polyethylene waxes.

The composition may also comprise at least one additional wax. Preferably, the additional wax(es) may be chosen from linear, hydroxylated, preferably saturated C18-C24 fatty acids.

Linear hydroxylated C18-C24 fatty acid:

Preferably, the linear hydroxylated C18-C24 fatty acid is 12-hydroxystearic acid. This compound is especially sold under the reference 12-Hydroxystearic Acid Premium Grade 12H-P by the company Thai Kawaken.

If the composition according to the invention comprises any, the total content of linear hydroxylated C18-C24 fatty acid(s) is preferentially between 0.1 % and 5% by weight, better still preferably from 0.1 % to 4% by weight and preferably from 0.5% to 3% by weight, relative to the total weight of the composition.

Mineral thickener:

The composition according to the invention may comprise at least one mineral thickener chosen from optionally modified clays and optionally modified silicas, or mixtures thereof. More particularly, the content of mineral thickener, expressed as active material, represents from 0.5% to 30% by weight, preferably from 0.5% to 20% by weight and even more preferentially between 1 % and 15% by weight, relative to the weight of the composition.

In accordance with an advantageous embodiment of the invention, the content of mineral thickener is such that the weight ratio, expressed as active material, of polymer particles/thickener ranges from 0.5 to 80, preferentially from 5 to 50 and even more particularly from 10 to 30. i) Optionally modified clays

Clays are silicates containing a cation that may be chosen from calcium, magnesium, aluminium, sodium, potassium and lithium cations, and mixtures thereof.

Examples of such products that may be mentioned include clays of the smectite family, and also of the vermiculite, stevensite and chlorite families. These clays can be of natural or synthetic origin.

Mention may more particularly be made of smectites, such as saponites, hectorites, montmorillonites, bentonites or beidellite and in particular synthetic hectorites (also known as laponites), such as the products sold by Rockwood Additives

Limited under the names Laponite® XLS, Laponite® XLG, Laponite® RD, Laponite® RDS and Laponite® XL21 (these products are sodium magnesium silicates and in particular sodium lithium magnesium silicates); bentonites, such as the product sold under the name Bentone HC by Rheox; magnesium aluminium silicates, which are in particular hydrated, such as the products sold by Vanderbilt Company under the name Veegum Ultra, Veegum HS or Veegum DGT, or also calcium silicates and in particular that in synthetic form sold by the company under the name Micro-Cel C.

Preferably, use is made of organophilic clays, more particularly modified clays, such as montmorillonite, bentonite, hectorite, attapulgite and sepiolite, and mixtures thereof. The clay is preferably a bentonite or a hectorite.

These clays are modified with a chemical compound chosen from quaternary amines, tertiary amines, amine acetates, imidazolines, amine soaps, fatty sulfates, alkylarylsulfonates and amine oxides, and mixtures thereof.

Mention may thus be made of hectorites modified with a quaternary amine, more specifically with a C10 to C22 fatty acid ammonium halide, such as a chloride, such as hectorite modified with distearyldimethylammonium chloride (CTFA name: Disteardimonium hectorite), for instance the product sold under the name Bentone 38V®, Bentone 38V CG or Bentone EW CE by the company Elementis, or stearalkonium hectorites, such as Bentone 27 V by the company Elementis.

Mention may also be made of quaternium-18 bentonites, such as those sold under the names Bentone 34 by the company Elementis, Tixogel VP by the company United Catalyst and Claytone 40 by the company Southern Clay; stearalkonium bentonites, such as those sold under the names Tixogel LG by the company United Catalyst and Claytone AF and Claytone APA by the company Southern Clay; or quaternium-18/benzalkonium bentonites, such as that sold under the name Claytone HT by the company Southern Clay.

According to a preferred embodiment, the thickener is chosen from organophilic modified clays, in particular organophilic modified hectorites, in particular modified with benzyldimethylammonium stearate chloride or with distearyldimethylammonium chloride.

In accordance with one variant of the invention, the content of optionally modified clay ranges from 0.5% to 10% by weight relative to the weight of the composition, expressed as active material. ii) Optionally modified silicas

Mention may also be made of fumed silica optionally subjected to a hydrophobic surface treatment, the particle size of which is less than 1 μηη. This is because it is possible to chemically modify the surface of the silica, by chemical reaction generating a reduced number of silanol groups present at the surface of the silica. It is possible in particular to replace silanol groups with hydrophobic groups: a hydrophobic silica is then obtained. The hydrophobic groups may be:

- trimethylsiloxyl groups, which are obtained especially by treating fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are known as Silica silylate according to the CTFA (6th Edition, 1995). They are sold, for example, under the references Aerosil R812® by the company Degussa, and Cab-O-Sil TS-530® by the company Cabot;

- dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained in particular by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are known as silica dimethyl silylate according to the CTFA (6th Edition, 1995). They are sold, for example, under the references Aerosil R972® and Aerosil R974® by the company Degussa, and Cab-O-Sil TS-610® and Cab-O-Sil TS-720® by the company Cabot. The hydrophobic fumed silica in particular has a particle size that may be nanometric to micrometric, for example ranging from about 5 to 200 nm.

The composition according to the invention comprises at least silica aerogel particles.

Silica aerogels are porous materials obtained by replacing (by drying) the liquid component of a silica gel with air.

They are generally synthesized via a sol-gel process in a liquid medium and then dried, usually by extraction with a supercritical fluid, the one most commonly used being supercritical C02. This type of drying makes it possible to avoid shrinkage of the pores and of the material. The sol-gel process and the various drying processes are described in detail in Brinker CJ., and Scherer G.W., Sol-Gel Science: New York: Academic Press, 1990.

The hydrophobic silica aerogel particles used in the present invention have a specific surface area per unit mass (SM) ranging from 500 to 1500 m²/g, preferably from 600 to 1200 m²/g and better still from 600 to 800 m²/g, and a size expressed as the volume mean diameter (D[0.5]) ranging from 1 to 1500 μηη, better still from 1 to 1000 μηη, preferably from 1 to 100 μηη, in particular from 1 to 30 μηη, more preferably from 5 to 25 μηη, better still from 5 to 20 μηη and even better still from 5 to 15 μηη.

According to one embodiment, the hydrophobic silica aerogel particles used in the present invention have a size expressed as the volume mean diameter (D[0.5]) ranging from 1 to 30 μηη, preferably from 5 to 25 μηη, better still from 5 to 20 μηη and even better still from 5 to 15 μηη.

The specific surface area per unit mass may be determined by the nitrogen absorption method, known as the BET (Brunauer-Emmett-Teller) method, described in The Journal of the American Chemical Society, vol. 60, page 309, February 1938 and corresponding to international standard ISO 5794/1 (appendix D). The BET specific surface area corresponds to the total specific surface area of the particles under consideration.

The sizes of the silica aerogel particles may be measured by static light scattering using a commercial particle size analyser such as the MasterSizer 2000 machine from Malvern. The data are processed on the basis of the Mie scattering theory. This theory, which is exact for isotropic particles, makes it possible to determine, in the case of non-spherical particles, an "effective" particle diameter. This theory is especially described in the publication by Van de Hulst, H.C., Light Scattering by Small Particles, Chapters 9 and 10, Wiley, New York, 1957. According to an advantageous embodiment, the hydrophobic silica aerogel particles used in the present invention have a specific surface area per unit mass (SM) ranging from 600 to 800 m²/g and a size expressed as the volume mean diameter (D[0.5]) ranging from 5 to 20 μηη and even better still from 5 to 15 μηη.

The silica aerogel particles used in the present invention may advantageously have a tapped density σ ranging from 0.02 g/cm³ to 0.10 g/cm³, preferably from 0.03 g/cm³ to 0.08 g/cm³ and preferably from 0.05 g/cm³ to 0.08 g/cm³.

In the context of the present invention, this density, known as the tapped density, may be assessed according to the following protocol:

40 g of powder are poured into a measuring cylinder; the measuring cylinder is then placed on a Stav 2003 machine from Stampf Volumeter; the measuring cylinder is then subjected to a series of 2500 tapping actions (this operation is repeated until the difference in volume between two consecutive tests is less than 2%); the final volume Vf of tapped powder is then measured directly on the measuring cylinder. The tapped density is determined by the ratio m/Vf, in this instance 40/Vf (Vf being expressed in cm³ and m in g).

According to a preferred embodiment, the hydrophobic silica aerogel particles used in the present invention have a specific surface area per unit of volume SV ranging from 5 to 60 m²/cm³, preferably from 10 to 50 m²/cm³ and better still from 15 to 40 m²/cm³.

The specific surface area per unit of volume is given by the relationship: SV = SM x σ where σ is the tapped density expressed in g/cm³ and SM is the specific surface area per unit of mass expressed in m²/g, as defined above.

Preferably, the hydrophobic silica aerogel particles according to the invention have an oil-absorbing capacity, measured at the wet point, ranging from 5 to 18 ml/g, preferably from 6 to 15 ml/g and better still from 8 to 12 ml/g.

The absorbing capacity measured at the wet point, noted Wp, corresponds to the amount of oil that needs to be added to 100 g of particles in order to obtain a homogeneous paste.

It is measured according to what is known as the wet point method or the method for determining the oil uptake of a powder described in standard NF T 30-022. It corresponds to the amount of oil adsorbed onto the available surface of the powder and/or absorbed by the powder by measurement of the wet point, described below:

An amount m = 2 g of powder is placed on a glass plate, and the oil (isononyl isononanoate) is then added dropwise. After addition of 4 to 5 drops of oil to the powder, mixing is carried out using a spatula, and addition of oil is continued until conglomerates of oil and powder have formed. From this point, the oil is added at the rate of one drop at a time and the mixture is subsequently triturated with the spatula. The addition of oil is stopped when a firm, smooth paste is obtained. This paste must be able to be spread on the glass plate without cracking or forming lumps. The volume Vs (expressed in ml) of oil used is then noted.

The oil uptake corresponds to the ratio Vs/m.

The aerogels used according to the present invention are hydrophobic silica aerogels, preferably of silyl silica (INCI name: silica silylate).

The term "hydrophobic silica" means any silica whose surface is treated with silylating agents, for example halogenated silanes such as alkylchlorosilanes, siloxanes, in particular dimethylsiloxanes such as hexamethyldisiloxane, or silazanes, so as to functionalize the OH groups with silyl groups Si-Rn, for example trimethylsilyl groups.

As regards the preparation of hydrophobic silica aerogel particles that have been surface-modified by silylation, reference may be made to document US 7 470 725.

Use will preferably be made of hydrophobic silica aerogel particles surface- modified with trimethylsilyl groups.

As hydrophobic silica aerogels that may be used in the invention, examples that may be mentioned include the aerogel sold under the name VM-2260 (INCI name: Silica silylate), by the company Dow Corning, the particles of which have a mean size of about 1000 microns and a specific surface area per unit of mass ranging from 600 to 800 m²/g.

Mention may also be made of the aerogels sold by the company Cabot under the references Aerogel TLD 201 , Aerogel OGD 201 , Aerogel TLD 203, Enova®

Aerogel MT 1 100 and Enova Aerogel MT 1200.

Use will preferably be made of the aerogel sold under the name VM-2270

(INCI name: Silica silylate), by the company Dow Corning, the particles of which have a mean size ranging from 5 to 15 microns and a specific surface area per unit of mass ranging from 600 to 800 m²/g.

Preferably, when the composition comprises at least one thickener chosen from optionally modified silicas, these silicas are chosen from hydrophobic silica aerogel particles. In accordance with one variant of the invention, the content of optionally modified silica, expressed as active material, ranges from 0.5% to 20% by weight and more particularly from 0.5% to 15% by weight relative to the weight of the composition. Preferably, the mineral thickeners are chosen from lipophilic clays, in particular modified hectorites; hydrophobic-treated fumed silica; hydrophobic silica aerogels, or mixtures thereof.

Preferably, the composition comprises at least one thickener chosen in particular from organophilic modified clays, in particular organophilic modified hectorites, in particular modified with benzyldimethylammonium stearate chloride or with distearyldimethylammonium chloride.

Dyestuff:

The composition according to the invention may also comprise at least one dyestuff which may be chosen from organic or mineral dyestuffs, materials with an optical effect, and mixtures thereof.

For the purposes of the present invention, the term "dyestuff" means a compound that is capable of producing a coloured optical effect when it is formulated in sufficient amount in a suitable cosmetic medium.

Pigments

The term "pigments" should be understood as meaning white or coloured, inorganic (mineral) or organic particles, which are insoluble in the liquid organic phase, and which are intended to colour and/or opacify the composition and/or the deposit produced with the composition.

The pigments may be chosen from mineral pigments, organic pigments and composite pigments (i.e. pigments based on mineral and/or organic materials).

The pigments may be chosen from monochromatic pigments, lakes and pigments with an optical effect, for instance goniochromatic pigments and nacres.

The mineral pigments may be chosen from metal oxide pigments, chromium oxides, iron oxides (black, yellow, red), titanium dioxide, zinc oxides, cerium oxides, zirconium oxides, chromium hydrate, manganese violet, Prussian blue, ultramarine blue, ferric blue, metal powders such as aluminium powders and copper powder, and mixtures thereof. Organic lakes are organic pigments formed from a dye attached to a substrate.

The lakes, which are also known as organic pigments, may be chosen from the materials below, and mixtures thereof:

- cochineal carmine;

- organic pigments of azo dyes, anthraquinone dyes, indigoid dyes, xanthene dyes, pyrene dyes, quinoline dyes, triphenylmethane dyes or fluoran dyes.

Among the organic pigments that may in particular be mentioned are those known under the following names: D&C Blue No. 4, D&C Brown No. 1 , D&C Green No. 5, D&C Green No. 6, D&C Orange No. 4, D&C Orange No. 5, D&C Orange No. 10, D&C Orange No. 1 1 , D&C Red No. 6, D&C Red No. 7, D&C Red No. 17, D&C Red No. 21 , D&C Red No. 22, D&C Red No. 27, D&C Red No. 28, D&C Red No. 30, D&C Red No. 31 , D&C Red No. 33, D&C Red No. 34, D&C Red No. 36, D&C Violet No. 2, D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10, D&C Yellow No. 1 1 , FD&C Blue No. 1 , FD&C Green No. 3, FD&C Red No. 40, FD&C Yellow No. 5, FD&C Yellow No. 6;

- the organic lakes may be insoluble sodium, potassium, calcium, barium, aluminium, zirconium, strontium or titanium salts of acidic dyes such as azo, anthraquinone, indigoid, xanthene, pyrene, quinoline, triphenylmethane or fluoran dyes, these dyes possibly comprising at least one carboxylic or sulfonic acid group.

The organic lakes may also be supported on an organic support such as rosin or aluminium benzoate, for example.

Among the organic lakes, mention may be made in particular of those known under the following names: D&C Red No. 2 Aluminium lake, D&C Red No. 3 Aluminium lake, D&C Red No. 4 Aluminium lake, D&C Red No. 6 Aluminium lake, D&C Red No. 6 Barium lake, D&C Red No. 6 Barium/Strontium lake, D&C Red No. 6 Strontium lake, D&C Red No. 6 Potassium lake, D&C Red No. 7 Aluminium lake, D&C Red No. 7 Barium lake, D&C Red No. 7 Calcium lake, D&C Red No. 7 Calcium/Strontium lake, D&C Red No. 7 Zirconium lake, D&C Red No. 8 Sodium lake, D&C Red No. 9 Aluminium lake, D&C Red No. 9 Barium lake, D&C Red No. 9 Barium/Strontium lake, D&C Red No. 9 Zirconium lake, D&C Red No. 10 Sodium lake, D&C Red No. 19 Aluminium lake, D&C Red No. 19 Barium lake, D&C Red No. 19 Zirconium lake, D&C Red No. 21 Aluminium lake, D&C Red No. 21 Zirconium lake, D&C Red No. 22 Aluminium lake, D&C Red No. 27 Aluminium lake, D&C Red No. 27 Aluminium/Titanium/Zirconium lake, D&C Red No. 27 Barium lake, D&C Red No. 27 Calcium lake, D&C Red No. 27 Zirconium lake, D&C Red No. 28 Aluminium lake, D&C Red No. 30 lake, D&C Red No. 31 Calcium lake, D&C Red No. 33 Aluminium lake, D&C Red No. 34 Calcium lake, D&C Red No. 36 lake, D&C Red No. 40 Aluminium lake, D&C Blue No. 1 Aluminium lake, D&C Green No. 3 Aluminium lake, D&C Orange No. 4 Aluminium lake, D&C Orange No. 5 Aluminium lake, D&C Orange No. 5 Zirconium lake, D&C Orange No. 10 Aluminium lake, D&C Orange No. 17 Barium lake, D&C Yellow No. 5 Aluminium lake, D&C Yellow No. 5 Zirconium lake, D&C Yellow No. 6 Aluminium lake, D&C Yellow No. 7 Zirconium lake, D&C Yellow No. 10 Aluminium lake, FD&C Blue No. 1 Aluminium lake, FD&C Red No. 4 Aluminium lake, FD&C Red No. 40 Aluminium lake, FD&C Yellow No. 5 Aluminium lake, FD&C Yellow No. 6 Aluminium lake.

Mention may also be made of liposoluble dyes, for instance Sudan Red, DC Red 17, DC Green 6, β-carotene, soybean oil, Sudan Brown, DC Yellow 1 1 , DC Violet 2, DC Orange 5 and quinoline yellow.

The chemical materials corresponding to each of the organic dyestuffs mentioned previously are mentioned in the publication "International Cosmetic Ingredient Dictionary and Handbook", 1997 edition, pages 371 to 386 and 524 to 528, published by The Cosmetic, Toiletries and Fragrance Association, the content of which is incorporated into the present patent application by reference.

The pigments may also have been subjected to a hydrophobic treatment.

The hydrophobic treatment agent may be chosen from silicones such as methicones, dimethicones, alkoxysilanes and perfluoroalkylsilanes; fatty acids such as stearic acid; metal soaps such as aluminium dimyristate, the aluminium salt of hydrogenated tallow glutamate, perfluoroalkyl phosphates, perfluoroalkylsilanes, perfluoroalkylsilazanes, polyhexafluoropropylene oxides, polyorganosiloxanes comprising perfluoroalkyl perfluoropolyether groups and amino acids; N-acylamino acids or salts thereof; lecithin, isopropyl triisostearyl titanate, and mixtures thereof.

The N-acylamino acids may comprise an acyl group containing from 8 to 22 carbon atoms, for instance a 2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl or cocoyl group. The salts of these compounds may be aluminium, magnesium, calcium, zirconium, zinc, sodium or potassium salts. The amino acid may be, for example, lysine, glutamic acid or alanine.

The term "alkyl" mentioned in the compounds cited above especially denotes an alkyl group containing from 1 to 30 carbon atoms and preferably containing from 5 to 16 carbon atoms. Hydrophobic-treated pigments are described especially in patent application EP-A-1 086 683.

Nacres

For the purposes of the present patent application, the term "nacre" means coloured particles of any form, which may or may not be iridescent, in particular produced by certain molluscs in their shell, or alternatively synthesized, and which have a colour effect via optical interference.

Examples of nacres that may be mentioned include nacreous pigments such as titanium mica coated with an iron oxide, mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica coated with an organic dye in particular of the abovementioned type, and also nacreous pigments based on bismuth oxychloride.

They may also be mica particles, at the surface of which are superposed at least two successive layers of metal oxides and/or of organic dyestuffs.

The nacres may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or coppery colour or glint.

As illustrations of nacres that may be introduced as interference pigments into the first composition, mention may be made of the gold-coloured nacres sold in particular by the company BASF under the name Brilliant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica) and Monarch gold 233X (Cloisonne); the bronze nacres sold in particular by the company Merck under the name Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by the company BASF under the name Super bronze (Cloisonne); the orange nacres sold in particular by the company BASF under the name Orange 363C (Cloisonne) and by the company Merck under the name Passion orange (Colorona) and Matte orange (17449) (Microna); the brown-tinted nacres sold in particular by the company Engelhard under the name Nu- antique copper 340XB (Cloisonne) and Brown CL4509 (Chroma-lite); the copper-tinted nacres sold in particular by the company BASF under the name Copper 340A (Timica); the red-tinted nacres sold in particular by the company Merck under the name Sienna fine (17386) (Colorona); the yellow-tinted nacres sold in particular by the company BASF under the name Yellow (4502) (Chromalite); the gold-tinted red nacres sold in particular by the company BASF under the name Sunstone G012 (Gemtone); the pink nacres sold in particular by the company BASF under the name Tan opal G005 (Gemtone); the gold-tinted black nacres sold in particular by the company BASF under the name Nu antique bronze 240 AB (Timica), the blue nacres sold in particular by the company Merck under the name Matte blue (17433) (Microna), the silvery-tinted white nacres sold in particular by the company Merck under the name Xirona Silver, and the golden-green pink-orange nacres sold in particular by the company Merck under the name Indian summer (Xirona), and mixtures thereof.

Goniochromatic pigments

For the purposes of the present invention, the term "goniochromatic pigment" denotes a pigment which makes it possible to obtain, when the composition is spread onto a support, a colour path in the a^*b^* plane of the CIE 1976 colorimetric space that corresponds to a variation Dh° in the hue angle h° of at least 20° when the angle of observation relative to the normal is varied between 0° and 80°, for an incident light angle of 45°.

The colour path may be measured, for example, using an Instrument Systems brand spectrogonioreflectometer of reference GON 360 Goniometer, after the composition has been spread in fluid form to a thickness of 300 μηη using an automatic spreader onto an Erichsen brand contrast card of reference Typ 24/5, the measurement being taken on the black background of the card.

The goniochromatic pigment may be chosen, for example, from multilayer interference structures and liquid-crystal colouring agents.

In the case of a multilayer structure, it may comprise, for example, at least two layers, each layer being made, for example, from at least one material chosen from the group consisting of the following materials: MgF2, CeF3, ZnS, ZnSe, Si, Si02, Ge, Te, Fe203, Pt, Va, AI203, MgO, Y203, S203, SiO, Hf02, Zr02, Ce02, Nb205, Ta205, Ti02, Ag, Al, Au, Cu, Rb, Ti, Ta, W, Zn, MoS2, cryolite, alloys and polymers, and combinations thereof.

The multilayer structure may or may not have, relative to a central layer, symmetry in the chemical nature of the stacked layers.

Different effects are obtained depending on the thickness and the nature of the various layers.

Examples of symmetrical multilayer interference structures are, for example, the following structures: Fe203/Si02/Fe203/Si02/Fe203, a pigment having this structure being sold under the name Sicopearl by the company BASF; MoS2/Si02/mica-oxide/Si02/MoS2; Fe203/Si02/mica-oxide/Si02/Fe203; Ti02/Si02/Ti02 and Ti02/AI203/Ti02, pigments having these structures being sold under the name Xirona by the company Merck.

The liquid-crystal colouring agents comprise, for example, silicones or cellulose ethers onto which are grafted mesomorphic groups. Examples of liquid-crystal goniochromatic particles that may be used include those sold by the company Chenix and also the product sold under the name Helicone® HC by the company Wacker.

Goniochromatic pigments that may also be used include certain nacres, pigments with effects on a synthetic substrate, especially a substrate such as alumina, silica, borosilicate, iron oxide or aluminium, or interference flakes obtained from a polyterephthalate film.

Non-limiting examples of goniochromatic pigments that may be mentioned in particular, alone or as mixtures, include the goniochromatic pigments SunShine® sold by Sun, Cosmicolor Celeste® from Toyo Aluminium K.K., Xirona® from Merck and Reflecks Multidimensions® from BASF.

These particles may optionally comprise or be covered with optical brightener(s) (or white organic fluorescent substances).

Optical brighteners are compounds well known to a person skilled in the art. Such compounds are described in "Fluorescent Whitening Agent", Encyclopedia of Chemical Technology, Kirk-Othmer, Vol. 1 1 , pp. 227-241 , 4th Edition, 1994, Wiley.

Their use in cosmetics in particular exploits the fact that they consist of chemical compounds having fluorescence properties, which absorb in the ultraviolet region (maximum absorption at a wavelength of less than 400 nm) and re-emit energy by fluorescence for a wavelength of between 380 and 830 nm. They may be defined more particularly as compounds that absorb essentially in the UVA region between 300 and 390 nm and re-emit essentially between 400 and 525 nm. Their lightening effect is based more particularly on an emission of energy between 400 and 480 nm, which corresponds to an emission in the blue part of the visible region, which contributes to lightening the skin visually when this emission takes place on the skin.

Optical brighteners that are especially known include stilbene derivatives, in particular polystyrylstilbenes and triazinylstilbenes, coumarin derivatives, in particular hydroxycoumarins and aminocoumarins, oxazole, benzoxazole, imidazole, triazole and pyrazoline derivatives, pyrene derivatives, porphyrin derivatives and mixtures thereof.

The optical brighteners that may be used may also be in the form of copolymers, for example of acrylates and/or methacrylates, grafted with optical brightener groups as described in patent application FR 99 10942. If the composition comprises a dyestuff, its content is advantageously between 0.01 % and 20% by weight relative to the total weight of the composition.

According to a particular embodiment of the invention, the composition according to the invention does not comprise any dyestuff.

Adjuvant:

In a known manner, the composition according to the invention may also contain adjuvants that are common in cosmetics, such as lipophilic gelling agents, preserving agents, fragrances, fillers, plant extracts, antioxidants and nonionic, anionic, cationic or amphoteric surfactants.

The amounts of these various adjuvants are those conventionally used in the field under consideration, for example from 0.01 to 20% of the total weight of the composition. Depending on their nature, these adjuvants may be introduced into the first oily phase and/or into the second oily phase and/or into the third oily phase.

Processes:

The compositions according to the invention may be prepared according to the following protocols.

It is thus possible to prepare, in a first stage, the third oily phase and, where appropriate, the resin and the pasty fatty substances, which are mixed together, and then, in a second stage, the first oily phase and the second oily phase.

Next, the process for preparing the emulsion may be continued, for example, according to the variants described below.

According to a first variant, the process for preparing the emulsion comprises the following steps, in this order:

- mixing of the third oily phase and, where appropriate, of the resin and the pasty fatty substances,

- stirring of the mixture until the resin has dissolved,

- addition of the first oily phase and of the second oily phase that have been premixed and homogenized together,

- introduction of the solid microparticles into the emulsion,

- emulsification of the mixture. The emulsification of these three oily phases leads to the creation of two interfaces, and more particularly a dispersion of one or two of the oily phases in the third oily phase.

In a third stage, the solid microparticles are added to the emulsion formed and the mixture is then agitated, either by means of a combination of shear forces or by ultrasonication.

According to a second variant, the process for preparing the emulsion is such that the solid microparticles are introduced into the first oily phase or into the second oily phase or into the third oily phase.

In this case, the process comprises the following steps, in this order:

- introduction of the solid microparticles, respectively, into the first oily phase or into the second oily phase or into the third oily phase and, where appropriate, of the resin and the pasty fatty substances,

- introduction, respectively, of the third oily phase and, where appropriate, of the resin and the pasty fatty substances, or of the first oily phase or the second oily phase,

- emulsification of the mixture.

According to this second variant, the microparticles are first introduced into one of the three oily phases, and a combination of shear forces or ultrasonication is then applied, so as to obtain a homogeneous dispersion of said microparticles in said oily phase. The other two oily phases are then added.

According to a third variant, the process for preparing the emulsion comprises the following steps, in this order:

- simultaneous introduction of the solid microparticles, the first oily phase, the second oily phase and the third oily phase and, where appropriate, of the resin and the pasty fatty substances,

- emulsification of the mixture.

According to this variant, the emulsion is obtained by mixing the solid microparticles and the three oily phases with vigorous stirring.

Emulsification takes place by subjecting the mixture of the three oily phases and the solid microparticles to a combination of shear forces or ultrasonication, to obtain homogeneity thereof. The term "homogeneity" of an emulsion is intended to denote an emulsion in which the drops of inner phases are uniformly dispersed in the continuous or outer oily phase.

The drops of dispersed phases in the emulsion may be very fine, in particular ranging from 0.1 to 10 μηη, or may be coarser, in particular ranging from 10 μηη to 1 cm.

A person skilled in the art may choose the conditions and the device that are the best suited for obtaining the combination of forces necessary for obtaining the targeted type of emulsion, especially for obtaining the targeted droplet size.

This combination of forces may be obtained by subjecting the first, second and third oily phases or the emulsion to manual stirring or to mechanical stirring with a blender such as a Moritz, Rayneri or Ultra-Turrax blender, or alternatively by ultrasonic homogenization.

The speed of blending or stirring for obtaining a homogeneous phase or emulsion may depend on various factors such as its composition or its volume.

The various stirring parameters, especially the speed, may be determined by a person skilled in the art on the basis of his general knowledge and, where appropriate, by means of a few routine tests. In the description and in the examples that follow, unless otherwise indicated, the percentages are weight percentages and the ranges of values written in the form "between ... and ..." include the stated lower and upper limits.

The examples below are presented as non-limiting illustrations of the field of the invention.

Example:

Compositions according to the invention as defined above were prepared and tested as regards their level of tack and also the satisfactory persistence of the colour after 1 hour (the contents are indicated as weight of starting material, unless otherwise indicated).

Protocol for preparing said compositions:

1 . The oils that constitute the third oily phase are first weighed out, along with the resin and the pasty fatty substance. The whole constitutes phase A. This phase A is introduced into a tank, heated to 1 10°C and then mixed with a Rayneri blender at 300 rpm for 20 minutes until the resin has fully dissolved.

2. The oils constituting the first oily phase and the second oily phase are weighed out in a beaker and then mixed and homogenized by hand. This constitutes phase B. This phase B is introduced into the tank at 1 10°C and then mixed with a Rayneri blender at 700 rpm.

3. The solid microparticles (phase C) are introduced into the tank and stirred for 15 minutes.

4. The constituents of phase D are weighed out and then introduced into the tank at 1 10°C and stirred for 5 minutes.

5. The dyestuffs of phase E are added to the tank and stirred for 10 minutes.

Composition Composition

Phase Ingredients

A1 A2

Polybutene (Indopol H 100 from Ineos) 7 -

Pentaerythrityl tetraisostearate

17 17 (Crodamol PTIS-LQ-(MH) from Croda)

Bis-diglyceryl poly(2-acyladipate)

6 13

Phase A (Softisan 649 from Cremer Oleo)

Hydrogenated

styrene/methylstyrene/indene copolymer

15 15 (Regalite R1 100 CG Hydrocarbon Resin

from Eastman Chemical)

Trimethyl pentaphenyl trisiloxane (Dow

Corning PH-1555 HRI Cosmetic Fluid 13 13

Phase B from Dow Corning)

Polyphenyltrimethylsiloxydimethylsiloxan

30 30 e (Belsil PDM 1000 from Wacker)

Methylsilanol/silicate crosspolymer (NLK

Phase C 2 2

506 from Takemoto Oil & Fat)

Waxes - 3

Phase D

Mineral thickener 5.2 2.2

Phase E Dyestuffs qs 100 qs 100 Makeup tests:

The persistence is evaluated by means of a Samba polarimetric camera and a Chromasphere SEI-M-0738-CHRO-10 as described in patent application FR 2 829 344.

The persistence over time of a cosmetic composition reflects its ability to withstand mechanical or physical stresses, such as friction or stretching of the made-up surface.

The persistence over time of a composition of the invention may be evaluated via various protocols, for example as described below.

Evaluation of the colour persistence is performed after a series of standardized tests ("kisses" on a paper handkerchief, the consumption of cold and/or hot drinks, and the consumption of a small standardized meal).

In order to evaluate the colour persistence, the compositions are applied to the lips of a panel of six individuals with fleshy, light-coloured lips.

Evaluation of the tack is performed by a panel of experts (20 trained individuals). Thus, just after application, the compositions according to the invention have a low level of tack. One hour after application, the compositions according to the invention are still sparingly tacky.

The compositions according to the invention also have good colour persistence after testing.

Protocol for measuring the stability:

In order to check the maintenance of the solid particles in the compositions, centrifugations were performed at room temperature. The samples of composition (gloss) were placed in tubes (about 16 g of composition) and then in the centrifuge (10 minutes at 450 rpm).

The thermal stability of the compositions of the invention was also checked: no leaching of oil is observed after 2 months at room temperature and at 47°C.

Centrifugation of the compositions according to the invention for 10 minutes at 450 rpm does not show any instability. Example 2:

The following compositions according to the invention are prepared the contents are indicated as weight of starting material, unless otherwise indicated):

The protocol used for preparing the compositions is similar to that detailed previously. However, the oily phases are introduced into a tank heated to 80°C after melting of the resin.

Composition Composition

Phase Ingredients

B1 B2

Polybutene (Indopol H 100 from Ineos) 6 6

Pentaerythrityl tetraisostearate (Crodamol

14 14 PTIS-LQ-(MH) from Croda)

Bis-diglyceryl poly(2-acyladipate) (Softisan

5 5 649 from Cremer Oleo)

Phase A Hydrogenated

styrene/methylstyrene/indene copolymer

15 15 (Regalite R1 100 CG Hydrocarbon Resin

from Eastman Chemical)

Isohexadecane (Isohexadecane from

- 6 Ineos)

Trimethyl pentaphenyl trisiloxane (Dow

Corning PH-1555 HRI Cosmetic Fluid from 12 12 Dow Corning)

Polyphenyltrimethylsiloxydimethylsiloxane

Phase B 27 27

(Belsil PDM 1000 from Wacker)

Cyclohexadimethylsiloxane (Xiameter

PMX-0246 Cyclohexasiloxane from Dow 6 - Corning)

Methylsilanol/silicate crosspolymer (NLK

Phase C 2 2

506 from Takemoto Oil & Fat)

Phase D Waxes 3 3 Mineral thickener 2.3 2.3

Phase E Dyestuffs qs 100 qs 100

The compositions according to the invention have good gloss on application and also a low level of tack.

Claims

1 . Composition in the form of an oil/oil (O/O) emulsion, which is more particularly intended for making up and/or caring for the lips, comprising at least:

- at least a first oily phase comprising at least one oil chosen from silicone oils and fluoro oils, preferably silicone oils,

- at least a second oily phase comprising at least one oil chosen from silicone oils and fluoro oils, preferably silicone oils, and

2. Composition according to Claim 1 , in which the solid microparticles comprise one or more curvatures, preferably several curvatures.

3. Composition according to either of the preceding claims, in which the solid microparticles have a hollow hemispherical shape, i.e. of "bowl" type.

4. Composition according to any one of the preceding claims, in which the solid microparticles are formed from methylsilanol/silicate crosslinked polymer.

5. Composition according to any one of the preceding claims, in which the total amount of solid microparticles ranges from 0.01 % to 5%, preferably from 0.1 % to 4% by weight and even more preferentially from 0.1 % to 3% by weight relative to the total weight of the emulsion.

6. Composition according to any one of the preceding claims, in which the first oily phase comprises at least one oil chosen from non-volatile phenyl silicone oils optionally bearing a dimethicone fragment, and more preferentially the first oily phase comprises at least one oil not bearing any dimethicone fragments; even more preferentially, the oil constituting the first oily phase is 1 ,3,5-trimethyl-1 ,1 ,3,5,5- pentaphenyltrisiloxane.

7. Composition according to any one of the preceding claims, in which the second oily phase comprises at least one oil chosen from non-volatile phenyl silicone oils optionally bearing at least one dimethicone fragment, and more preferentially the second oily phase comprises at least one oil bearing at least one dimethicone fragment; preferably, the oil constituting the second oily phase is polyphenyltrimethylsiloxydimethylsiloxane.

8. Composition according to any one of the preceding claims, in which the content of first oily phase is between 2% and 40% by weight, preferably between 5% and 35% by weight and even more preferentially between 10% and 35% by weight relative to the total weight of the composition.

9. Composition according to any one of the preceding claims, in which the content of second oily phase is between 2% and 40% by weight, preferably between 5% and 35% by weight and even more preferentially between 10% and 35% by weight relative to the total weight of the composition.

10. Composition according to any one of the preceding claims, in which the third oily phase comprises at least one polar non-volatile hydrocarbon-based oil and at least one apolar non-volatile hydrocarbon-based oil and mixtures thereof, in particular a mixture of one or more polar non-volatile hydrocarbon-based oils and one or more apolar non-volatile hydrocarbon-based oils.

1 1 . Composition according to any one of the preceding claims, in which the content of third oily phase is between 5% and 60%, preferably between 10% and 55% and even more preferentially between 15% and 55% by weight relative to the total weight of the composition.

12. Composition according to any one of the preceding claims, characterized in that it comprises at least one thickener chosen in particular from organophilic modified clays, in particular organophilic modified hectorites, in particular modified with benzyldimethylammonium stearate chloride or with distearyldimethylammonium chloride.

13. Composition according to Claim 12, characterized in that the content of mineral thickener, expressed as active material, represents from 0.5% to 30% by weight, preferably from 0.5% to 20% by weight and even more preferentially between 1 % and 15% by weight, relative to the weight of the composition.

14. Composition according to any one of the preceding claims, characterized in that it comprises at least one pasty fatty substance chosen in particular from esters of glycerol oligomers, esters of hydrogenated castor oils, totally or partially hydrogenated plant oils, and mixtures thereof, in particular chosen from esters of glycerol oligomers, especially diglycerol esters, in particular condensates of adipic acid and of diglycerol.

15. Composition according to the preceding claim, characterized in that the content of fatty substance that is pasty at room temperature and atmospheric pressure represents from 1 % to 20% by weight and preferably from 3% to 15% by weight relative to the total weight of the composition.

16. Composition according to any one of the preceding claims, in that it comprises at least one hydrocarbon-based resin having a number-average molecular weight of less than or equal to 10 000 g/mol.

17. Composition according to the preceding claim, characterized in that the hydrocarbon-based resin(s) has/have a softening point ranging from 70 to 130°C and in particular are chosen from aliphatic hydrocarbon-based resins, particularly preferably from the group formed by:

- hydrogenated indene/methylstyrene/styrene copolymers;

- aliphatic pentanediene resins;

- diene resins of cyclopentanediene dimers , of methyldicyclopentanediene, of other pentanediene dimers, and mixtures thereof;

- hydrogenated resins derived from the polymerization of pentanediene;

- and mixtures thereof,

and are more preferentially chosen from hydrogenated indene/methylstyrene/styrene copolymers.

18. Composition according to any one of the preceding claims 16 or 17, characterized in that the content of hydrocarbon-based resin is from 0.5% to 30%, preferably from 1 % to 25% and even more preferentially from 1.5% to 20% by weight relative to the total weight of the composition.

19. Composition according to any one of the preceding claims, characterized in that it comprises at least one polar wax in particular of the type such as waxes corresponding to the total esters of a saturated, optionally hydroxylated Ci₆- C₃₀ carboxylic acid with glycerol, and at least one apolar wax in particular of the type such as polyethylene waxes and a mixture thereof, in particular a mixture of a polar wax of the type such as waxes corresponding to the total esters of a saturated, optionally hydroxylated Ci₆-C₃₀ carboxylic acid with glycerol and of an apolar wax of the type such as polyethylene waxes.

20. Process for making up and/or caring for the lips, in which the composition according to any one of the preceding claims is applied.