FR3117032A1 - Gel composition comprising silica airgel and ethylguar as thickening agents - Google Patents

Abstract

Gelled composition comprising a silica airgel and ethylguar as thickening agents The present invention relates to a cosmetic composition comprising, in a physiologically acceptable medium, at least one non-volatile liquid fatty phase, at least ethylguar, and at least silica airgel. It also relates to a cosmetic process for making up and/or caring for or cleansing keratin materials or even for sun protection, comprising at least one step consisting in applying to said keratin materials at least one composition of the invention. Figure for abstract: None

Description

Gel composition comprising silica airgel and ethylguar as thickening agents

The present invention aims to provide a thickened or gelled cosmetic composition, comprising a silica airgel and ethylguar as thickening agents, and a non-volatile liquid fatty phase, having good cosmetic properties, particularly in terms of slipperiness on application. .

The cosmetic field to which the application of the composition targeted by the present invention may extend is in particular the field of make-up and/or care and/or hygiene of keratin materials, the field of sun protection or else the capillary area.

The term “keratin materials” means human keratin materials, in particular the skin, the face, the lips, the eye contour, the eyelids, the body, the nails and in particular the keratin fibers.

By “keratin fibres”, is meant in particular the hair, the eyelashes and/or the eyebrows.

By “thickener”, is meant any compound capable of increasing the viscosity of a cosmetic composition.

In cosmetic compositions, it is common to thicken non-aqueous phases to obtain the desired consistency. The thickened compositions make it easier to take the product out of its packaging without significant loss, to limit the diffusion of the product to the local treatment area, to distribute the product evenly over the local treatment area or even to be able to use the product in quantities sufficient to obtain the desired cosmetic effect.

This thickening is particularly essential for compositions such as those of care, hygiene or make-up products or even for photoprotection which must be well distributed evenly over the local surface to be treated as well as for hair compositions which must spread and distribute evenly along the keratinous fibers and do not trickle onto the forehead, neck, face or eyes.

To thicken the compositions, it is known to add fumed silica as a thickening agent (see application FR-A-1453089). It is also known to combine this fumed silica with a second thickening agent such as polysaccharide alkyl ether in cosmetic compositions as disclosed in patents FR2767698B1 and FR2767718B1.

However, when it is desired to prepare sufficiently thickened compositions, it is necessary to add a large quantity of fumed silica.

At the same time, compositions have already been proposed comprising particles of hydrophobic silica airgel combined with alkylcellulose, a film-forming agent known for its properties for improving the adhesion and holding of the films comprising it. Thus, patent FR2992205A1 describes aqueous cosmetic compositions comprising hydrophobic silica airgel particles and alkylcellulose in a particular liquid fatty phase, intended in particular to overcome the problems of annoying volatilization from a point of view of the cosmetic properties, of the solvents commonly used for the solubilization of the alkylcellulose, namely the mono-alcohols.

However, as with fumed silica and despite the combination with alkyl cellulose, it is necessary to add a significant amount of silica airgel, which has the effect of altering the cosmetic properties of the composition. In particular, we deplore at too high a content, the obtaining of an unpleasant touch, in particular rough, not very smooth or squeaky on the keratin materials, which is of course to be avoided.

There is a need to have gelled or thickened cosmetic compositions comprising a reduced quantity of thickening agents, which are homogeneous and stable over time (which do not form grains and do not phase out), which are easy to apply, and which make it possible to obtain a homogeneous, semi-gloss or low-gloss and comfortable deposit, in particular not or not very sticky, and advantageously having a satisfactory level of staying power.

There is more particularly a need to have gelled or thickened cosmetic compositions comprising at least one silica airgel as a thickener for a fatty liquid phase, in a sufficiently reduced content to improve the properties on application to keratin materials. , especially from the point of view of spreading.

The object of the present invention is precisely to meet these needs.

Thus, a first object of the present invention is to provide cosmetic compositions whose texturizing or rheological properties are finely adjustable.

Another object of the present invention is to provide a low-gloss cosmetic composition, which can be sought to obtain a more natural makeup effect on keratin materials.

Another object of the present invention is to provide a cosmetic composition that can be modulated according to its use, in terms of application property, more particularly spreadability property.

More particularly, the present invention provides a cosmetic composition that is easy to apply to keratin materials. The ease of application is reflected in particular in terms of ease of spreading. Even more particularly, the present invention proposes a cosmetic composition having an improved slipperiness.

Unexpectedly, the inventors have found that it is possible to increase the shear-thinning character of a composition by combining silica airgel with ethylguar, while maintaining a high viscosity at low shear at rest. The viscosity of the composition at rest may even be higher compared to that of compositions individually comprising each of these two constituents.

Thus, the present invention relates, according to a first of its aspects, to a composition comprising, in a physiologically acceptable medium comprising:
- at least one non-volatile liquid fatty phase,

- at least ethylguar, and

- at least silica airgel.

Unexpectedly, the inventors have indeed observed that the presence of the combination of silica airgel and ethylguar in a non-volatile liquid fatty phase, makes it possible to obtain gelled or thickened compositions whose quantity of raw materials thickeners is reduced.

As will be seen from the following, these new compositions are advantageous in several respects.

Thus, a cosmetic composition according to the invention is homogeneous, stable (no exudation or phase shift phenomenon) over time (especially after 3 months at room temperature), with low shine, easy to apply to keratin materials and provides access to a homogeneous deposit, while having good application and comfort properties.

As emerges from the examples below, the compositions in accordance with the invention and based on the implementation of the combination of silica airgel and ethylguar prove to be very advantageous in terms of texturizing or rheological properties, inducing good properties both on application and visually, in particular with regard to a low shine, which is desirable when natural makeups are desired.

Thus, compositions according to the invention can have a thickened or gelled texture which can be finely adjustable thanks to the implementation of the thickening combination required according to the invention. In particular, the compositions of the invention may have a shear-thinning texture that is particularly appreciated for application with a slippery effect or, in other words, without a "braking effect".

This same composition can thus have a high viscosity at rest, for example from 0.1 to 10000 Pa.s, in particular from 1 to 1000 Pa.s. This is why it may turn out to be particularly appreciable for said composition to be easily applicable from the point of view of spreading.

The term “braking effect” means a sensation of resistance to spreading when the composition is applied to a support or keratin material.

Also, compositions having a low gloss or a semi-gloss effect can be obtained within the scope of the present invention.

According to another of its aspects, the subject of the present application is a cosmetic process for making up and/or caring for or hygienizing keratin materials or even sun protection, comprising at least one step consisting in applying to said keratin materials at least a composition as defined previously.

Brief description of figures

represents the viscoelastic spectra of compositions comprising ethylguar (EG), or ethylguar (EG) and silica airgel, in octyldodecanol, over a frequency range from 0.1 to 100 Hz, related to Example 1.

represents the viscoelastic spectra of compositions comprising ethylguar (EG), or ethylguar (EG) and silica airgel in octyldodecanol, over a frequency range from 0.1 to 100 Hz, in relation to Example 2.

shows the flow curves of compositions comprising ethylguar (EG), or silica airgel, or ethylguar (EG) and silica airgel, in octyldodecanol, over a range of shear rate ranging from 0.01 to 1000 s ^-1 , in relation to example 2.

detailed description

ETHYLGUAR

The composition according to the invention comprises at least ethylguar.

Ethylguar is known by the INCI name: C1-C5 alkyl galactomannan.

It more particularly has a degree of substitution of 2 to 3, and in particular of 2.5 to 2.8.

Alkylated guar gums (with C1-C6 alkyl group), including ethylguar, are described in particular in patent application EP 708114 and document RD9537807 (October 1995), as well as their method of preparation.

The ethylguar concentration depends on the desired consistency for the composition.

Advantageously, the ethylguar content varies from 0.5% to 16% by weight, more particularly from 1% to 16% by weight and preferably from 1% to 12% by weight, and even more particularly from 1% to 10% by weight, relative to the total weight of the non-volatile liquid fatty phase.

SILICA AIRGELS

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

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

They are generally synthesized by a sol-gel process in a liquid medium and then usually dried by extraction of a supercritical fluid, the most commonly used being supercritical CO ₂ . This type of drying avoids the contraction of the pores and the material. The sol-gel process and the various drying methods are described in detail in Brinker CJ., and Scherer GW, Sol-Gel Science: New York: Academic Press, 1990.

The silica aerogels obtained at the end of this process are hydrophilic and the particles can then be rendered hydrophobic, in particular at the surface, for example by a reaction with a silylating agent, as explained below. Thanks to such a hydrophobic structure, silica airgel can absorb up to more than eight times its weight of oils and thus act as an oil gelling agent.

According to a particular embodiment, the silica airgel particles used in the compositions of the invention are hydrophobic silica airgel particles.

The silica airgel particles used in the present invention may have a specific surface area per unit mass (SM) ranging from 500 to 1500 m ² /g, preferably from 600 to 1200 m ² /g and better still from 600 to 800 m ² /g.

The silica airgel particles used in the present invention may have a size expressed as volume average diameter (D[0.5]) ranging from 1 to 1500 μm, better still from 1 to 1000 μm, preferably from 1 to 100 μm, in particular from 1 to 30 μm, more preferably from 5 to 25 μm, better still from 5 to 20 μm and even better still better from 5 to 15 μm.

Thus, according to one embodiment, the cosmetic composition according to the invention is characterized in that the silica airgel particles used have a specific surface area per unit mass ranging from 500 to 1500 m ² /g, preferably from 600 at 1200 m ² /g, and preferably from 600 to 800 m ² /g and a size expressed as volume average diameter (D[0.5]) ranging from 1 to 1500 μm, preferably from 1 to 1000 μm, even more preferentially from 1 to 100 μm, in particular from 1 to 30 μm, more preferably from 5 to 25 μm, better still from 5 to 20 μm and even better still from 5 to 15 μm.

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

The specific surface per unit mass can be determined by the nitrogen absorption method called the BET (Brunauer-Emmet-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 corresponds to the total specific surface of the particles considered.

The sizes of the silica airgel particles can be measured by static light scattering using a commercial particle sizer of the MasterSizer 2000 type from Malvern. The data is processed based on Mie scattering theory. This theory, exact for isotropic particles, makes it possible to determine in the case of non-spherical particles, an "effective" particle diameter. This theory is notably described in the work of Van de Hulst, H.C., “Light Scattering by Small Particles”, Chapters 9 and 10, Wiley, New York, 1957.

According to an advantageous embodiment, the silica airgel particles used in the present invention have a specific surface area per unit mass (SM) ranging from 600 to 800 m ² /g.

The silica airgel particles used in the present invention can advantageously have a packed density ρ ranging from 0.02 g/cm ³ to 0.10 g/cm ³ , preferably from 0.03 g/cm ³ to 0, 08 g/cm ³ , in particular ranging from 0.05 g/cm ³ to 0.08 g/cm ³ .

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

40 g of powder are poured into a graduated cylinder; then the specimen is placed on the STAV 2003 device from Stampf Volumeter; the specimen is then subjected to a series of 2500 compactions (this operation is repeated until the difference in volume between 2 consecutive tests is less than 2%); then the final volume Vf of packed powder is measured directly on the test piece. The packed density is determined by the m/Vf ratio, in this case 40/Vf (Vf being expressed in cm ³ and m in g).

According to a preferred embodiment, the hydrophobic silica airgel particles used in the present invention have a specific surface area per unit volume SV ranging from 5 to 60 m ² /cm ³ , preferably from 10 to 50 m ² /cm ³ and better from 15 to 40 m ² /cm ³ .

The specific surface per unit volume is given by the relationship: S _V = S _M x ρ; where ρ is the packed density expressed in g/cm ³ and SM is the specific surface per unit mass expressed in m ² /g, as defined above.

Preferably, the hydrophobic silica airgel particles according to the invention have an oil absorption 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 at 12ml/g.

The absorption capacity measured at the Wet Point, and noted Wp, corresponds to the quantity of oil that must be added to 100 g of particles to obtain a homogeneous paste.

It is measured according to the so-called Wet Point method or method for determining powder oil uptake described in standard NF T 30-022. It corresponds to the quantity of oil adsorbed on the available surface of the powder and/or absorbed by the powder by measuring the Wet Point, described below:

A quantity m = 2 g of powder is placed on a glass plate and then the oil (isononyl isononanoate) is added drop by drop. After adding 4-5 drops of oil to the powder, mix with a spatula and continue adding oil until conglomerates of oil and powder form. From this moment, add the oil one drop at a time and then triturate the mixture with the spatula. We stop adding oil when we obtain a firm and smooth paste. This paste must be spread on the glass plate without cracks or formation of lumps. The volume Vs (expressed in ml) of oil used is then noted.

The oil uptake corresponds to the Vs/m ratio.

As indicated above, according to a particular embodiment of the invention, the aerogels used are hydrophobic silica aerogels, preferably silylated silica (INCI name: silica silylate).

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

According to a particular embodiment, the hydrophobic silica airgel is obtained by replacing the hydroxyl groups present at the surface of the silica airgel with trimethylsiloxane or hexamethyldisiloxane groups.

Regarding the preparation of hydrophobic silica airgel particles surface-modified by silylation, reference may be made to document US 7,470,725.

Particles of hydrophobic silica airgels modified at the surface with trimethylsilyl groups, preferably with the INCI name Silica silylate, will preferably be used.

According to one embodiment, the cosmetic composition is characterized in that the silica airgel particles are hydrophobic silica airgel particles surface-modified with trimethylsilyl groups, preferably hydrophobic silica airgel particles with the INCI name Silica silylate.

As hydrophobic silica airgels which can be used in the invention, mention may be made, for example, of the airgel marketed under the name VM-2260 or VM-2270 (INCI name: Silica silylate), by the company Dow Corning. The VM-2260 particles have an average size of approximately 1000 microns and a specific surface area per unit mass ranging from 600 to 800 m ² /g. The VM-2270 particles have an average size ranging from 5 to 15 microns and a specific surface area per unit mass ranging from 600 to 800 m ² /g.

Mention may also be made of the aerogels marketed by Cabot under the references Aerogel TLD 201®, Aerogel OGD 201®, Airgel TLD 203®, ENOVA Aerogel MT 1100®, ENOVA Aerogel MT 1200®, CAB-O-SIL TS-530, CAB-O-SIL TS-610, CAB-O-SIL TS-720.

Preferably, the silica airgel particles are present in the composition according to the invention in a content of active material ranging from 0.1% to 15% by weight, preferably from 0.1% to 10% by weight. , and even more preferably from 1% to 5% by weight, relative to the total weight of the non-volatile liquid fatty phase.

According to a particular embodiment, the compositions according to the invention advantageously comprise at least from 0.1% to 15% by weight of silica airgel and from 2% to 16% by weight of ethylguar relative to the total weight of the non-volatile liquid fatty phase.

According to a particularly preferred embodiment, the ethylguar and the silica airgel are used in the composition according to the invention in an ethylguar/silica airgel weight ratio of between 0.1 and 10, preferably between 0. 1 and 5.

As emerges from the examples below, the silica airgel and the ethylguar required according to the invention, when they are combined and both used in an "effective amount", make it possible to obtain compositions whose texture can be fine tuned. The inventors have observed that the rheological behavior of the gel obtained was particularly advantageous. Indeed, the measurements of the parameters G' and G'', as defined below, show that it is possible to obtain a structured gel over the entire frequency range tested. As illustrated in Example 1, it is found that the curves G' and G'' do not intersect. In other words, the composition tends towards a stable homogeneous gelled system which can be suspensive in the event of the presence of particulate compounds of the filler or dye type.

The inventors have thus demonstrated an increase in the shear-thinning character at increasing shear speed of the combination of silica airgel and ethylguar for the thickening of a non-volatile liquid fatty phase.

By "effective amount" is meant within the meaning of the present invention an amount sufficient to obtain the expected effect, as described above.

Without being bound by any theory, the inventors have put forward several hypotheses that could justify this increase in the shear-thinning character of the combination of ethylguar and silica airgel particles:

- obtaining an entanglement between the polymer chains of ethylguar and the hydrophobic chains grafted to the surface of the silica airgel particles,

- the formation of hydrogen bonds between the silica airgel particles and the ethylguar because the ethylguar still presents OH groups on its polymer chains and likewise on the surface of the airgel which can present OH groups at its surface. Ethylguar can then form bridges between the silica particles, thus reinforcing the 3D network formed by the silica airgel particles, resulting in a gel that can be described as "strong".

Within the meaning of the present invention, the term "strong gel" is understood to mean a gel having a ratio between the elastic modulus (G') and the viscous modulus (G'') greater than 5, whatever the frequency of stress.

FAT LIQUID PHASE

The composition according to the invention comprises at least one liquid fatty phase.

NON-VOLATILE FAT LIQUID PHASE

The composition according to the invention comprises at least one non-volatile liquid fatty phase.

According to an even more particular embodiment, the non-volatile liquid fatty phase comprises at least one non-volatile protic polar oil.

This polar protic non-volatile oil is referred to as "first oil" in the following description.

According to another particular embodiment, the liquid fatty phase comprises at least one non-volatile liquid fatty phase, and in particular at least one first non-volatile polar protic oil, and optionally at least one second non-volatile oil chosen from silicone oils and / or fluorinated and / or non-volatile hydrocarbon oils other than said first oil.

Preferably, the non-volatile liquid fatty phase comprises:

- at least one first non-volatile polar protic oil, and

- at least one second non-volatile oil chosen from silicone and/or fluorinated oils, and/or non-volatile hydrocarbon oils different from said first oil.

By “oil”, we mean a non-aqueous compound, immiscible with water, liquid at room temperature (25°C) and atmospheric pressure (760 mm Hg).

By "non-volatile", we mean an oil whose vapor pressure at room temperature and atmospheric pressure is non-zero and less than 0.02 mm Hg (2.66 Pa) and better still less than 10 ^-3 mm Hg (0.13Pa).

FIRST NON-VOLATILE OIL PROTIC FLEECE

According to a particular embodiment, the composition according to the invention comprises one or more “first polar protic non-volatile oil(s)”.

By “polar oil”, within the meaning of the present invention, is meant an oil whose solubility parameter δ _a at 25° C. is different from 0 (J/cm ³ ) ^½ . In particular, the term "polar oil" means an oil whose chemical structure is essentially formed, or even constituted, of carbon and hydrogen atoms, and comprising at least one strongly electronegative heteroatom such as an oxygen atom , nitrogen, silicon or phosphorus.

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

According to this Hansen space:

- δ _D characterizes the LONDON dispersion forces resulting from the formation of dipoles induced during molecular shocks;

- δ _p characterizes the DEBYE interaction forces between permanent dipoles as well as the KEESOM interaction forces between induced dipoles and permanent dipoles;

- δ _h characterizes the forces of specific interactions (type hydrogen bonds, acid/base, donor/acceptor, etc.); and

- δ _a is determined by the equation: δ _a = (δ _p ² + δ _h ²) ^½ .

The parameters δ _p , δ _h , δ _D and δ _a are expressed in (J/cm ³ ) ^½ _.

Preferably, the polar oils used according to the present invention have a δ _a greater than 3.

By “protic oil”, is meant an oil capable of forming hydrogen bonds, namely whose solubility parameter δ _h is non-zero.

Preferably, the protic polar non-volatile oil can be a hydrocarbon oil.

By "hydrocarbon oil" is meant an oil formed essentially, or even consisting, of carbon and hydrogen atoms, and optionally of oxygen atoms and free of heteroatoms such as N, Si, F and P. L Hydrocarbon oil is therefore distinct from a silicone oil and a fluorinated oil.

In the present case, the protic polar non-volatile oil comprises at least one oxygen atom.

In particular, the non-volatile polar protic oil comprises at least one alcohol function (it is then an "alcohol oil") and/or at least one ester function (it is then an "ester oil ").

The ester oils that can be used in the compositions according to the invention can in particular be hydroxylated.

As first non-volatile polar protic oil, mention may be made in particular of:

- hydrocarbon oils of animal origin,

- hydrocarbon oils of plant origin such as phytostearyl esters, such as phytostearyl oleate, physostearyl isostearate and lauroyl/octyldodecyl/phytostearyl glutanate, for example sold under the name ELDEW PS203 by AJINOMOTO, triglycerides consisting of esters of fatty acids and of glycerol, the fatty acids of which may have chain lengths varying from C4 to C24, the latter possibly being linear or branched, saturated or unsaturated; these oils are in particular heptanoic or octanoic triglycerides, oils of wheat germ, sunflower, grape seed, sesame, corn, apricot, castor, camelina, shea, avocado, olive, soya, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, squash, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, bankoulier, passionflower, muscat rose; shea butter; or caprylic/capric acid triglycerides such as those sold by the company STEARINERIES DUBOIS or those sold under the names MIGLYOL 810®, 812® and 818® by the company DYNAMIT NOBEL, refined vegetable perhydrosqualene marketed under the name fitoderm by the company Cognis;

- synthetic esters, such as the oils of formula R ₁ COOR ₂ , in which R ₁ represents a residue of a linear or branched fatty acid comprising from 1 to 40 carbon atoms and R ₂ represents a hydrocarbon chain, in particular branched containing from 1 to 40 carbon atoms provided that R ₁ + R ₂ is greater than or equal to 10. The esters can be, in particular, chosen from alcohol and fatty acid esters, such as, for example, octanoate esters of isopropyl alcohol, such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, isopropyl stearate, octyl, hydroxylated esters, such as isostearyl lactate, octyl hydroxystearate, alcohol or polyalcohol ricinoleates, hexyl laurate, neopentanoic acid esters, such as isodecyl neopentanoate, isotridecyl neopentanoate, esters of isononanoic acid, such as isonony isononanoate le, isotridecyl isononanoate,

- polyol esters and pentaerythritol esters, such as dipentaerythritol tetrahydroxystearate/tetraisostearate,

- fatty alcohols that are liquid at room temperature with a branched and/or unsaturated carbon chain having 12 to 26 carbon atoms, such as 2-octyldodecanol, isostearyl alcohol, oleic alcohol,

- higher C ₁₂ -C ₂₂ fatty acids, such as oleic acid, linoleic acid, linolenic acid, and mixtures thereof,

According to a particular embodiment, said first non-volatile protic polar oil is chosen from hydrocarbon oils of plant origin, synthetic esters and fatty alcohols which are liquid at room temperature with a branched and/or unsaturated carbon chain having from 12 to 26 carbon atoms.

Among the non-volatile polar protic oils which can be used according to the invention, use is more particularly made of triesters of glycerides and in particular of triglycerides of caprylic/capric acids, synthetic esters and in particular isopropyl myristate and ethylhexylpalmitate, and alcohols fat including octyldodecanol. Preferably, said first oil is chosen from triglycerides of caprylic/capric acids, isopropyl myristate, and octyldodecanol, and preferably is at least octyldodecanol.

According to a particular embodiment, a composition according to the invention comprises one or more first non-volatile oil(s) polar protic(s) in a content ranging from 5% to 75%, in particular from 10% to 50% by weight, preferably from 20% to 45% by weight, relative to its total weight.

According to a particularly preferred embodiment, the nonvolatile polar protic oil and ethylguar are used in the composition according to the invention in a weight ratio "raw) oil (s)" nonvolatile polar (s) ) protic(s)/ethylguar comprised between 10 and 60, preferably comprised between 15 and 40. Particularly preferably, the weight ratio “first oil(s)” polar protic(s)/ethylguar is between 10 and 40.

SECOND NON-VOLATILE OIL

According to one of its aspects, a composition according to the invention further comprises at least one second non-volatile oil chosen from silicone oils and/or fluorinated oils and/or non-volatile hydrocarbon-based oils different from said first oil, in particular is at least one silicone oil.

Preferably, the non-volatile oil(s) chosen from silicone oils and/or non-volatile fluorinated and/or hydrocarbon-based oils different from said first oil is/are present in a total content ranging from 5% to 75% by weight, preferably from 10% to 40% by weight, or else from 15% to 30% by weight, relative to the total weight of said composition.

According to a particularly preferred embodiment, the composition comprises a total content of non-volatile oils (that is to say all the non-volatile oils of the composition, whatever their nature) of between 40% and 80% by weight , preferably between 45% and 75% by weight relative to the total weight of the composition.

According to a particularly preferred embodiment, the non-volatile oils (that is to say all the non-volatile oils of the composition, whatever their nature) and ethylguar are used in the composition according to the invention. in a non-volatile oil(s)/ethylguar weight ratio of between 10 and 60, preferably between 15 and 40.

Non-volatile silicone oil

According to a first preferred embodiment, the non-volatile oil is a silicone oil.

By “silicone oil” is meant an oil comprising at least one Si atom.

The non-volatile silicone oil that can be used in the invention may in particular be chosen from silicone oils having in particular a viscosity at 25° C. greater than or equal to 9 centistokes (cSt) (9×10 ^-6 m ² /s), and less at 800,000 cSt, preferably between 50 and 600,000 cSt, preferably between 100 and 500,000 cSt. The viscosity of this silicone can be measured according to the ASTM D-445 standard.

According to a first embodiment, the non-volatile silicone oil is a non-phenylated silicone oil.

The non-volatile non-phenylated silicone oil can be chosen from:

- non-volatile polydimethylsiloxanes (PDMS),

- PDMS comprising pendant alkyl or alkoxy groups and/or at the ends of the silicone chain, groups each having from 2 to 24 carbon atoms,

- PDMS comprising aliphatic and/or aromatic groups, or functional groups such as hydroxyl, thiol and/or amine groups,

- polyalkylmethylsiloxanes optionally substituted with a fluorinated group such as polymethyltrifluoropropyldimethylsiloxanes,

- polyalkylmethylsiloxanes substituted with functional groups such as hydroxyl, thiol and/or amine groups,

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

According to one embodiment, a composition according to the invention contains at least one non-phenylated silicone oil, in particular such as a linear oil (that is to say non-cyclic)

As representative of these non-volatile and non-phenylated linear silicone oils, mention may be made of polydimethylsiloxanes; alkyldimethicones; vinylmethyl methicones; as well as silicones modified with aliphatic groups, optionally fluorinated, or with functional groups such as hydroxyl, thiol and/or amine groups.

The non-phenyl silicone oil can in particular be chosen from the silicones of formula (I):

(I)

in which :

R ₁ , R ₂ , R ₅ and R ₆ are, together or separately, an alkyl radical having 1 to 6 carbon atoms,

R ₃ and R ₄ are, together or separately, an alkyl radical having from 1 to 6 carbon atoms, a vinyl radical, an amine radical or a hydroxyl radical,

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

n and p being integers chosen so as to have a fluid compound, in particular the viscosity of which at 25° C. is between 9 centistokes (cSt) (9×10 ^-6 m ² /s) and 800,000 cSt.

As non-volatile silicone oil that can be used according to the invention, mention may be made of the compounds of formula (I) for which:

- the substituents R ₁ to R ₆ and X represent a methyl group, p and n are such that the viscosity is 500,000 cSt, such as that sold under the name SE30 by the company General Electric, that sold under the name AK 500000 by the company Waker, that sold under the name Mirasil DM 500,000 by the company Bluestar and that sold under the name Dow Corning 200 Fluid 500,000 cSt by the company Dow Corning.

- the substituents R ₁ to R ₆ and X represent a methyl group, p and n are such that the viscosity is 60,000 cSt, such as that sold under the name Dow Corning 200 Fluid 60000 CS by the company Dow Corning and that sold under the denomination Wacker Belsil DM 60,000 by the company Wacker.

- the substituents R ₁ to R ₆ and X represent a methyl group, p and n are such that the viscosity is 350 cSt, such as that sold under the name Dow Corning 200 Fluid 350 CS by the company Dow Corning.

- R substituents₁at R₆represent a methyl group, the group X represents a hydroxy group, n and p are such that the viscosity is 700 cSt, such as that sold under the name Baysilone Fluid T0.7 by the company Momentive.

According to another embodiment, a composition according to the invention contains at least one non-volatile phenyl silicone oil as second non-volatile oil.

As representatives of these phenylated non-volatile silicone oils, mention may be made of:

- phenyl silicone oils corresponding to the following formula:

(II)

in which the R groups represent independently of each other a methyl or a phenyl, provided that at least one R group represents a phenyl. Preferably, in this formula, the phenyl silicone oil comprises at least three phenyl groups, for example at least four, at least five or at least six.

- phenyl silicone oils corresponding to the following formula:

(III)

in which the R groups represent independently of each other a methyl or a phenyl, provided that at least one R group represents a phenyl.

Preferably in this formula, said organopolysiloxane comprises at least three phenyl groups, for example at least four or at least five. Mixtures of the phenylated organopolysiloxanes described above can be used. Mention may be made, for example, of mixtures of triphenyl, tetra- or penta-phenyl organopolysiloxanes.

- phenyl silicone oils corresponding to the following formula:

(IV)

wherein Me represents methyl, Ph represents phenyl. Such a phenyl silicone is notably manufactured by Dow Corning under the reference PH-1555 HRI or even Dow Corning 555 Cosmetic Fluid (chemical name: 1,3,5-trimethyl 1,1,3,5,5-pentaphenyl trisiloxane, INCI name : trimethylpentaphenyl trisiloxane). Dow Corning 554 Cosmetic Fluid can also be used.

- phenyl silicone oils corresponding to the following formula:

(V)

in which Me represents methyl, y is between 1 and 1000, and X represents –CH ₂ -CH(CH ₃ )(Ph).

- phenyl silicone oils corresponding to the following formula (VI):

(VI)

in which Me is methyl and Ph is phenyl, OR' represents an -OSiMe ₃ group and y is 0 or varies between 1 and 1000, z varies between 1 and 1000, such that the compound (VI) is a non-volatile oil .

According to a first preferred embodiment, y varies between 1 and 1000. It is possible to use, for example, trimethyl Siloxyphenyl Dimethicone, in particular sold under the reference BELSIL PDM 1000 marketed by the company Wacker.

According to another embodiment, y is equal to 0. It is possible to use, for example, PHENYL TRIMETHYLSILOXY TRISILOXANE, in particular sold under the reference DOW CORNING 556 COSMETIC GRADE FLUID.

- phenyl silicone oils corresponding to the following formula (VII), and mixtures thereof:

(VII)

in which :

- R ₁ to R ₁₀ , independently of each other, are hydrocarbon radicals, saturated or unsaturated, linear, cyclic or branched, C ₁ -C ₃₀ ,

- m, n, p and q are, independently of each other, whole numbers between 0 and 900, provided that the sum 'm+n+q' is different from 0.

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

- phenyl silicone oils corresponding to the following formula (VIII), and mixtures thereof:

(VIII)

in which :

- R ₁ to R ₆ , independently of each other, are hydrocarbon radicals, saturated or unsaturated, linear, cyclic or branched, C ₁ -C ₃₀ ,

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

Preferably, R ₁ to R ₆ , independently of each other, represent a saturated hydrocarbon radical, linear or branched, C ₁ -C ₃₀ , in particular C ₁ -C ₁₂ , and in particular a methyl, ethyl, propyl radical or butyl.

In particular, R ₁ to R ₆ can be identical, and in addition can be a methyl radical.

Preferably, one can have m=1 or 2 or 3, and/or n=0 and/or p=0 or 1, in the formula (VIII).

- phenyl silicone oils corresponding to formula (IX), and mixtures thereof:

(IX)

in which :

- R is a C ₁ -C ₃₀ alkyl radical, an aryl radical or an aralkyl radical,

- n is an integer ranging from 0 to 100, and

- m is an integer varying from 0 to 100, provided that the sum n+m varies from 1 to 100.

In particular, the radicals R of formula (IX) and R ₁ to R ₁₀ previously defined, can each represent a linear or branched, saturated or unsaturated alkyl radical, in particular C ₂ -C ₂₀ , in particular C ₃ -C ₁₆ and more particularly C ₄ -C ₁₀ , or a mono- or polycyclic C ₆ -C ₁₄ aryl radical, in particular C ₁₀ -C ₁₃ or an aralkyl radical whose aryl and alkyl residues are as defined previously.

Preferably, R of formula (IX) and R ₁ to R ₁₀ can each represent a methyl, ethyl, propyl, isopropyl, decyl, dodecyl or octadecyl radical, or else a phenyl, tolyl, benzyl or phenethyl radical.

According to one embodiment, it is possible to use a phenyl silicone oil of formula (IX) having a viscosity at 25° C. of between 5 and 1500 mm ² /s (i.e. 5 to
1500 cSt), preferably having a viscosity between 5 and 1000 mm ² /s (i.e. 5 to
1000 cSt).

As phenyl silicone oil of formula (IX), it is possible to use in particular phenyltrimethicones such as DC556 from Dow Corning (22.5 cSt), Silbione 70663V30 oil from Rhône Poulenc (28 cSt), or diphenyldimethicones such as Belsil, including Belsil PDM1000 (1000cSt), Belsil PDM 200 (200 cSt) and Belsil PDM 20 (20cSt) from Wacker. Values in parentheses represent viscosities at 25°C.

- phenyl silicone oils corresponding to the following formula, and mixtures thereof:

(X)

in which :

R ₁ , R ₂ , R ₅ and R ₆ are, together or separately, an alkyl radical having 1 to 6 carbon atoms,

R ₃ and R ₄ are, together or separately, an alkyl radical having from 1 to 6 carbon atoms, or an aryl radical,

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

n and p being chosen so as to give the oil a molecular mass by weight of less than 200,000 g/mol, preferably less than 150,000 g/mol and even more preferably less than 100,000 g/mol.

- the phenyl silicones are more particularly chosen from phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, and 2-phenylethyl trimethylsiloxysilicates, and mixtures thereof.

More particularly, the phenyl silicones are chosen more from phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, and 2-phenylethyl trimethylsiloxysilicates, and mixtures thereof.

Preferably, the molecular weight by weight of the non-volatile phenyl silicone oil according to the invention varies from 500 to 10,000 g/mol.

By way of example of preferred non-volatile silicone oils, mention may be made of silicone oils such as:

- phenyl silicones (also called phenyl silicone oil) such as TRIMETHYLSILOXYPHENYL DIMETHICONE (as BELSIL PDM 1000 from WACKER (MW=9000 g/mol) (see above formula (VI), phenyl trimethicones (such as phenyl trimethicone sold under the trade name DC556 by Dow Corning), phenyl dimethicones, phenyl trimethylsiloxy diphenyl siloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenylethyl trimethylsiloxysilicates, trimethylpentaphenyl trisiloxane (such as that sold under the name Dow Corning PH-1555 HRI cosmetic fluid by Dow Corning) (see formula (IV) above ),

- non-volatile polydimethylsiloxanes (PDMS), polydimethylsiloxanes comprising alkyl or alkoxy groups, pendent and/or at the end of the silicone chain, groups each having from 2 to 24 carbon atoms;

- and mixtures thereof.

Preferably, the second non-volatile oil is a phenyl silicone oil.

According to a preferred embodiment, the phenyl silicone oil is chosen from trimethylsiloxyphenyldimethicones.

According to a preferred embodiment, the non-volatile silicone oil(s) is/are present in a total content ranging from 5% to 75% by weight, in particular from 10% to 40% by weight, preferably from 15 to 30% by weight, relative to the total weight of said composition.

Non-volatile fluorinated oil

According to a second embodiment, the second non-volatile oil is a fluorinated oil.

By “fluorinated oil” is meant an oil comprising at least one fluorine atom.

The fluorinated oils that can be used according to the invention can be chosen from fluorosilicone oils, fluorinated polyethers, fluorinated silicones as described in document EP-A-847752 and perfluorinated compounds.

By perfluorinated compounds is meant according to the invention compounds in which all the hydrogen atoms have been substituted by fluorine atoms.

According to a particularly preferred embodiment, the fluorinated oil according to the invention is chosen from perfluorinated oils.

By way of example of perfluorinated oils that can be used in the invention, mention may be made of perfluorodecalins and perfluoperhydrophenanthrenes.

According to a particularly preferred embodiment, the fluorinated oil chosen from perfluoperhydrophenanthrenes, and in particular the ^Fiflow® products marketed by the company Créations Couleurs. In particular, it is possible to use fluorinated oil, the INCI name of which is perfluoperhydrophenanthrene, marketed under the reference FIFLOW 220 by the company F2 Chemicals.

Non-volatile hydrocarbon oil different from the first oil

The non-volatile hydrocarbon oil different from said first oil can be an apolar oil.

By “nonpolar oil” within the meaning of the present invention, is meant an oil whose solubility parameter at 25° C., δ _a , is equal to 0 (J/cm ³ ) ^½ .

The non-volatile apolar hydrocarbon oil is free of oxygen atoms.

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

- paraffin oil or its derivatives,

- Vaseline oil,

- naphthalene oil,

- polybutylenes such as INDOPOL H-100 (molar mass or MW=965 g/mol), INDOPOL H-300 (MW=1340 g/mol), INDOPOL H-1500 (MW=2160 g/ mol) marketed or manufactured by AMOCO,

- hydrogenated polyisobutylenes such as Parléam ^® marketed by the company NIPPON OIL FATS, the PANALANE H-300 E marketed or manufactured by the company AMOCO (MW = 1340 g/mol), the VISEAL 20000 marketed or manufactured by the company SYNTEAL ( MW=6000 g/mol), REWOPAL PIB 1000 marketed or manufactured by WITCO (MW=1000 g/mol),

- decene/butene copolymers, polybutene/polyisobutene copolymers, in particular Indopol L-14,

-polydecenes and hydrogenated polydecenes such as: PURESYN 10 (MW=723 g/mol), PURESYN 150 (MW=9200 g/mol) marketed or manufactured by the company MOBIL CHEMICALS,

- and mixtures thereof.

According to a particular embodiment, the present invention relates to a composition comprising a second non-volatile oil being a silicone oil chosen from non-phenyl silicone oils and phenyl silicone oils, and in particular is at least one phenyl silicone oil, preferably the trimethyl Siloxyphenyl Dimethicone.

According to another particular embodiment, the composition also comprises at least one volatile oil.

VOLATILE OILS

By “volatile oil” is meant any oil capable of evaporating on contact with the skin in less than one hour, at ambient temperature and atmospheric pressure. The volatile oil is a volatile cosmetic compound, liquid at ambient temperature, having in particular a non-zero vapor pressure, at ambient temperature and atmospheric pressure, in particular having a vapor pressure ranging from 0.13 Pa to 40,000 Pa (10 ^{- 3} at 300 mm Hg), in particular ranging from 1.3 Pa to 13000 Pa (0.01 to 100 mm Hg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mm Hg ).

The volatile oils can be hydrocarbon-based or silicone-based.

According to a particular embodiment of the invention, when it is present, the volatile oil is apolar.

“Apolar oil” means an oil whose solubility parameter at 25° C., δ _a , is equal to 0 (J/cm ³ ) ^½ .

The definition and calculation of the solubility parameters in Hansen's 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:
- δ _D characterizes the London dispersion forces resulting from the formation of dipoles induced during molecular shocks;
- δ _p characterizes the Debye interaction forces between permanent dipoles as well as the Keesom interaction forces between induced dipoles and permanent dipoles;
- δ _h characterizes the forces of specific interactions (type hydrogen bonds, acid/base, donor/acceptor, etc.); and
- δ _a is determined by the equation: δ _a = (δp² + δh²) ^½ .
The parameters δ _p , δ _h , δ _D and δ _a are expressed in (J/cm ³ ) ^½ .

Thus, according to a particular embodiment, the composition also comprises a volatile oil, in particular apolar oil.

According to an even more particular embodiment, the liquid fatty phase comprises at least one first non-volatile polar protic oil, and at least one volatile oil, in particular apolar oil.

Among the apolar volatile oils, mention may in particular be made, among the volatile hydrocarbon oils having from 8 to 16 carbon atoms, of the branched C ₈ -C ₁₆ alkanes such as the C ₈ -C ₁₆ iso-alkanes (also called isoparaffins), the isododecane, isodecane, isohexadecane and, for example, the oils sold under the trade names Isopars or Permetyls, branched C ₈ -C ₁₆ esters such as iso-hexyl neopentanoate, and mixtures thereof. In particular, the volatile hydrocarbon-based oil is chosen from volatile hydrocarbon-based oils having from 8 to 16 carbon atoms and mixtures thereof.

Preferably, the volatile oil is isododecane.

Mention may also be made of volatile linear alkanes comprising from 8 to 16 carbon atoms, in particular from 10 to 15 carbon atoms, and more particularly from 11 to 13 carbon atoms, for example such as n-dodecane (C ₁₂ ) and n-tetradecane (C ₁₄ ) sold by Sasol respectively under the references Parafol 12-97 and Parafol 14-97, as well as their mixtures, the undecane-tridecane mixture, the mixtures of n-undecane (C ₁₁ ) and of n -tridecane (C ₁₃ ) obtained in examples 1 and 2 of application WO 2008/155059 from Cognis, and mixtures thereof.

As volatile silicone oils, mention may be made of linear volatile silicone oils such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, tetradecamethylhexasiloxane, hexadecamethylheptasiloxane and dodecamethylpentasiloxane.

As volatile cyclic silicone oils, mention may be made of hexamethylcyclotrisiloxane, octamethylcylotetrasiloxane, decamethylcyclopentasiloxane, cyclohexasiloxane and dodecamethylcyclohexasiloxane, and in particular cyclohexasiloxane.

In addition to the oils described above, the composition under consideration according to the invention may also comprise at least one solid fatty substance such as waxes.

Raincoats)

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

By “wax” within the meaning of the present invention, is meant a lipophilic compound, solid at room temperature (25° C.), with a reversible solid/liquid state change, having a melting point greater than or equal to 30° C. go up to 120°C.

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

Preferably, the measurement protocol is as follows:

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

The wax may in particular 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 force in compression measured at 20° C. using the texturometer sold under the name TA-TX2i by the company RHEO, equipped with a stainless steel cylinder with a diameter of 2 mm moving at the measurement speed of 0.1 mm/s, and penetrating the wax to a penetration depth of 0.3 mm.

The waxes can be hydrocarbon, silicone or fluorinated and be of vegetable, mineral, animal and/or synthetic origin.

In particular, the waxes have a melting point above 30°C and better still above 45°C.

Apolar wax

By “non-polar wax”, within the meaning of the present invention, is meant a wax whose solubility parameter δ _a at 25° C. as defined below is equal to 0 (J/cm ³ ) ^½ .

Apolar waxes are in particular hydrocarbon waxes consisting solely of carbon and hydrogen atoms and free of heteroatoms such as N, O, Si and P.

In particular, by apolar wax is meant a wax which consists solely of apolar wax and not a mixture which would also include other types of waxes which are not apolar waxes.

By way of illustration of apolar waxes suitable for the invention, mention may in particular be made of hydrocarbon waxes such as microcrystalline waxes, paraffin waxes, ozokerite, polymethylene waxes, polyethylene waxes, microwaxes, in particular of polyethylene.

As polyethylene waxes, mention may be made of PERFORMALENE 500-L POLYETHYLENE and PERFORMALENE 400 POLYETHYLENE marketed by New Phase Technologies and ASENSA SC 211 marketed by HONEYWELL.

As polymethylene wax, mention may be made of CIREBELLE108 marketed by Cirebelle.

As ozokerite, we can mention OZOKERITE WAX SP 1020 P.

As microcrystalline waxes that can be used, mention may be made of MULTIWAX W 445 ^® marketed by the company SONNEBORN and MICROWAX HW ^® and BASE WAX 30540 ^® marketed by the company PARAMELT.

As microwaxes which can be used in the O/O emulsions according to the invention as apolar wax, mention may in particular be made of polyethylene microwaxes such as those marketed under the names of Micropoly 200 ^® , 220 ^® , 220L ^® and 250S ^® by the company MICROPOWDERS.

polar wax

By “polar wax”, within the meaning of the present invention, is meant a wax whose solubility parameter δ _a at 25° C. is different from 0 (J/cm ³ ) ^½ .

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

The polar waxes can in particular be hydrocarbon-based, fluorinated or silicone-based, and preferably hydrocarbon-based or silicone-based.

By “silicone wax”, is meant an oil comprising at least one silicon atom, and in particular comprising Si—O groups.

By "hydrocarbon wax" is meant a wax formed essentially, or even consisting, of carbon and hydrogen atoms, and optionally of oxygen and nitrogen atoms, and not containing any silicon or fluorine. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.

Hydrocarbon waxes

According to a first preferred embodiment, the polar wax is a hydrocarbon wax.

As hydrocarbon-based polar wax, a wax chosen from ester waxes and alcohol waxes is particularly preferred.

By “ester wax”, is meant according to the invention a wax comprising at least one ester function. The ester waxes can additionally be hydroxylated.

By “alcohol wax”, is meant according to the invention a wax comprising at least one alcohol function, that is to say comprising at least one free hydroxyl (OH) group.

It is possible in particular to use as ester wax:

- ester waxes such as those chosen from:

i) waxes of formula R ₁ COOR ₂ in which R ₁ and R ₂ represent linear, branched or cyclic aliphatic chains whose number of atoms varies from 10 to 50, possibly containing a heteroatom such as O, N or P and whose melting point temperature varies from 25°C to 120°C. In particular, it is possible to use as ester wax a C ₂₀ -C ₄₀ alkyl (hydroxystearyloxy) stearate (the alkyl group comprising from 20 to 40 carbon atoms), alone or as a mixture, or a C ₂₀ alkyl stearate -C ₄₀ . Such waxes are in particular sold under the names “Kester Wax K 82 ^P® ”, “Hydroxypolyester K 82 ^P® ”, “Kester Wax K 80 ^P® ”, or “KESTER WAX K82H” by the company KOSTER KEUNEN.
It is also possible to use a glycol and butylene glycol montanate (octacosanoate) such as LICOWAX KPS FLAKES wax (INCI name: glycol montanate) marketed by the company Clariant.

ii) di-(1,1,1-trimethylol propane) tetrastearate, sold under the name Hest 2T- ^4S® by the company HETERENE.

iii) diester waxes of a dicarboxylic acid of general formula R ₃ -(-OCO-R ₄ -COO-R ₅ ), in which R ₃ and R ₅ are identical or different, preferably identical and represent an alkyl group in C ₄ -C ₃₀ (alkyl group comprising from 4 to 30 carbon atoms) and R ₄ represents a linear or branched aliphatic C ₄ -C ₃₀ group (alkyl group comprising from 4 to 30 carbon atoms) and which may or may not contain one or more unsaturations. Preferably, the C ₄ -C ₃₀ aliphatic group is linear and unsaturated.

iv) Mention may also be made of the waxes obtained by catalytic hydrogenation of animal or vegetable oils having fatty chains, linear or branched, C ₈ -C ₃₂ , for example such as hydrogenated jojoba oil, sunflower oil hydrogenated castor oil, hydrogenated coconut oil, as well as 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 SOPHIM. Such waxes are described in application FR-A-2792190. As waxes obtained by hydrogenation of olive oil esterified with stearyl alcohol, mention may be made of those sold under the name “PHYTOWAX Olive 18 L 57”.

v) Waxes corresponding to partial or total esters, preferably total, of a C ₁₆ -C ₃₀ carboxylic acid, saturated, optionally hydroxylated, with glycerol. By total esters, it is meant that all the hydroxyl functions of the glycerol are esterified.
By way of example, mention may be made of trihydroxystearin (or glyceryl trihydroxystearate), tristearin (or glyceryl tristearate), tribehenin (or glyceryl tribehenate), alone or as a mixture. Among suitable compounds, mention may be made of triesters of glycerol and of 12-hydroxystearic acid, or of hydrogenated castor oil, such as for example Thixcin R, Thixcin E, marketed by Elementis Specialties.

vi) Mention may also be made of the ester of behenic acid and glycerol, and in particular mixtures of esters of behenic acid and glycerol, such as for example the mixture glyceryl dibehenate, tribehenin, glyceryl behenate marketed by the company Gattefossé under the reference COMPRITOL 888 CG ATO.

vii) Mention may also be made of beeswax, synthetic beeswax, polyglycerolated beeswax, carnauba wax, candelilla wax, oxypropylene lanolin wax, rice bran wax, Ouricury wax, Alfa wax, Cork fiber wax, Sugar cane wax, Japan wax, Sumac wax, Montan wax, Orange wax, Laurel wax , hydrogenated jojoba wax, and mixtures thereof.

According to another embodiment, the polar wax can be an alcohol wax.

Mention may be made, as alcohol wax, of alcohols, preferably linear, preferably saturated, comprising from 16 to 60 carbon atoms, the melting point of which is between 25 and 120°C. As an alcohol wax, mention may be made, for example, of Performacol 550-L Alcohol wax from New Phase Technology, stearic alcohol, cetyl alcohol, myristic alcohol, palmitic alcohol, behenic alcohol, erucic alcohol, arachidyl alcohol, or mixtures thereof.

Silicone waxes

By “silicone wax”, is meant an oil comprising at least one silicon atom, and in particular comprising Si—O groups.

Among the commercial silicone waxes of this type, mention may be made in particular of those sold under the names Abilwax 9810 (GOLDSCHMIDT), KF910 and KF7002 (SHIN ETSU), or 176-11481 (GENERAL ELECTRIC).

The silicone waxes that can be used can also be alkyl or alkoxydimethicones, as well as (C ₂₀ -C ₆₀ )alkyldimethicones, in particular (C ₃₀ -C ₄₅ )alkyldimethicones such as the silicone wax sold under the name SF-1642 by the company GE-Bayer Silicones or C _{30-45 ALKYLDIMETHYLSILYL} POLYPROPYL SILSESQUIOXANE under the name SW- ^8005® C30 RESIN WAX marketed by the company DOW CORNING.

Mention may also be made of silicone waxes obtained by esterification with a (poly)alkoxylated silicone such as silicone beeswax, silicone candelilla wax, silicone carnauba wax.

Preferably, the wax or waxes are chosen from ester waxes, and more particularly is cetyl alcohol.

Thus, according to a preferred embodiment, the wax(es) is/are present in a total content ranging from 0.1% to 5% by weight, in particular from 0.25% to 2.5% by weight. , preferably from 0.5% to 2% by weight, relative to the total weight of said composition.

AQUEOUS PHASE

A composition according to the invention may comprise an aqueous phase.

The term “aqueous phase” means a phase comprising water and in general any molecule in the dissolved state in the water in the composition. Preferably, the aqueous phase is an aqueous solution.

According to one embodiment, the aqueous phase according to the invention may contain water.

According to a preferred embodiment, the aqueous phase may also comprise water-soluble solvents.

By “water-soluble solvent”, is meant in the present invention a compound that is liquid at room temperature and miscible with water (miscibility in water greater than 50% by weight at 25° C. and atmospheric pressure).

The water-soluble solvents that can be used in the compositions according to the invention can also be volatile.

Among the water-soluble solvents which can be used in the compositions in accordance with the invention, mention may in particular be made of lower monoalcohols having from 1 to 5 carbon atoms, such as ethanol and isopropanol, glycols having from 2 to 8 carbon atoms. carbon such as ethylene glycol, propylene glycol, 1,3-butylene glycol and dipropylene glycol, C ₃ and C ₄ ketones and C ₂ -C ₄ aldehydes.

According to one embodiment, the aqueous phase may be present in a total content ranging from 2 to 95% by weight, preferably ranging from 5 to 60% by weight, and more particularly ranging from 10 to 50% by weight, relative to the total weight of the composition.

The aqueous phase according to the invention can also comprise at least one hydrophilic thickener and/or at least one surfactant. However, the aqueous phase content previously indicated does not include the contents of each of the compounds mentioned above.

SURFACTANTS

The composition according to the invention may contain an emulsifying system comprising one or more surfactants present, in particular in a content ranging from 0.1% to 20% by weight relative to the total weight of the composition, or even 0.5% to 15 % by weight, preferably ranging from 1% to 10% by weight.

Advantageously, when the composition comprises a surfactant, it is present in a content such that the weight ratio total content of non-volatile oils / content of surfactant(s) is between 1 and 40, preferably between 5 and 35. Preferably, they are present in a total non-volatile oil content/surfactant(s) content weight ratio of between 8 and 25.

In particular, it is possible to use an emulsifying surfactant having, at 25° C., an HLB balance (hydrophilic-lipophilic balance) within the meaning of GRIFFIN, greater than or equal to 8.

It is also possible to use an emulsifying surfactant having, at 25° C., an HLB balance (hydrophilic-lipophilic balance) within the meaning of GRIFFIN, of less than 8.

The HLB value according to GRIFFIN is defined in J. Soc. Cosm. Chem. 1954 (volume 5), pages 249-256.

These surfactants can be chosen from nonionic, anionic, cationic, amphoteric surfactants and mixtures thereof. Reference may be made to the document “Encyclopedia of Chemical Technology, KIRK-OTHMER”, volume 22, p. ^333-432 , 3rd edition, 1979, WILEY, for the definition of the properties and emulsifying functions of surfactants, in particular p. 347-377 of this reference, for anionic, amphoteric and nonionic surfactants.

According to a first embodiment, the composition comprises at least one hydrocarbon surfactant.

Examples of hydrocarbon surfactants suitable for the invention are described below.

Nonionic surfactants

The nonionic surfactants can be chosen in particular from alkyl- and polyalkyl- esters of poly (ethylene oxide), oxyalkylenated alcohols, alkyl- and polyalkyl- ethers of poly (ethylene oxide), alkyl- and polyalkyl - sorbitan esters, polyoxyethylenated or not, alkyl- and polyalkyl- ethers of sorbitan, polyoxyethylenated or not, alkyl- and polyalkyl-glycosides or polyglycosides, in particular alkyl- and polyalkyl-glucosides or polyglucosides, alkyl- and polyalkyl - esters of sucrose, alkyl- and polyalkyl-esters of glycerol, polyoxyethylenated or not, alkyl- and polyalkyl- ethers of glycerol, polyoxyethylenated or not and mixtures thereof.

1) As alkyl- and polyalkyl-esters of poly(ethylene oxide), those having a number of ethylene oxide (EO) units ranging from 2 to 200 are preferably used. Mention may be made, for example, of stearate 40 EO, 50 EO stearate, 100 EO stearate, 20 EO laurate, 40 EO laurate, 150 EO distearate.

2) As poly(ethylene oxide) alkyl- and polyalkyl-ethers, those having a number of ethylene oxide (EO) units ranging from 2 to 200 are preferably used. Mention may be made, for example, of cetyl ether 23 EO, oleyl ether 50 EO, phytosterol 30 EO, steareth 40, steareth 100, beheneth 100.

3) As oxyalkylenated alcohols, in particular oxyethylenated and/or oxypropylene alcohols, those which may contain from 1 to 150 oxyethylene and/or oxypropylene units, in particular having from 20 to 100 oxyethylene units, are preferably used, in particular fatty alcohols, in particular C ₈ -C ₂₄ , and preferably C ₁₂ -C ₁₈ , ethoxylated such as stearyl alcohol ethoxylated with 20 oxyethylene units (CTFA name "Steareth-20") such as BRIJ 78 marketed by the company UNIQEMA, cetearyl alcohol ethoxylated with 30 oxyethylene units (CTFA name "Ceteareth-30") and the mixture of C ₁₂ -C ₁₅ fatty alcohols comprising 7 oxyethylene units (CTFA name "C _12-15 Pareth-7") such as that marketed under the name NEODOL 25-7® by SHELL CHEMICALS; or in particular oxyalkylenated (oxyethylenated and/or oxypropylene) alcohols having from 1 to 15 oxyethylene and/or oxypropylene units, in particular C ₈ -C ₂₄ , and preferably C ₁₂ -C ₁₈ , ethoxylated fatty alcohols such as stearyl alcohol ethoxylated with 2 oxyethylene units (CTFA name “Steareth-2”) such as BRIJ 72 marketed by the company UNIQEMA;

4) As alkyl- and polyalkyl-esters of sorbitan, polyoxyethylenated or not, those having a number of ethylene oxide (EO) units ranging from 0 to 100 are preferably used. Mention may be made, for example, of sorbitan laurate 4 or 20 EO, in particular polysorbate 20 (or polyoxyethylene (20) sorbitan monolaurate) such as the product Tween 20 marketed by the company Uniqema, sorbitan palmitate 20 EO, sorbitan stearate 20 EO, sorbitan oleate 20 OE or the Crémophor (RH 40, RH 60, etc.) from BASF. As non-polyoxyethylenated sorbitan alkyl and polyalkyl esters, a mixture of sorbitan stearate and sucrose cocoate is preferably used, preferably that marketed under the reference Arlacel 2121 U from CRODA.

5) As alkyl- and polyalkyl- ethers of sorbitan, polyoxyethylenated or not, those having a number of ethylene oxide (EO) units ranging from 0 to 100 are preferably used.

6) As alkyl- and polyalkyl-glucosides or polyglucosides, those containing an alkyl group containing from 6 to 30 carbon atoms and preferably from 6 to 18, or even from 8 to 16 carbon atoms, and containing a glucoside group preferably comprising from 1 to 5, in particular 1, 2 to 3 glucoside units. The alkylpolyglucosides can be chosen for example from decylglucoside (Alkyl-C ₉ /C ₁₁ -polyglucoside (1.4)) such as the product sold under the name Mydol 10 ^® by the company Kao Chemicals or the product sold under the name Plantacare 2000 UP ^® by the company Henkel and the product marketed under the name ^ORAMIX NS 10® by the company SEPPIC; caprylyl/capryl glucoside, such as the product marketed under the name Plantacare KE ^3711® by the company Cognis or ^ORAMIX CG 110® by the company SEPPIC; laurylglucoside, such as the product marketed under the name Plantacare 1200 ^UP® by the company Henkel or Plantaren 1200 ^N® by the company Henkel; cocoglucoside, such as the product marketed under the name Plantacare 818 ^UP® by the company Henkel; caprylylglucoside, such as the product marketed under the name Plantacare 810 ^UP® by the company Cognis; and their mixtures.

More generally, surfactants of the alkylpolyglycoside type are defined more specifically below.

7) As alkyl- and polyalkyl-esters of sucrose, mention may be made, for example, of Crodesta F150, sucrose monolaurate marketed under the name Crodesta SL 40, the products marketed by Ryoto Sugar Ester such as, for example, sucrose palmite marketed under the reference Ryoto Sugar Ester P1670, Ryoto Sugar Ester LWA 1695, Ryoto Sugar Ester 01570.

8) As alkyl- and polyalkyl- esters of glycerol, polyoxyethylenated or not, preferably used are those having a number of ethylene oxide (EO) units ranging from 0 to 100 and a number of glycerol units ranging from 1 to 30. Mention may be made, for example, of hexaglyceryl monolaurate and PEG-30 glyceryl stearate.

9) As alkyl- and polyalkyl- ethers of glycerol, polyoxyethylenated or not, preferably used are those having a number of ethylene oxide (EO) units ranging from 0 to 100 and a number of glycerol units ranging from 1 to 30. Examples include Nikkol Batyl alcohol 100, Nikkol chimyl alcohol 100.

Anionic surfactants

The anionic surfactants can be chosen from alkyl ether sulfates, carboxylates, derivatives of amino acids, sulfonates, isethionates, taurates, sulfosuccinates, alkylsulfoacetates, phosphates and alkylphosphates, polypeptides, metal salts of acids bold in C₁₀-VS₃₀, especially in C₁₂-VS₂₀, in particular metallic stearates and their mixtures.

1) As alkyl ether sulphates, mention may be made, for example, of sodium lauryl ether sulphate (C12-14 70-30) (2.2 EO) marketed under the names SIPON AOS225 or TEXAPON N702 by the company Henkel, lauryl ether sulphate ammonium (C12-14 70-30) (3 EO) marketed under the name SIPON LEA 370 by the company Henkel, the alkyl (C ₁₂ -C ₁₄ ) ether (9 EO) ammonium sulphate marketed under the name RHODAPEX AB/20 by the company Rhodia Chimie, and the mixture of lauryl and oleyl ether sulphate of sodium and magnesium marketed under the name EMPICOL BSD 52 by the company Albright & Wilson.

2) As carboxylates, mention may be made, for example, of the salts (for example alkaline) of N-acylamino acids, glycol carboxylates, amido ether carboxylates (AEC) and salts of polyoxyethylenated carboxylic acids.

The surfactant of the glycol carboxylate type can be chosen from alkyl glycol carboxylic or 2-(2-hydroxyalkyloxy acetate), salts thereof and mixtures thereof. These carboxylic alkyl glycols comprise a linear or branched, saturated or unsaturated, aliphatic and/or aromatic alkyl chain having from 8 to 18 carbon atoms. These carboxylics can be neutralized by mineral bases such as potash or soda.

As surfactants of the carboxylic glycol type, mention may be made, for example, of sodium lauryl glycol carboxylate or sodium 2-(2-hydroxyalkyloxy acetate) such as the product marketed under the name Beaulight Shaa ^® by the company Sanyo, Beaulight LCA-25N ^® or the corresponding acid form Beaulight Shaa (Acid form) ^® .

As amido ether carboxylate (AEC), mention may be made, for example, of sodium lauryl amido ether carboxylate (3 EO), marketed under the name AKYPO FOAM ^30® by the company Kao Chemicals.

As polyoxyethylenated carboxylic acid salt, mention may be made, for example, of sodium lauryl ether carboxylate (C _12-14-16 65/25/10) oxyethylenated (6 EO) marketed under the name AKYPO SOFT 45 ^NV® by the company Kao Chemicals, polyoxyethylenated and carboxymethylated fatty acids of olive oil origin marketed under the name OLIVEM 400 ^® by the company BIOLOGIA E TECNOLOGIA, oxyethylenated sodium tri-decyl ether carboxylate (6 EO) marketed under the name NIKKOL ECTD-6NEX ^® by the Nikkol company.

3) As derivatives of amino acids, mention may be made in particular of the alkaline salts of amino acids, such as:

• sarcosinates, such as sodium lauroyl sarcosinate marketed under the name SARKOSYL NL 97 ^® by the company Ciba or marketed under the name ORAMIX L 30 ^® by the company Seppic, sodium myristoyl sarcosinate marketed under the name NIKKOL SARCOSINATE MN ^® by the company Nikkol, the sodium palmitoyl sarcosinate marketed under the name NIKKOL SARCOSINATE PN ^® by the company Nikkol.
• alaninates, such as sodium N-lauroyl-N methyl amidopropionate marketed under the name SODIUM NIKKOL ALANINATE LN 30 ^® by the company Nikkol, or marketed under the name ALANONE ALE ^® by the company Kawaken, N-lauroyl N-methyl alanine triethanolamine marketed under the name ALANONE ^ALTA® by the company Kawaken.
• glutamates, such as mono-cocoyl glutamate of triethanolamine marketed under the name ^{ACYLGLUTAMATE} CT-12® by the company Ajinomoto, lauroylglutamate of triethanolamine marketed under the name ^{ACYLGLUTAMATE} LT-12® by the company Ajinomoto.

The salts and/or derivatives of glutamic acid are described more precisely below.

• aspartates, such as the mixture of N-lauroyl aspartate of triethanolamine/N-myristoyl aspartate of triethanolamine marketed under the name ^ASPARACK® by the company Mitsubishi.
• glycine derivatives (glycinates), such as sodium N-cocoyl glycinate marketed under the names AMILITE GCS-12® and ^AMILITE GCK 12 by the company Ajinomoto.
• citrates such as the citric mono-ester of oxyethylenated coconut alcohols (9 moles), marketed under the name WITCONOL EC 1129 by the company Goldschmidt.
• galacturonates such as sodium dodecyl D-galactoside uronate marketed by the company Soliance.

4) As sulfonates, mention may be made, for example, of alpha-olefin sulfonates such as sodium alpha-olefin sulfonate (C ₁₄ - ₁₆ ) marketed under the name BIO-TERGE AS-40 ^® by the company Stepan, marketed under the names WITCONATE AOS PROTEGE ^® and SULFRAMINE AOS PH 12 ^® by the company Witco or marketed under the name BIO-TERGE AS-40 CG ^® by the company Stepan, the secondary sodium olefin sulphonate marketed under the name HOSTAPUR SAS 30 ^® by the company Clarifying;

5) As isethionates, mention may be made of acylisethionates such as sodium cocoyl-isethionate, such as the product marketed under the name JORDAPON CI P ^® by the company Jordan.

6) As taurates, mention may be made of the sodium salt of palm kernel oil methyltaurate marketed under the name HOSTAPON CT ^PATE® by the company Clariant; N-acyl N-methyltaurates such as sodium N-cocoyl N-methyltaurate marketed under the name HOSTAPON LT-SF ^® by the company Clariant or marketed under the name NIKKOL CMT-30-T ^® by the company Nikkol, palmitoyl methyltaurate of sodium marketed under the name NIKKOL ^PMT® by the company Nikkol.

7) As sulfosuccinates, mention may be made, for example, of lauryl alcohol mono-sulfosuccinate (C₁₂/VS₁₄70/30) oxyethylenated (3 EO) marketed under the names SETACIN 103 SPECIAL^®, REWOPOL SB-FA 30 K 4^®by the company Witco, the disodium salt of a hemi-sulfosuccinate of alcohols C₁₂-VS₁₄, marketed under the name SETACIN F SPECIAL PASTE^®by the company Zschimmer Schwarz, the oxyethylenated disodium oleamidosulfosuccinate (2 EO) marketed under the name STANDAPOL SH 135^®by the company Henkel, oxyethylenated lauric amide mono-sulfosuccinate (5 EO) marketed under the name LEBON A-5000^®by the company Sanyo, the di-sodium salt of oxyethylenated lauryl citrate monosulfosuccinate (10 EO) marketed under the name REWOPOL SB CS 50^®by Witco, ricinoleic monoethanolamide monosulfosuccinate marketed under the name REWODERM S 1333^®by the company Witco. It is also possible to use polydimethylsiloxane sulfosuccinates such as the disodium PEG-12 dimethicone sulfosuccinate marketed under the name MACKANATE-DC30 by the company Mac Intyre.

8) As alkyl sulfoacetate, mention may be made, for example, of the mixture of sodium lauryl sulfoacetate, di-sodium lauryl ether sulfosuccinate, marketed under the name STEPAN-MILD LSB by the company Stepan.

9) As phosphates and alkylphosphates, mention may be made, for example, of monoalkylphosphates and dialkyl phosphates, such as the lauryl monophosphate marketed under the name MAP ^20® by the company Kao Chemicals, the potassium salt of dodecyl-acid phosphoric, mixture of mono- and diester (predominant diester) marketed under the name CRAFOL AP-31 ^® by the company Cognis, the mixture of monoester and diester of octylphosphoric acid, marketed under the name CRAFOL AP-20 ^® by the company Cognis, the mixture of monoester and diester of ethoxylated 2-butyloctanol phosphoric acid (7 moles of EO), marketed under the name ISOFOL 12 7 EO-PHOSPHATE ESTER ^® by the company Condea, the potassium or triethanolamine salt mono-alkyl (C ₁₂ -C ₁₃ ) phosphate sold under the references ARLATONE MAP 230K-40 ^® and ARLATONE MAP 230T-60 ^® by the company Uniqema, potassium lauryl phosphate sold under the name DERMALCAR E MAP XC-99/ ^09® by Rhodia Chimie, and potassium cetyl phosphate marketed under the name ARLATONE MAP 160K by Uniqema.

10) The polypeptides are obtained for example by condensation of a fatty chain on cereal amino acids and in particular wheat and oats. As polypeptides, mention may be made, for example, of the potassium salt of hydrolyzed lauroyl wheat protein, marketed under the name AMINOFOAM W OR by the company Croda, the triethanolamine salt of hydrolyzed cocoyl soy protein, marketed under the name MAY-TEIN SY by the company Maybrook, the sodium salt of oat lauroyl amino acids, marketed under the name PROTEOL OAT by the company Seppic, the hydrolyzate of collagen grafted on coconut fatty acid, marketed under the name GELIDERM 3000 by Deutsche Gelatine, soy proteins acylated with hydrogenated copra acids, marketed under the name PROTEOL VS 22 by Seppic.

11) As metal salts of C ₁₀ -C ₃₀ fatty acids, in particular C ₁₂ -C ₂₀ fatty acids, mention may be made in particular of metal stearates, such as sodium stearate and potassium stearate, as well as polyhydroxy stearates .

Cationic surfactants

The cationic surfactants can be chosen from:

• alkylimidazolidiniums such as isostearyl-ethylimidonium etho-sulphate,
• ammonium salts such as (C _12-30 alkyl)-tri(C _1-4 alkyl)ammonium halides such as N,N,N-trimethyl-1-docosanaminium chloride (or Behentrimonium chloride ).

Amphoteric surfactants

The compositions according to the invention may also contain one or more amphoteric surfactants such as N-acyl-amino acids such as N-alkyl-aminoacetates and disodium cocoamphodiacetate, and amine oxides such as stearamine oxide, or even silicone surfactants such as dimethicone copolyol phosphates such as that sold under the name PECOSIL PS 100® by the company PHOENIX CHEMICAL.

Preferably, the composition according to the invention comprises at least one nonionic surfactant as stabilizing agent, preferably chosen from alkyl ether sulphates, in particular sodium lauryl ether sulphate, and the alkyl- and polyalkyl- esters of sorbitan, in particular non-polyethylenated, and better still a mixture of sorbitan stearate and sucrose cocoate, preferably that marketed under the reference Arlacel 2121 from Croda.

HYDROPHILIC GELLING POLYMER

The term “gelling polymer of the aqueous phase” within the meaning of the present application means a polymer capable of gelling the aqueous phase of the compositions according to the invention.

The gelling polymer which can be used according to the invention can in particular be characterized by its ability to form in water, above a certain concentration C*, a gel characterized by oscillatory rheology (μ=1 Hz) by a threshold of 'flow _c at least equal to 10 Pa. This concentration C* can vary widely depending on the nature of the gelling polymer considered.

By way of illustration, this concentration is between 1 and 2% by weight for a sodium acrylamide/acrylamido-2-methyl propane sulfonate copolymer in a 40% inverse emulsion in polysorbate 80/I-C16 such as that marketed under the name “Simulgel 600” by the company SEPPIC, and is approximately 0.5% by weight for an AMPS/ethoxylated cetearyl methacrylate (25 EO) copolymer crosslinked with trimethylolpropane triacrylate (TMPTA) of the ARISTOFLEX HMS type.

The gelling polymer may be present in the composition in an amount sufficient to adjust the modulus of rigidity G*(1Hz, 25° C.) of the composition to a value greater than or equal to 10,000 Pa, in particular ranging from 10,000 Pa to 100,000 Pa. The method for measuring the modulus of rigidity G*(1Hz, 25° C.) of the composition is described in more detail below.

The gelling polymer is a hydrophilic polymer and is therefore present in the aqueous phase of the composition.

More particularly, this gelling polymer can be chosen from:

- homo- or copolymers of acrylic or methacrylic acids or their salts and their esters and in particular the products sold under the names
“VERSICOL F” or “VERSICOL K” by ALLIED COLLOID,
"UTRAHOLD 8" by the company CIBA-GEIGY, polyacrylic acids of the SYNTHALEN K type, and salts, in particular of sodium, of polyacrylic acid (responding to the INCI name sodium acrylate copolymer) and more particularly a crosslinked sodium polyacrylate (responding in the INCI name sodium acrylate copolymer (and) caprylic/capric triglyceride) sold under the name “LUVIGEL EM” by the company,

- the copolymers of acrylic acid and acrylamide sold in the form of their sodium salt under the names “RETEN” by the company HERCULES, the sodium polymethacrylate sold under the name “DARVAN N°7” by the company VANDERBILT, the sodium salts of polyhydroxycarboxylic acids sold under the name "HYDAGEN F" by the company HENKEL,

- polyacrylic acid/alkyl acrylate copolymers, preferably modified or unmodified carboxyvinyl polymers, very particularly preferred according to the present invention are acrylate/C ₁₀ -C ₃₀ -alkylacrylate copolymers (INCI name Acrylates/C10-30 Alkyl acrylate Crosspolymer) such as the products marketed by the company Lubrizol under the trade names PEMULEN TR1, PEMULEN TR2, CARBOPOL 1382, CARBOPOL EDT 2020 and even more preferably PEMULEN TR-2;

- AMPS (polyacrylamidomethyl propane sulphonic acid partially neutralized with ammonia and highly cross-linked) marketed by CLARIANT,

- AMPS/acrylamide copolymers of the SEPIGEL or SIMULGEL type marketed by the company SEPPIC,

- polyoxyethylenated AMPS/alkyl methacrylate copolymers (crosslinked or not) of the ARISTOFLEX HMS type marketed by the company CLARIANT,

- and mixtures thereof.

As other examples of hydrophilic gelling polymers, mention may be made of:

- anionic, cationic, amphoteric or nonionic chitin or chitosan polymers;

- cellulose polymers, distinct from alkylcellulose, chosen from hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, as well as quaternized derivatives of cellulose;

- vinyl polymers, such as polyvinylpyrrolidones, copolymers of methylvinyl ether and malic anhydride, copolymer of vinyl acetate and crotonic acid, copolymers of vinylpyrrolidone and vinyl acetate; copolymers of vinylpyrrolidone and caprolactam; polyvinyl alcohol;

- polymers of natural origin, possibly modified, such as gum arabic, Ghatti gum, Konjac gum, Gellan gum, Fennugreek gum, Tragacanth gum, Arabic gum, acacia gum , hydroxypropylguar (Jaguar HP105, Rhodia), hydroxypropylguar modified with sodium methylcarboxylate groups (Jaguar XC97-1, Rhodia), hydroxypropyl tri-methyl ammonium guar chloride,

- microbial gums including:

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

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

3) scleroglucan gum (polymer of glucose);

- gums from seaweed including:

1) agar (polymer derived from galactose and anhydrogalactose),

2) alginates (polymers of mannuronic acid and glucuronic acid),

3) carrageenans and furcellerans (polymers of galactose sulphate and anhydrogalactose sulphate),

- glycoaminoglycans, hyaluronic acid and its derivatives;

- deoxyribonucleic acid;

- muccopolysaccharides such as hyaluronic acid, chondroitin sulphate, and mixtures thereof.

- starch,

- inulin,

- pectin.

As other examples of additional hydrophilic gelling agents, mention may also be made of polysaccharide alkyl ethers, different from ethylguar as defined above.

The term “polysaccharide alkyl ether” means a polysaccharide comprising at least two different osidic units, each unit comprising at least one hydroxyl group substituted by a C ₁ -C ₂₄ , preferably C ₁ -C _{10 , alkyl chain.}

The term “alkyl chain” is understood to mean a saturated chain, linear or branched, comprising from 1 to 24, preferably from 1 to 10, better still from 1 to 5, and more especially from 1 to 3 carbon atoms. In particular, the alkyl chain is chosen from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, preferably ethyl, groups.

Polysaccharide alkyl ethers are described in particular in documents EP898958B1 and FR3048179B1.

According to the invention, a polysaccharide alkyl ether having a molecular weight greater than 100,000 g/mol, and preferably greater than 200,000 g/mol, is preferred. This molecular weight can go up to 1 million g/mol.

This alkyl ether can comprise from one to six and better still from two to four hydroxyl groups per unit, substituted by an alkyl chain as previously described.

The osidic cycles are chosen in particular from mannose, galactose, glucose, furanose, rhamnose, arabinose.

Preferably, the polysaccharide alkyl ether is an alkyl ether of a gum and more particularly of a globally nonionic gum, that is to say comprising little or no ionic group, preferably nonionic.

As suitable gums, mention may be made, for example, of galactomannans such as guar gum, the unit of which comprises a galactose and a mannose, locust bean gum, the unit of which comprises a galactose and a mannose; karaya gum which is a complex mixture of rhamnose, galactose and galacturonic acid; gum tragacanth which is a complex mixture of arabinose, galactose and galacturonic acid.

Preferably, the additional polysaccharide alkyl ether is a derivative of guar gum, always different from ethylguar.

According to a particular embodiment, the present invention is characterized in that the polysaccharide alkyl ether comprising at least two different osidic units, each unit comprising at least one hydroxyl group substituted by a C ₁ -C ₂₄ alkyl chain, preferably in C ₁ -C ₁₀ , the osidic units being able to be chosen from mannose, galactose, glucose, furanose, rhamnose, arabinose and the alkyl chain being able to be chosen from methyl, ethyl, n-propyl groups, isopropyl, n-butyl, isobutyl, tertiobutyl, preferably ethyl, said polysaccharide alkyl ether being in particular a galactomannan such as guar gum, locust bean gum, karaya gum, tragacanth gum.

According to a particularly preferred embodiment, the gelling agent is chosen from associative polymers.

By "associative polymer" within the meaning of the present invention, is meant any amphiphilic polymer comprising in its structure at least one fatty chain and at least one hydrophilic portion. The associative polymers in accordance with the present invention can be anionic, cationic, nonionic or amphoteric.

Associative anionic polymers

Among the associative anionic polymers, mention may be made of those comprising at least one hydrophilic unit, and at least one fatty chain allyl ether unit, more particularly among those whose hydrophilic unit consists of an ethylenically unsaturated anionic monomer, more particularly of a vinyl carboxylic acid and most particularly by an acrylic acid, a methacrylic acid or mixtures thereof, and whose fatty chain allyl ether unit corresponds to the monomer of formula (XI) below:

(XI)

in which R' denotes H or CH ₃ , B denotes the ethyleneoxy radical, n is zero or denotes an integer ranging from 1 to 100, R denotes a hydrocarbon radical chosen from alkyl, arylalkyl, aryl, alkylaryl, cycloalkyl radicals, comprising 8 to 30 carbon atoms, preferably 10 to 24, and more particularly still from 12 to 18 carbon atoms.

Anionic amphiphilic polymers of this type are described and prepared, according to an emulsion polymerization process, in patent EP-0 216 479.

Among the associative anionic polymers, mention may also be made of maleic anhydride/C ₃₀ -C ₃₈ α-olefin/alkyl maleate terpolymers such as the product (maleic anhydride/C ₃₀ -C ₃₈ α-olefin copolymer/ isopropyl maleate) sold under the name PERFORMA V 1608 by the company NEWPHASE TECHNOLOGIES.

Among the associative anionic polymers, it is possible, according to a preferred embodiment, the copolymers comprising among their monomers an α,β-monoethylenically unsaturated carboxylic acid and an α,β-monoethylenically unsaturated carboxylic acid ester and a fatty alcohol oxyalkylene.

Preferably, these compounds also comprise, as monomer, an ester of an α,β-monoethylenically unsaturated carboxylic acid and of a C ₁ -C ₄ alcohol.

As an example of this type of compound, mention may be made of ACULYN 22® sold by the company ROHM and HAAS, which is a terpolymer of methacrylic acid/ethyl acrylate/oxyalkylenated stearyl methacrylate (comprising 20 EO units) or l 'Aculyn 28 (methacrylic acid/ethyl acrylate/behenyl oxyethylene methacrylate (25EO) terpolymer.

As associative anionic polymers, mention may also be made of anionic polymers comprising at least one hydrophilic unit of the olefinic unsaturated carboxylic acid type, and at least one hydrophobic unit exclusively of the (C ₁₀ -C ₃₀ ) alkyl ester type of unsaturated carboxylic acid . Mention may be made, by way of example, of the anionic polymers described and prepared according to US Pat. Nos. 3,915,921 and 4,509,949.

Cationic associative polymers

As cationic associative polymers, mention may be made of quaternized cellulose derivatives and polyacrylates with amino side groups.

The quaternized cellulose derivatives are, in particular:

- quaternized celluloses modified by groups comprising at least one fatty chain, such as alkyl, arylalkyl, alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof,

- quaternized hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl, alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof.

Polyacrylates with amine side groups, quaternized or not, have for example hydrophobic groups of the steareth 20 type (polyoxyethylenated(20) stearyl alcohol).

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

Mention may be made, as examples of quaternized alkylhydroxyethyl celluloses with C ₈ -C ₃₀ fatty chains, of the products QUATRISOFT LM 200, QUATRISOFT LM-X 529-18-A, QUATRISOFT LM-X 529-18B (C ₁₂ alkyl) and QUATRISOFT LM-X 529-8 (C ₁₈ alkyl) marketed by the company AMERCHOL and the products CRODACEL QM, CRODACEL QL (C ₁₂ alkyl) and CRODACEL QS (C 18 alkyl) marketed by the company CRODA.

As examples of polyacrylates with amino side chains, mention may be made of the polymers 8781-121B or 9492-103 from the company NATIONAL STARCH.

Non-ionic associative polymers

The non-ionic associative polymers can be chosen from:

- celluloses modified by groups comprising at least one
fatty chain such as for example hydroxyethylcelluloses modified by groups comprising at least one fatty chain such as alkyl groups, in particular C ₈ -C ₂₂ , arylalkyl, alkylaryl, such as NATROSOL PLUS GRADE 330 CS (C ₁₆ alkyl) sold by the company AQUALON,

- celluloses modified with polyalkylene glycol ether of alkyl phenol groups, such as the product AMERCELL POLYMER HM-1500 (polyethylene glycol (15) ether of nonyl phenol) sold by the company AMERCHOL,

- guars such as hydroxypropylguar,

- copolymers of vinyl pyrrolidone and fatty chain hydrophobic monomers;

- copolymers of C ₁ -C ₆ alkyl methacrylates or acrylates and amphiphilic monomers comprising at least one fatty chain,

- copolymers of hydrophilic methacrylates or acrylates and hydrophobic monomers comprising at least one fatty chain such as, for example, polyethylene glycol methacrylate/lauryl methacrylate copolymer,

- associative polyurethanes

Associative polyurethanes are nonionic block copolymers comprising in the chain both hydrophilic sequences of a nature most often polyoxyethylenated (polyurethanes can then be called polyether polyurethanes) and hydrophobic sequences which can be aliphatic sequences alone and/or or cycloaliphatic and/or aromatic chains.

In particular, these polymers comprise at least two lipophilic hydrocarbon chains, having from C ₆ to C ₃₀ carbon atoms, separated by a hydrophilic sequence, the hydrocarbon chains can be pendant chains or chains at the end of a hydrophilic sequence. In particular, it is possible that one or more hanging chains are provided. In addition, the polymer may comprise a hydrocarbon chain at one end or at both ends of a hydrophilic block.

Associative polyurethanes can be sequenced in triblock or multiblock form. The hydrophobic blocks can therefore be at each end of the chain (for example: triblock copolymer with a hydrophilic central block) or distributed both at the ends and in the chain (multiblock copolymer for example). These polymers can also be in grafts or in stars. Preferably, the associative polyurethanes are triblock copolymers whose hydrophilic sequence is a polyoxyethylenated chain comprising from 50 to 1000 oxyethylenated groups. In general, associative polyurethanes have a urethane bond between the hydrophilic sequences, hence the origin of the name.

According to a preferred embodiment, a nonionic associative polymer of polyurethane type is used as gelling agent.

By way of example of polyurethane polyethers that cannot be used in the invention, mention may be made of the polymer C ₁₆ -OE ₁₂₀ -C ₁₆ from the company SERVO DELDEN (under the name SER AD FX1100, molecule with urethane function and average molecular weight by weight of 1300), EO being an oxyethylenated unit.

As polyurethane associative polymer, it is also possible to use Rheolate 205 with a urea function sold by the company RHEOX or alternatively Rheolate 208 or 204 or alternatively Rheolate FX 1100 by Elementis. These associative polyurethanes are sold in pure form. The product DW 1206B from RHOM & HAAS with a C ₂₀ alkyl chain and urethane bond, sold at 20% dry matter in water, can also be used.

It is also possible to use solutions or dispersions of these polymers, in particular in water or in an aqueous-alcoholic medium. By way of example, such polymers include SER AD FX1010, SER AD FX1035 and SER AD 1070 from SERVO DELDEN, Rheolate 255, Rheolate 278 and Rheolate 244 sold by RHEOX. It is also possible to use the product Aculyn 46, DW 1206F and DW 1206J, as well as Acrysol RM 184 or Acrysol 44 from the company ROHM & HAAS, or even Borchigel LW 44 from the company BORCHERS, and their mixtures. .

According to a preferred embodiment, the hydrophilic gelling agent is chosen from:

- hydroxypropyl guar,

- vinyl polymers, such as polyvinyl alcohol;

- anionic associative polymers derived from (meth)acrylic acid, such as the non-crosslinked copolymer obtained from methacrylic acid and steareth-20 methacrylate, sold under the name Aculyn 22 by Rohm & Haas,

- nonionic associative polymers of polyurethane polyether type, such as STEARETH-100/PEG-136/HDI COPOLYMER sold under the name Rhéolate FX 1100 by Elementis).

According to a particularly preferred mode, the hydrophilic gelling agent can be hydroxypropyl guar.

Amphoteric associative polymers

Among the associative amphoteric polymers of the invention, mention may be made of amphoteric polymers, crosslinked or uncrosslinked, branched or unbranched, capable of being obtained by the copolymerization

1) of at least one monomer of formula (XIIa) or (XIIb):

(XIIa)

(XIIb)

in which R ₄ and R ₅ , which are identical or different, represent a hydrogen atom or a methyl radical,

R ₆ , R ₇ and R ₈ , identical or different, represents a linear or branched alkyl radical having from 1 to 30 carbon atoms,

Z represents an NH group or an oxygen atom,

n is an integer from 2 to 5,

A ^- is an anion derived from an organic or mineral acid, such as a methosulfate anion or a halide such as chloride or bromide.

2) at least one monomer of formula (XIII):

(XIII)

in which R ₉ and R ₁₀ , identical or different, represent a hydrogen atom or a methyl radical;

Z ₁ represents an OH group or an NHC(CH ₃ ) ₂ CH ₂ SO ₃ H group;

3) at least one monomer of formula (XIV):

(XIV)

in which R ₉ and R ₁₀ , which are identical or different, represent a hydrogen atom or a methyl radical, X denotes an oxygen or nitrogen atom and R ₁₁ denotes a linear or branched alkyl radical having from 1 to 30 atoms of carbon;

4) optionally at least one crosslinking or branching agent; at least one of the monomers of formula (XIIa), (XIIb) or (XIV) comprising at least one fatty chain having from 8 to 30 carbon atoms and the said compounds of the monomers of formula (XIIa), (XIIb), ( XIII) and (XIV) which can be quaternized for example with a C ₁ -C ₄ alkyl halide or a C ₁ -C ₄ dialkyl sulphate.

The monomers of formula (XIIa) and (XIIb) of the present invention are preferably chosen from the group consisting of:

- dimethylaminoethylmethacrylate, dimethylaminoethylacrylate,

- diethylaminoethylmethacrylate, diethylaminoethylacrylate,

- dimethylaminopropylmethacrylate, dimethylaminopropylacrylate,

- dimethylaminopropylmethacrylamide, dimethylaminopropylacrylamide, optionally quaternized for example with a C1-C4 alkyl halide or a C ₁ -C ₄ dialkyl sulphate.

More particularly, the monomer of formula (XIIa) is chosen from acrylamidopropyl trimethyl ammonium chloride and methacrylamidopropyl trimethyl ammonium chloride.

The compounds of formula (XIII) of the present invention are preferably chosen from the group consisting of acrylic acid, methacrylic acid, crotonic acid, 2-methylcrotonic acid, 2- acrylamido-2-methylpropane sulfonic and 2-methacrylamido-2-methylpropane sulfonic acid. More particularly, the monomer of formula (XIII) is acrylic acid.

The monomers of formula (XIV) of the present invention are preferably chosen from the group consisting of C ₁₂ -C ₂₂ and more particularly C ₁₆ -C ₁₈ alkyl acrylates or methacrylates.

The crosslinking or branching agent is preferably chosen from N,N'-methylene bis-acrylamide, triallyl methyl ammonium chloride, allyl methacrylate, n-methylolacrylamide, polyethylene glycol dimethacrylates, dimethacrylate ethylene glycol, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate and allyl sucrose.

The polymers according to the invention may also contain other monomers such as nonionic monomers and in particular such as C ₁ -C ₄ alkyl acrylates or methacrylates.

The ratio of the number of cationic charges/anionic charges in these amphoteric polymers is preferably equal to approximately 1.

The weight-average molecular weights of the associative amphoteric polymers have a weight-average molecular mass greater than 500, preferably between 10,000 and 1,000,000 and even more preferably between 100,000 and 8,000,000.

Preferably, the associative amphoteric polymers of the invention contain from 1 to 99 mol%, more preferably from 20 to 95 mol% and even more preferably from 25 to 75 mol% of compound(s) of formula (XIIa) or (XIIb) . They also preferably contain from 1 to 80 mol%, more preferably from 5 to 80 mol% and even more preferably from 25 to 75 mol% of compound(s) of formula (XIII). The content of compound(s) of formula (XIV) is preferably between 0.1 and 70 mol%, more preferably between 1 to 50 mol% and even more preferably between 1 to 10 mol%. The crosslinking or branching agent when it is present is preferably between 0.0001 and 1 mole% and even more preferably between 0.0001 and 0.1 mole%.

Preferably, the molar ratio between the compound(s) of formula (XIIa) or (XIIb) and the compound(s) of formula (XIII) ranges from 20:80 to 95:5 and more preferably from 25:75 to 75:25.

The associative amphoteric polymers according to the invention are for example described in patent application WO9844012.

The particularly preferred amphoteric polymers according to the invention are chosen from acrylic acid/acrylamidopropyl trimethyl ammonium chloride/stearyl methacrylate copolymers.

The hydrophilic gelling polymer(s), and in particular the associative polymers, can be present in the composition according to the invention in a total active ingredient content ranging from 0.1 % to 10% by weight relative to the total weight of the aqueous phase, preferably from 0.2% to 5% by weight.

ADJUVANTS

Dyestuffs

A composition according to the invention may also comprise at least one dyestuff, whether particulate or not, water-soluble or not, and preferably in an amount of at least 0.01% by weight relative to the total weight of the composition.

For obvious reasons, this quantity is likely to vary significantly with regard to the intensity of the color effect sought and the color intensity provided by the coloring materials considered and its adjustment is clearly within the competence of the man of the art.

A composition according to the invention may comprise from 0.01% to 25% by weight, in particular from 0.1% to 15% by weight, in particular from 0.1% to 10% by weight, and preferably from 0, 1% to 5% by weight of dyestuffs, relative to the total weight of said composition.

As specified above, the dyestuffs suitable for the invention can be water-soluble but also fat-soluble.

By “water-soluble coloring matter”, within the meaning of the invention, is meant any generally organic compound, natural or synthetic, soluble in an aqueous phase or water-miscible solvents and capable of coloring.

Mention may in particular be made, as water-soluble dyes suitable for the invention, of synthetic or natural water-soluble dyes such as, for example, FDC Red 4, DC Red 6, DC Red 22, DC Red 28, DC Red 30, DC Red 33, DC Orange 4, DC Yellow 5, DC Yellow 6, DC Yellow 8, FDC Green 3, DC Green 5, FDC Blue 1, betanin (beetroot), carmine, chlorophyllin copper, methylene blue, anthocyanins (enocianine, black carrot, hibiscus, elderberry), caramel, riboflavin.

Water-soluble colorants are, for example, beet juice and caramel.

By “fat-soluble coloring matter”, within the meaning of the invention, is meant any generally organic compound, natural or synthetic, soluble in an oily phase or solvents miscible with a fatty substance and capable of coloring.

As fat-soluble dyes suitable for the invention, mention may in particular be made of fat-soluble, synthetic or natural dyes such as, for example, DC Red 17, DC Red 21, DC Red 27, DC Green 6, DC Yellow 11 , DC Violet 2, DC Orange 5, Sudan red, carotenes (β-carotene, lycopene), xanthophylls (capsanthine, capsorubin, lutein), palm oil, Sudan brown, quinoline yellow , annatto, curcumin.

The coloring particulate materials may be present in a proportion of 0.01% to 15% by weight, relative to the total weight of the composition containing them.

It may in particular be pigments, nacres and/or particles with metallic reflections.

By “pigments”, it is necessary to understand white or colored, mineral or organic particles, insoluble in an aqueous solution, intended to color and/or opacify the composition containing them.

A composition according to the invention may comprise from 0.01% to 25% by weight, in particular from 0.1% to 25% by weight, in particular from 1% to 25% by weight, and preferably from 2.5% to 15% by weight of pigments, relative to the total weight of said composition.

Preferably, when the composition according to the invention is a makeup composition, it may comprise at least 2.5%, and preferably at least 10% by weight of pigments, relative to the total weight of said composition.

The pigments can be white or colored, mineral and/or organic.

As inorganic pigments that can be used in the invention, mention may be made of titanium, zirconium or cerium oxides or dioxides, as well as zinc, iron or chromium oxides, ferric blue, manganese violet, ultramarine blue and chromium hydrate, and mixtures thereof.

It may also be a pigment having a structure which may for example be of the sericite/brown iron oxide/titanium dioxide/silica type. Such a pigment is marketed for example under the reference Coverleaf NS or JS by the company Chemicals And Catalysts and has a contrast ratio close to 30.

They may also be pigments having a structure which may be, for example, of the silica microsphere type containing iron oxide. An example of a pigment having this structure is that marketed by the Miyoshi company under the reference PC Ball PC-LL-100 P, this pigment consisting of silica microspheres containing yellow iron oxide.

Advantageously, the pigments in accordance with the invention are iron oxides and/or titanium dioxides.

By "pearl", it is necessary to understand colored particles of any shape, iridescent or not, in particular produced by certain molluscs in their shell or else synthesized, and which have a color effect by optical interference.

A composition according to the invention may comprise from 0% to 15% by weight of nacres, relative to the total weight of said composition.

The nacres can be chosen from pearlescent pigments, such as titanium mica covered with an iron oxide, titanium mica covered with bismuth oxychloride, titanium mica covered with chromium oxide, titanium mica covered with with an organic dye, as well as pearlescent pigments based on bismuth oxychloride. It can also be particles of mica on the surface of which are superimposed at least two successive layers of metal oxides and/or organic coloring matter.

Mention may also be made, by way of example of nacres, of natural mica coated with titanium oxide, iron oxide, natural pigment or bismuth oxychloride.

Among the nacres available on the market, mention may be made of the Timica, Flamenco and Duochrome nacres (based on mica) marketed by the company ENGELHARD, the Timiron nacres marketed by the company Merck, the nacres based on Prestige mica marketed by the company Eckart and the nacres based on Sunshine synthetic mica marketed by the company Sun Chemical.

The nacres may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or copper color or sheen.

Advantageously, the nacres in accordance with the invention are micas covered with titanium dioxide or iron oxide as well as bismuth oxychloride.

By “particles with a metallic reflection”, within the meaning of the present invention, is meant any compound whose nature, size, structure and surface condition allows it to reflect incident light, in particular in a non-iridescent manner.

The particles with a metallic sheen that can be used in the invention are chosen in particular from particles of at least one metal and/or of at least one metal derivative; the particles comprising a substrate, organic or inorganic, single-material or multi-material, covered at least partially by at least one layer with a metallic sheen comprising at least one metal and/or at least one metallic derivative; and mixtures of said particles.

Among the metals which may be present in said particles, mention may be made, for example, of Ag, Au, Cu, Al, Ni, Sn, Mg, Cr, Mo, Ti, Zr, Pt, Va, Rb, W, Zn, Ge, Te , Se and their mixtures or alloys. Ag, Au, Cu, Al, Zn, Ni, Mo, Cr, and mixtures or alloys thereof (eg, bronzes and brasses) are preferred metals.

The term "metal derivatives" denotes compounds derived from metals, in particular oxides, fluorides, chlorides and sulphides.

By way of illustration of these particles, mention may be made of aluminum particles, such as those marketed under the names Starbrite 1200 EAC ^® by the company Siberline and Metalure ^® by the company Eckart and glass particles covered with a metallic layer in particular those described in the documents JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

Hydrophobic treatment of dyestuffs

The pulverulent dyestuffs as described above can be surface-treated, totally or partially, with a hydrophobic agent, to make them more compatible with the oily phase of the composition of the invention, in particular so that they have good wettability with the oils. Thus, these treated pigments are well dispersed in the oily phase. Hydrophobic treated pigments are described in particular in document EP-A-1086683.

The hydrophobic treatment agent can be chosen from silicones such as methicones, dimethicones, perfluoroalkylsilanes; fatty acids such as stearic acid; metallic soaps such as aluminum dimyristate, aluminum salt of hydrogenated tallow glutamate; perfluoroalkyl phosphates; hexafluoropropylene polyoxides; perfluoropolyethers; amino acids; N-acylated amino acids or their salts; lecithin, isopropyl trisostearyl titanate, isostearyl sebacate, and mixtures thereof.

The term alkyl mentioned in the compounds mentioned above denotes in particular an alkyl group having from 1 to 30 carbon atoms, preferably having from 5 to 16 carbon atoms.

Assets

A composition according to the invention may comprise at least one moisturizing agent (also called humectant), in particular for a care application.

Preferably, the moisturizing agent is glycerine.

The hydrating agent(s) may be present in the composition in a content ranging from 0.1% to 15% by weight, in particular from 0.5% to 10% by weight, or even from 1% to 6% by weight, relative to the total weight of said composition.

As other active agents that can be used in the composition of the invention, mention may be made, for example, of vitamins, sunscreens and mixtures thereof, and in particular vitamins such as tocopherol.

Preferably, a composition according to the invention comprises at least one active ingredient, chosen in particular from moisturizing agents, preferably glycerin, vitamins, preferably tocopherol, and mixtures thereof.

According to a preferred embodiment, a composition according to the invention also comprises at least one active ingredient.

Preferably, the active ingredient is chosen from shea butter, sodium hyaluronate and their mixture.

In addition, a composition according to the invention may comprise at least one dispersing agent.

It is part of the routine operations of those skilled in the art to adjust the nature and the quantity of the additives present in the compositions in accordance with the invention, so that the desired cosmetic properties of these are not not affected.

COSMETIC COMPOSITION

As stated above, a composition according to the invention is preferably cosmetic.

A composition according to the invention is generally suitable for topical application to the skin and therefore generally comprises a physiologically acceptable medium, that is to say compatible with the skin.

It is preferably a cosmetically acceptable medium, that is to say one that has a pleasant color, smell and feel and does not generate unacceptable discomfort, that is to say tingling, tightness , redness, likely to distract the user from applying this composition.

A cosmetic composition according to the invention can be in all the dosage forms conventionally used in the cosmetics field, knowing that it has at least one fatty phase as defined above, as well as optionally an aqueous phase, depending on the applications envisaged, in particular for topical application to keratin materials.

For topical application to keratinous materials, and in particular the skin or its appendages or even to the hair, a composition may in particular take the form of an oily solution or dispersion of the lotion or serum type, of emulsions of liquid or semi-liquid consistency. liquid of the milk type, obtained by dispersing a fatty phase in an aqueous phase (oil-in-water) or vice versa (water-in-oil), or suspensions or emulsions of soft consistency of the aqueous or anhydrous cream or gel type , or alternatively microcapsules or microparticles, or vesicular dispersions of the ionic and/or nonionic type. These compositions are prepared according to the usual methods.

A composition according to the invention can be prepared according to techniques well known to those skilled in the art.

According to a particular embodiment, the composition of the invention has a transparent appearance, in particular in the form of a transparent gel at room temperature.

With regard to the texture or rheology of the composition according to the invention, and as indicated above and illustrated in the examples below, it is adjustable in particular according to the respective contents of silica airgel and ethylguar, as well as as a function of the chain length of ethylguar. Furthermore, as illustrated in examples 2 and 3, the compositions according to the present invention exhibit shear-thinning properties making it possible to obtain ease of spreading, or even improved slip properties.

The composition according to the present invention can be implemented in several fields of cosmetic application. It can in particular take the form of compositions for making up or caring for keratin materials, including hair compositions, or else take the form of photoprotective compositions, also called sunscreen products or photoprotective products, dedicated to the anti-UV protection of keratin materials. .

The composition according to the invention can constitute a make-up composition for the body or the face; of cleaning ; protection ; treatment or care for the skin and/or keratin fibres, in particular of the body or face, for the hands, for the feet, for large anatomical folds or for the body, for example day creams, night cream, anti-ageing cream, make-up remover cream, sunscreen composition, protective or caring body milk, after-sun milks, make-up remover milks, lotions, gels for skin care, such as cleansing lotions, artificial tanning compositions; a bath composition; a deodorant composition; an aftershave composition; a depilatory composition and a hair composition.

The present invention relates in this respect to a cosmetic process for making up and/or caring for or cleansing keratin materials or even for sun protection, comprising at least one step consisting in applying to said keratin materials at least one composition as defined above. .

Throughout the description, including the claims, the expression "comprising a" must be understood as being synonymous with "comprising at least one", unless otherwise specified.

The expressions “between … and …”, “comprises of … to …”, “formed from … to …”, and “ranging from … to …” must be understood as limits included, unless otherwise specified.

The invention is illustrated in more detail by the examples and figures presented below. Unless otherwise indicated, the quantities indicated are expressed in percentage by mass.

Methodology for dynamic rheology measurements in oscillation

These are rheological measurements in harmonic regime which ensure the measurement of the elastic modulus.

The measurements are carried out using a Haake RS600 type rheometer on a product at rest, at 25°C with a Ø 60 mm plane-plane mobile and an air gap of 2 mm.

Measurements in harmonic regime make it possible to characterize the viscoelastic properties of products. The technique consists of subjecting a material to a stress which varies sinusoidally over time and measuring the response of the material to this stress. In a field where the behavior is linear viscoelastic (area where the deformation is proportional to the stress), the stress (τ) and the deformation (γ) are two sinusoidal functions of time which are written as follows: τ(t ) = τ ₀ sin (ωt) and γ(t) = γ ₀ sin (ωt + δ) where τ ₀ represents the maximum stress amplitude (Pa); γ ₀ represents the maximum amplitude of the deformation (-); ω=2ΠN represents the pulsation (rad.s ^-1 ) with N representing the frequency (Hz); and δ represents the phase shift of stress with respect to strain (rad).

Thus, the two functions have the same angular frequency but they are out of phase by an angle δ. Depending on the phase shift δ between τ(t) and γ(t), the behavior of the system can be apprehended: if δ = 0, the material is purely elastic; if δ = Π/2, the material is purely viscous (Newtonian fluid); and if 0 < δ < Π/2, the material is viscoelastic.

In general, stress and strain are written in complex form: τ*(t) = τ ₀ e ^iωt and γ*(t) = γ ₀ e ^{(iωt + δ )} .

A complex modulus of rigidity, representing the overall resistance of the material to deformation whether of elastic or viscous origin, is then defined by G* = τ*/ γ* = G' + iG'' where G' is the storage modulus or elastic modulus which characterizes the energy stored and totally released during a cycle, G' = (τ ₀ / γ ₀ ) cos δ; and G'' is the loss modulus or viscous modulus which characterizes the energy dissipated by internal friction during a cycle, G'' = (τ ₀ / γ ₀ ) sin δ.

The parameter retained is the average stiffness modulus G* noted at the plate measured at a frequency of 1 Hz.

Measurement methods

In the examples detailed below, the following measurement methods are used.

Viscosity measurement protocol

The rheological measurements were carried out at 25° C. using an MCR 502 rotary rheometer from ANTON PAAR, equipped with a Peltier effect element to regulate the temperature. A Ø 50 mm / 1° cone/plane geometry (5 μm sandblasted steel) was used as well as an anti-evaporation device in order to avoid evaporation phenomena during the measurement. Flow curves from 0.1 to 1000 s ⁻¹ , 20 seconds per point on 20 points were carried out. The rheological characterizations were carried out at least 24 hours after formulation.

Protocol for measuring vapor pressure

For example, the vapor pressure can be measured using the static method or the effusion method by isothermal thermogravimetry, depending on the vapor pressure (OECD standard 104).

EXAMPLE 1

Characterization of the ‘ increase shear-thinning character with increasing shear rate, with the association of silica airgel and ' ethylguar

The following compositions were prepared according to the general procedure detailed below.

For compositions (1) to (3), the silica airgel is dissolved cold in the non-volatile polar oil with magnetic stirring, then the ethylguar is dissolved at 50° C. for 2 to 3 hours in a water bath, under magnetic stirring. The two are then mixed under magnetic stirring.

For composition (4), the ethylguar is dissolved at 50° C. for 4 to 5 hours in a water bath, in a polar oil with magnetic stirring, in a water bath.

The results are summarized in the and indicate that the association between the silica airgel and the ethylguar leads to an increase in the shear-thinning character of compositions 1 to 3, in terms of the thickening of the oil used, compared to the ethylguar used alone in composition 4.

It is also observed that for composition 1, where the ratio between the ethylguar and the airgel is equal to 0.5, a gelled system is obtained, thanks to the combination of the ethylguar and the silica airgel, on the entire frequency range. It is observed that the curves remain parallel, without approaching or crossing over the entire frequency range.

EXAMPLE 2

The following compositions were prepared according to the general procedure detailed below.

For compositions (5) and (6), the ethylguar is dissolved at 50° C. for 4 to 5 hours in a water bath, in a non-volatile polar oil with magnetic stirring.

For composition (7), the silica airgel is cold dissolved in the non-volatile polar oil.

For composition (8), the silica airgel is dissolved in the cold in non-volatile polar oil with magnetic stirring, then the ethylguar is dissolved at 50° C. for 4 to 5 hours in a water bath, with magnetic stirring.

The results are summarized in Figures 2 and 3.

Composition 8 is transparent.

The results observed in the (viscoelastic spectrum) indicate that composition 8 makes it possible to obtain, thanks to the ethylguar/silica airgel combination in octyldodecanol, a more shear-thinning gelled system than compositions 5 and 6. Comparative compositions 5 and 6 for their part correspond to viscoelastic liquids (crossing point observed between G' and G'').

The results observed in the (Flow curve) indicate that composition 8, due to the consequent reduction with increasing shear rate, namely due to this shear-thinning property, is particularly advantageous for better spreading. In other words, no braking effect is to be feared following the application of such a composition to keratin materials, in particular the hair.

EXAMPLE 3

Compositions 9 to 14 are prepared as described below with the proportions indicated in Tables 3 and 4.

Phase A and B are prepared separately: the silica airgel is solubilized in the cold in the volatile apolar oil isododecane and the ethylcellulose/ethylguar is dissolved at 50° C. for 2 to 3 hours in the non-polar polar oil. volatile in a water bath.

At t+3 days, compositions 12, 13 and 14 show better stability and are more homogeneous than compositions 9, 10 and 11 outside the invention, since the latter are more cloudy and out of phase. Compositions 12, 13 and 14 are transparent.

The ethylguar / silica airgel combination makes it possible to formulate stable compositions in mixtures of oils that are more apolar than the ethylcellulose / silica airgel combination.

EXAMPLE 4

The following compositions were prepared according to the general procedure detailed below.

1) The aqueous dispersion of ethylcellulose (composition A – as described in patent FR2992205A1) or ethylguar (compositions C) was mixed with the non-volatile polar oil with stirring and heated for 1 to 2 hours at 55°C.

2) The surfactant was added and mixed with stirring at 55°C until the mixture was homogeneous.

3) The hydroxypropyl guar was added until a homogeneous mixture was obtained and allowed to cool to room temperature.

4) The non-volatile silicone oil was then added, still stirring.

5) The fillers were then sprinkled with silica (aerogel) stirring with a spatula until the mixture was homogeneous, under BOA.

6) The mixture was then placed in Cleopatra jars.

Evaluation of the compositions

A/ Gloss measurement protocol

The gloss of a deposit resulting from the application of a composition can be commonly measured using various methods, such as that using a Sheen brand TriGloss master 20°/60°/85° gloss meter.

Principle of measurement using this Glossmeter

The device illuminates the sample to be analyzed at a certain incidence and measures the intensity of the specular reflection.

The intensity of the reflected light depends on the material and the angle of illumination. For non-ferrous materials (paint, plastic), the intensity of reflected light increases with the angle of illumination. The rest of the incident light penetrates the material and depending on the shade of the color, it is either partially absorbed or diffused.

The measurement results of the reflectometer are not based on the amount of incident light but on a black, polished glass standard of defined refractive index.

The measurement is normalized with respect to an internal standard and adjusted to a value out of 100: for this standard standard, the measurement value is set at 100 gloss units (calibration). The closer the measured value is to 100, the brighter the sample. The unit of measurement is the Gloss Unit (BU).

Test protocol

a- On a BYK brand contrast card and reference byko-chart Opacity 2A, spread a layer of 100 μm wet thickness of the composition whose average gloss is to be assessed, by leveling off the formula with a microscope in an area of the black background of the card delimited by two strips of tape each 100 µm thick. The layer overlays the black background of the map.

b- Measurement taken 12 minutes after deposition (room temperature).

c- Measure the gloss at 20°, 60° and 85° on the black background. (3 measurements) using a Sheen TriGloss master 20°/60°/85° gloss meter.

It is then necessary to compare the values measured in BU obtained for the various compositions tested. The lower the measured value, the duller the deposit.

Thus, at GU values greater than 70 GU measured at 20°, the tested composition belongs to the high-gloss range, at values between 10 and 70 GU measured at 60°, the tested composition belongs to the semi-gloss range, and at GU values of less than 10 GU measured at 85°, the composition tested belongs to the low-gloss, or even matte, range.

Results

The compositions were evaluated after 3 months of storage at room temperature.

Composition C according to the invention, which is in the form of an emulsion, has a result measured in UB, located in the semi-gloss range, lower than that obtained for comparative composition A, and is consequently the composition leading to a duller deposit.

B/ Slipperiness measurement protocol

The slip quality is assessed respectively during and after topical application of a sample of the composition tested on the surface of the back of a hand.

The slipperiness is assessed by evaluating the ease with which the fingers turn on the surface of the back of a hand during the application on this surface of a sample of the composition to be tested. To reinforce the tactile evaluation, the application is carried out using two fingers which are slid over the surface.

Slip legend:

0: braking

+: not very slippery

++: slippery

+++: very slippery

Results

It is observed that composition C comprising ethylguar according to the invention shows better sensory qualities in terms of ease of application and ease of spreading or slipperiness of the composition.

C/ Conclusion

From the results, it emerges that composition C comprising ethylguar according to the invention exhibits a better quality of slipperiness than the comparative composition comprising an aqueous dispersion of ethylcellulose and exhibits a deposit of low gloss, more matt than the comparative composition comprising an aqueous dispersion of ethylcellulose.

Claims (18)

Cosmetic composition comprising, in a physiologically acceptable medium comprising:
- at least one non-volatile liquid fatty phase,
- at least ethylguar, and
- at least silica airgel. Cosmetic composition according to Claim 1, characterized in that the silica airgel particles used have a specific surface area per unit mass ranging from 500 to 1500 m ² /g, preferably from 600 to 1200 m ² /g, and preferably from 600 to 800 m ² /g and a size expressed as volume average diameter (D[0.5]) ranging from 1 to 1500 μm, preferably from 1 to 1000 μm, even more preferably from 1 to 100 μm, in particular from 1 to 30 μm, more preferably from 5 to 25 μm, better still from 5 to 20 μm and even better still from 5 to 15 μm. Composition according to any one of the preceding claims, characterized in that the airgel particles have a packed density ranging from 0.02 g/cm ³ to 0.10 g/cm ³ , preferably from 0.03 g/cm ³ to 0.08 g/cm ³ . Composition according to any one of the preceding claims, characterized in that the airgel particles are hydrophobic and may have an oil absorption capacity measured at the WET POINT ranging from 5 to 18 ml/g of particles, preferably 6 to 15 ml/g and better from 8 to 12 ml/g. Cosmetic composition according to Claim 1 or 2, characterized in that the silica airgel particles are hydrophobic silica airgel particles surface-modified with trimethylsilyl groups, preferably hydrophobic silica airgel particles with the INCI name Silica silylate. Composition according to any one of the preceding claims, characterized in that the silica airgel particles are present in an active matter content ranging from 0.1% to 15% by weight, preferably from 0.1% to 10 % by weight, and more preferably from 1% to 5% by weight, relative to the total weight of the non-volatile liquid fatty phase. Composition according to any one of the preceding claims, characterized in that the ethylguar is present in a content of between 0.5% and 16% by weight, preferably between 1% and 16% by weight and more preferably between 1% and 12% by weight, more preferably between 1 and 10% by weight, relative to the total weight of the non-volatile liquid fatty phase. Composition according to any one of the preceding claims, in which the ethylguar and the silica airgel are used in the composition according to the invention in an ethylguar/silica airgel weight ratio of between 0.1 and 10, of preferably between 0.1 and 5. relative to the total weight of the non-volatile liquid fatty phase. Composition according to any one of the preceding claims, characterized in that the nonvolatile liquid fatty phase comprises at least one first nonvolatile protic polar oil, and optionally at least one second nonvolatile oil chosen from silicone and/or fluorinated oils and / or non-volatile hydrocarbon oils other than said first oil. Composition according to Claims 1 to 8, characterized in that it also comprises at least one volatile oil, in particular apolar oil. Composition according to Claim 9 or 10, characterized in that the said first non-volatile polar protic oil is chosen from hydrocarbon-based oils of animal origin, vegetable hydrocarbon-based oils, synthetic esters, polyol esters and pentaerythritol esters, fatty alcohols that are liquid at room temperature with a branched and/or unsaturated carbon chain containing from 12 to 26 carbon atoms and higher C ₁₂ -C ₂₂ fatty acids, and more particularly among hydrocarbon oils of plant origin, esters of synthesis and fatty alcohols that are liquid at room temperature with a branched and/or unsaturated carbon chain having from 12 to 26 carbon atoms. Cosmetic composition according to one of Claims 9 to 11, characterized in that the said first non-volatile polar protic oil is chosen from triglycerides of caprylic/capric acids, isopropyl myristate, ethylhexylpalmitate and octyldodecanol, and in in particular by the triglycerides of caprylic/capric acids, isopropyl myristate, and octyldodecanol, and preferably is at least octyldodecanol. Composition according to any one of Claims 9 to 12, characterized in that the said first non-volatile polar protic oil is present in a content ranging from 5% to 75%, in particular from 10% to 50% by weight, preferably from 20% to 45% by weight, relative to the total weight of the composition. Composition according to any one of Claims 9 to 13, characterized in that it comprises a content ranging from 5% to 75% by weight of second non-volatile silicone oil(s) and/or fluorinated(s) or non-volatile hydrocarbon(s) different from said first oil, in particular from 10% to 40% by weight, and more particularly from 15% to 30% by weight, with respect to its total weight. Composition according to any one of the preceding claims, characterized in that it comprises an aqueous phase, which may be present in a content of between 2% and 80% by weight, preferably between 5% and 60%, even more preferably between 10% and 50% by weight, relative to the total weight of the composition. Composition according to any one of the preceding claims, characterized in that the composition additionally comprises at least one hydrophilic thickener and/or at least one surfactant. Composition according to one of the preceding claims, characterized in that it has a transparent appearance, in particular in the form of a transparent gel at room temperature. Cosmetic process for making up and/or caring for or cleansing keratin materials or even for sun protection, comprising at least one step consisting in applying to said keratin materials at least one composition as defined in any one of the preceding claims.