FR3117832A1 - Two-step makeup process comprising on the one hand an amino acid and on the other hand an acid dye and kit - Google Patents

Abstract

Title: Two-step make-up process comprising, on the one hand, an amino acid and, on the other hand, an acid dye and kit The present invention therefore relates to a process for making up human keratin materials, consisting in successively applying a first composition aqueous, then a second composition comprising at least one oil; one of the compositions comprising at least one amino acid containing at least one additional cationizable function, its C1-C3 esters or the corresponding oligopeptides; and the other composition comprising at least one acid dye. It also relates to a cosmetic kit for implementing said process for making up human keratin materials.

Description

Two-step makeup process comprising on the one hand an amino acid and on the other hand an acid dye and kit

The subject of the present invention is a process for making up human keratin materials, in which two compositions are successively applied, the first aqueous, the second comprising at least one oil, one of the compositions comprising at least one particular amino acid, the another comprising at least one acid dye. The present invention also relates to a cosmetic kit for implementing said makeup process, comprising two parts, one for each of the two aforementioned compositions.

Today on the make-up market for keratin materials, many products claim day-long hold, resistant to external factors such as water, sebum, mechanical friction, etc. (waterproof mascara, foodproof lipsticks, foundation long-lasting complexion). Long-lasting make-up products for the lips, eyelashes, eyebrows or for the face, which can be used at home, are mainly based on film-forming synthetic polymers, in the presence of organic solvents. Compositions comprising, as coating agent, a silicone resin, for example resins of the trimethylsiloxysilicate, polypropylsilsesquioxane type, or even a silicone acrylate copolymer such as the product acrylates/polytrimethylsiloxymethacrylate copolymer (INCI name). Long-lasting make-up products for the eyelashes and/or eyebrows (mascaras, eyeliners) use waxes or film-forming polymer particles in aqueous suspension of the latex type, such as Styrene/Acrylates copolymers, for example).

In addition to these long-lasting products, the current trend is also in semi-permanent make-up. In fact, in recent years, classic make-up products have been challenged by the market for semi-permanent make-up in professional salons. It is found in the eye make-up sector (semi-permanent mascara), eyebrows (semi-pigmentation called microblading), complexion (freckles, moles, or entire face, luminous effect or healthy glow) or even lips (semi-permanent tattoo). This new trend pushes the consumer to look for more and more hold for more practicality and to avoid daily make-up and make-up removal, benefit from a healthy glow effect as soon as you wake up, etc... The disadvantage of this type of method is obviously the need to go through a professional, which in a way complicates the implementation. In addition, the processes proposed are no longer so innocuous, they are more invasive (tattooing), and their result, due to the expected advantage of durability, can become a disadvantage if the result is not pleasing.

The consumer is therefore essentially faced with these two alternatives, on the one hand a make-up whose hold does not go beyond the day at best, and on the other hand, a semi-permanent make-up with a visible result several weeks later. the treatment.

The subject of the present invention is therefore a make-up process, the result of which lies in the space left by the two methods described above. Indeed, the method according to the present invention makes it possible to achieve a color fastness going beyond one day, more particularly from 2 to 5 days after the treatment, while maintaining a homogeneous coloring during this period. This intermediate duration makes it possible to satisfy the consumer by limiting the obligation to redo the make-up of the treated area daily, without being too demanding. Furthermore, the make-up result is resistant to mechanical friction, sweat and perspiration, sebum, oil, water, cleaning products such as shower gels, shampoos, bi -phases and certain micellar waters. Finally, if it happened that the make-up result obtained was not the one expected, the latter would regularly fade in the following week, in a homogeneous manner, and could even be masked.

The method according to the invention has the advantage of being very simple to implement, without requiring the passage in a professional salon, nor the implementation of particular know-how or equipment.

A subject of the present invention is therefore a process for making up human keratin materials, consisting in successively applying a first aqueous composition, then a second composition comprising at least one oil; one of the compositions comprising at least one amino acid containing at least one additional cationizable function, its C ₁ -C ₃ esters or the corresponding oligopeptides; and the other composition comprising at least one acid dye. It also relates to a cosmetic kit for implementing said process for making up human keratin materials comprising:
* a first aqueous composition comprising at least one amino acid containing at least one additional cationizable function, its C ₁ -C ₃ esters or the corresponding oligopeptides;
* a second composition, in the form of an emulsion or in the form of a composition comprising less than 5% by weight of water relative to the weight of said composition, comprising at least one oil and at least one acid dye.

It likewise relates to a cosmetic kit for implementing said method, comprising:
* a first aqueous composition comprising at least one acid dye;
* a second composition, in the form of a composition comprising less than 5% by weight of water relative to the weight of said composition, or in the form of an emulsion, preferably a water-in-oil emulsion, comprising at least an oil and at least one amino acid containing at least one additional cationizable function, its C ₁ -C ₃ esters or the corresponding oligopeptides.

The compositions according to the invention can be applied to human keratin materials, such as the skin, the lips, the nails, but also the fibers such as, for example, the eyelashes, the eyebrows or the hair. These are therefore compositions comprising a physiologically acceptable medium, that is to say compatible with application to the skin and/or its appendages, which has a pleasant color, smell and feel and which does not cause discomfort. unacceptable (tingling, tightness), likely to discourage the consumer from using this composition.

The method according to the invention makes it possible in particular to confer a natural make-up giving a good-looking effect. It can thus be used alone for a discreet but visible effect, which remains natural, in particular if the second composition comprises little or no additional coloring matter. It is also not excluded to apply a moisturizing colorless composition, for example at the end of the process according to the invention. The process according to the invention can also be implemented before a conventional colored and/or covering make-up, so that, once this make-up has been eliminated over time, the good-looking effect mentioned above is left. It should be noted, moreover, that if the second composition comprises additional coloring materials in a quantity such that the resulting deposit is colored and covering, there will therefore be a first colored effect as a result, followed, later in the day, by the natural effect, healthy glow indicated above, once the second composition has disappeared.

It can bring more visibility for the eyebrows for example, and help draw a more precise arc.

The color fastness is evaluated according to the following protocol:

Equipment :
Chromalys Samba-Shiva Chromasphere including a SAMBA polarimetric camera; resolution 410x410 pixels. The method described in patent FR2829344 is implemented.
The coordinates L, a, b, of the color are measured in the CIELab space (illuminant D65).

Protocol :
1. The composition is applied to the keratin materials which have been cleansed beforehand and have been made-up-free, having also undergone a scrubbing step in the case of the skin and the lips.
2. A first measurement of the coloring of the keratin materials thus prepared is carried out.
3. The first composition is applied to the keratin materials and allowed to dry for the necessary time. For example, in the case of an application to the skin or the lips, the composition is allowed to dry for 15 minutes, without eating or drinking between the two applications.
4. The second composition is then applied, directly after the first has dried, and left to dry again. For example, in the case of an application to the skin or the lips, the composition is left to dry for 15 minutes, without eating or drinking.
5. A measurement is taken of the coloration of the keratin materials once the deposit has dried.
6. After 24 hours, a new color measurement is taken. During these 24 hours, the model continues her normal occupations (meals, sport, work) without however cleaning, removing make-up, re-applying, or applying make-up over the treated area. Moreover, in the case of an application to the skin or the lips, the first consumption of liquid or solid food takes place only 6 hours after the application of the last composition.
7. The same measurement is carried out 44 hours then 68 hours after the treatment.
The evaluation of the coloration and of the variation in the coloration of the keratin materials treated is carried out by visual comparison of the various photographs. It can also be carried out by determining the variation in ΔE between the initial coloration of said keratin materials and that after each of the measurements.

MAKEUP PROCEDURE

As indicated above, the method according to the present invention consists in successively applying a first aqueous composition, then a second composition comprising at least one oil, one of the compositions comprising at least one amino acid containing at least one additional cationizable function , its C ₁ -C ₃ esters or the corresponding oligopeptides, and the other composition comprising at least one acid dye.

More particularly, according to a first variant, a first aqueous composition is applied comprising at least one amino acid, one of its esters or a corresponding oligopeptide as described above, then a second composition comprising at least one oil and at least one dye acid, the second composition comprising less than 5% by weight of water relative to the weight of said composition, or being in the form of an emulsion, preferably a water-in-oil emulsion.

According to a second variant of the process according to the invention, a first aqueous composition comprising at least one acid dye is applied, then a second composition comprising at least one oil and at least one amino acid, one of its esters or a corresponding oligopeptide, such than described above, the second composition comprising less than 5% by weight of water relative to the weight of said composition, or being in the form of an emulsion, preferably a water-in-oil emulsion. Preferably, the second composition is in the form of a water-in-oil emulsion.

It should be noted that the amino acid containing at least one additional cationizable function, its C ₁ -C ₃ esters or the corresponding oligopeptides and the acid dye or dyes are not found simultaneously in the same composition.

Preferably, the application of the second composition is carried out once the deposit of the first composition is dry. Usually, the second composition is applied a few minutes after the application of the first composition. For example, if the composition is applied to the skin or the lips, this duration can vary between 2 to 15 minutes. If the composition is applied to human keratin fibres, such as the eyebrows, for example, this duration may vary, for example, from 5 to 20 minutes. Of course, these durations are given as an indication and longer durations can be envisaged. In addition, the second composition is preferably applied directly after the first, when the first deposit is dry. In other words, between the two deposits, nothing is advantageously brought into contact with the treated keratin materials. Thus, between the two depositions, the keratin materials are allowed to dry more particularly without applying or bringing said keratin materials into contact with water, a solvent, a cleansing or make-up-removing formulation, a drink, or food.

It is obviously recommended to carry out the treatment on bare human keratin materials.

Thus, it is preferable to cleanse, to remove make-up from human keratin materials.

It may also be advantageous, in the case of an application in particular on the skin or the lips, to carry out a preliminary stage of elimination of the dead cells (scrub), by means of an appropriate composition, or by implementing conventional mechanical means. Scrub compositions can be liquid, solid, anhydrous or include water. They usually contain particles with a size between 50 µm and a few millimetres. These particles can be wax particles, solid sugars, or even particles from plants, in particular kernels or bark.

It should be noted that for the subsequent applications of the two compositions according to the invention, the human keratin materials are preferably also bare.

AMINO ACID

The process according to the invention therefore uses at least one composition comprising at least one amino acid containing at least one additional cationizable function, its C ₁ -C ₃ esters or the corresponding oligopeptides, alone or in mixtures.

By cationizable function is meant a nonionic group capable of forming a cation as a function of the pH (more particularly when the latter is lower than the pKa of the molecule).

Preferably, the amino acids with an additional cationizable function implemented within the scope of the present invention comprise at least one additional primary or secondary amine function, and preferably comprise an additional primary or secondary amine function.

As regards the esters of said amino acids and/or corresponding oligopeptides, the methyl, ethyl, propyl, isopropyl esters, and preferably the ethyl esters, are preferred.

As regards the amino acid oligopeptides, the term more particularly refers to those whose average molecular weight is less than or equal to 550 g/mol. In other words, the oligopeptides that can be used in the context of the present invention more especially comprise at most five identical or different amino acid units, preferably at most four identical or different amino acid units, and even more preferably at most three amino acid units same or different. It should be noted that the oligopeptide comprises at least one amino acid motif with additional cationizable function. It may optionally comprise another amino acid unit, with or without an additional cationizable function. Preferably, said oligopeptide contains only amino acid units with additional cationizable function. And even more preferably, the oligopeptide contains the same amino acid motif with additional cationizable function.

More particularly, the natural amino acids chosen from arginine, histidine, lysine, asparagine, or synthetic such as ornithine, alone or in mixtures, or oligopeptides of the alaline-lysine type, as well as their esters or their addition salt with a mineral acid such as hydrochloric acid. Preferably, the amino acid(s) are chosen from arginine, arginine ethyl ester, lysine, lysine ethyl ester, histidine, histidine ethyl ester, as well as the corresponding hydrochlorides .

More particularly, the amino acid is soluble in the composition in which it is used, or in at least one of the phases of said composition, if the latter is in the form of a mixture of two or more immiscible phases. Thus, the amino acid is present more particularly at a content less than or equal to, preferably less than, its solubility limit in the medium in question.

The content of amino acid(s) containing at least one additional cationizable function, its/their C ₁ -C ₃ esters or the corresponding oligopeptides, varies from 1 to 20% by weight, more particularly from 2.5 to 15% by weight, and preferably from 5 to 15% by weight, relative to the weight of the composition comprising it or them.

ACID DYES S

The method according to the invention is implemented with at least one acid dye.

The term "acid dye" denotes species colored, or comprising at least one colored form depending on the pH or the nature of the medium in which it is found, comprising in its structure at least one carboxylic or sulphonic acid function; the acid function being in the free form or in a reduced form engaged in a heterocycle, more particularly with 5 or 6 atoms, for example in the form of a heterocycle of the butyro lactone type; the acid function being in ionic or non-ionic form.

More particularly, the acid dyes suitable for carrying out the present invention are soluble in the composition in which they are used, or in at least one of the phases of said composition, if the latter is in the form of a mixture of two or more immiscible phases. Thus, the acid dye is more particularly present at a content less than or equal to, preferably less than, its solubility limit in the medium in question.

Acid dyes can be aqueous or non-aqueous soluble.

Among the acid dyes capable of being used in the process in accordance with the present invention, mention may be made of azo, xanthene, anthraquinone, triarylmethane, azine, quinolin, nitroso, indigoid acid dyes and mixtures thereof, and preferably among azo and xanthenic dyes, as well as mixtures thereof. Reference may also be made to Annex IV of the Cosmetics Directive (Regulation (EC) No 1223/2009 of the European Parliament and of the Council of November 30, 2009).

As more specific examples of acid dyes, we can cite, alone or in combination:

Azo Dyes : Acid Black 1 (CI 20470), Black 2 (CI 27755), Food Black 1 (CI 28440), Acid Black 2 (CI 50420), FD&C Red 4 (CI 14700); FD&C Red 2 (CI 14815); Acid Red 14 (CI 14720); Pigment Red 68 (CI 15525); Pigment Red 51 (CI 15580); Acid Red 88 (CI 15620); Pigment Red 49 (CI 15630); Red 7 (CI 15850); Pigment Red 48:4 (CI 15865); Pigment Red 63:1 (CI 15880); FD&C Red 40 (CI 16035); Acid Red 27 (CI 16185); Acid Red 18 (CI 16255); Acid Red 41 (CI 16290); Acid Red 33 (CI 17200); Acid Red 1 (CI 18050); Acid Red 155 (CI 18130); Acid Red 180 (CI 18736); Acid Red 163 (CI 24790); Acid Red 73 (CI 27290); Acid Orange 6 (CI 14270); Acid Orange 7 (CI 15510); Orange GGN (CI 15980); Orange Yellow 5 (CI 15985); Acid Orange 10 (CI 16230); Acid Orange 24 (CI 20170); Direct Orange 46 (CI 40215); Acid Yellow 9 monosodium salt (CI 13015); Acid Yellow 11 (CI 18820); Acid Yellow 17 (CI 18965); Pigment Yellow 100 (CI 19140).

Xanthene dyes : Acid Violet 9 (CI 45190); Acid Red 52 (CI 45100); Acid Red 50 (CI 45220); Acid Red 87 (or DC Red 21 or 22; CI 45380); Acid Red 98 (CI 45405); D&C Red 27 or 28 (CI 45410); Acid Red 95 (CI 45425); Acid Red 51 (CI 45430); Acid Orange 11 (CI 45370); D&C Orange No.2 (CI 45396); Acid Yellow 73 (CI 45350).

Anthraquinone dyes : Acid Violet 43 (CI 60730), Acid Green 5 (CI 61570), Natural Red 41 (CI 75470), Acid Blue 80 (CI 61585), Acid Blue 62 (CI 62045).

Triarylmethane dyes : Food Green 3 (CI 42053), Acid Green 9 (CI 42100), Alkali Fast Green 10 GA (CI42170), Acid Green 50 (CI 44090), Acid Blue 1 (CI 42045), Acid Blue 3 (CI 42051) ), Acid Blue 7 (CI 42080), Acid Blue 9 (CI42090), Acid Blue 104 (CI 42735).

Preferably, the acid dye or dyes are chosen from acid dyes whose color is violet, red, pink, orange or yellow.

In accordance with a particularly preferred embodiment of the invention, the acid dye or dyes are chosen from the following species, alone or in mixtures: Acid Black 1 (CI 20470), Acid Black 2 (CI 50420), Acid Red 14 ( CI 14720); Acid Red 88 (CI 15620); Acid Red 27 (CI 16185); Acid Red 18 (CI 16255); Acid Red 41 (CI 16290); Acid Red 33 (CI 17200); Acid Red 1 (CI 18050); Acid Red 155 (CI 18130); Acid Red 180 (CI 18736); Acid Red 163 (CI 24790); Acid Red 73 (CI 27290); Acid Orange 6 (CI 14270); Acid Orange 7 (CI 15510); Orange GGN (CI 15980); Acid Orange 10 (CI 16230); Acid Orange 24 (CI 20170); Acid Yellow 9 monosodium salt (CI 13015); Acid Yellow 11 (CI 18820); Acid Yellow 17 (CI 18965) for azo dyes; and from Acid Violet 9 (CI 45190); Acid Red 52 (CI 45100); Acid Red 50 (CI 45220); Acid Red 87 (CI 45380); Acid Red 98 (CI 45405); D&C Red 27 or 28 (CI 45410); Acid Red 95 (CI 45425); Acid Red 51 (CI 45430); Acid Orange 11 (CI 45370); Acid Yellow 73 (CI 45350) for xanthene dyes; as well as their combinations.

Preferably, the acid dye or dyes are chosen from xanthene dyes of the “Red” type (xanthene dyes with a red or pink coloration), and even more preferably D&C Red 27 or 28 dye.

Advantageously, the content of acid dye(s) varies from 0.1 to 5% by weight, more particularly from 0.1 to 2% by weight, 0.1 to 1% by weight, relative to the weight of the composition comprising it or them.

ADDITIONAL COLORING MATERIALS

The method according to the present invention can be implemented in the presence of one or more additional dyestuffs, different from the acid dyes previously described.

The additional dyestuff(s) may be present in the first and/or in the second composition. Advantageously, the additional dyestuff(s) are present in the composition where the acid dye(s) are present.

The additional coloring material is a coloring material, synthetic, natural or of natural origin, chosen more particularly from coated or uncoated pigments, dyes different from the aforementioned acid dyes.

The term “pigments” means white or colored, mineral or organic particles, insoluble in the medium in which they are present, intended to color and/or opacify the composition and/or the resulting deposit.

According to a particular embodiment, the pigments used according to the invention are chosen from mineral pigments.

By "mineral pigment" is meant any pigment which meets the definition of the Ullmann encyclopedia in the chapter inorganic pigment. Mention may be made, among the mineral pigments useful in the present invention, of zirconium or cerium oxides, as well as zinc, iron (black, yellow or red) or chromium oxides, manganese violet, ultramarine blue , chromium hydrate and ferric blue, titanium dioxide, metal powders such as aluminum powder and copper powder. The following mineral pigments can also be used: Ta ₂ O ₅ , Ti ₃ O ₅ , Ti ₂ O ₃ , TiO, ZrO ₂ mixed with TiO ₂ , ZrO ₂ , Nb ₂ O ₅ , CeO ₂ , ZnS.

The size of the pigment useful in the context of the present invention is generally greater than 100 nm and can range up to 10 μm, preferably from 200 nm to 5 μm, and more preferably from 300 nm to 1 μm.

According to a particular form of the invention, the pigments have a size characterized by a D [50] greater than 100 nm and possibly up to 10 μm, preferably from 200 nm to 5 μm, and more preferably from 300 nm to 1μm.

The sizes are measured by static light scattering using a commercial particle sizer of the MasterSizer 3000® type from Malvern, making it possible to determine the particle size distribution of all the particles over a wide range which can go from 0.01 μm at 1000 µm. The data is processed based on the classical Mie scattering theory. This theory is the most suitable for size distributions ranging from submicron to multi-micron, it makes it possible to determine an “effective” particle diameter. This theory is described in particular in the work of Van de Hulst, H.C., "Light Scattering by Small Particles", Chapters 9 and 10, Wiley, New York, 1957. D[50] represents the maximum size that 50% by volume the particles.

In the context of the present invention, the mineral pigments are more particularly iron oxide and/or titanium dioxide. By way of example, mention may more particularly be made of titanium dioxide and iron oxide, coated with aluminum stearoyl glutamate, for example marketed under the reference NAI® by the company MIYOSHI KASEI.

As mineral pigments that can be used in the invention, mention may also be made of nacres.

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

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.

According to a particular embodiment, the pigments used according to the invention are chosen from mineral pigments.

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.

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

Among the pigments that can be used according to the invention, mention may also be made of those with an optical effect different from a simple conventional tint effect, that is to say unified and stabilized as produced by conventional dyestuffs, such as, for example , monochromatic pigments. Within the meaning of the invention, “stabilized” means devoid of any effect of color variability with the angle of observation or even in response to a change in temperature.

For example, this material can be chosen from particles with a metallic reflection, goniochromatic coloring agents, diffracting pigments, thermochromic agents, optical brightening agents, as well as fibers, in particular interference fibers. Of course, these different materials can be combined so as to provide the simultaneous manifestation of two effects, or even of a new effect in accordance with the invention.

According to a particular mode, the method can be implemented in the presence of at least one uncoated pigment.

According to another particular mode, the method can be implemented in the presence of at least one pigment coated with at least one lipophilic or hydrophobic compound.

This type of pigment is particularly advantageous. Insofar as they are treated with a hydrophobic compound, they show a preponderant affinity for an oily phase which can then convey them.

The coating can also comprise at least one additional non-lipophilic compound.

Within the meaning of the invention, the "coating" of a pigment according to the invention generally designates the total or partial surface treatment of the pigment by a surfactant, absorbed, adsorbed or grafted onto said pigment.

The surface-treated pigments can be prepared using chemical, electronic, mechano-chemical or mechanical surface treatment techniques well known to those skilled in the art. Commercial products can also be used.

The surfactant can be absorbed, adsorbed or grafted onto the pigments by solvent evaporation, chemical reaction and creation of a covalent bond.

According to a variant, the surface treatment consists of coating the pigments.

The coating can represent from 0.1% to 20% by weight, and in particular from
0.5% to 5% by weight, of the total weight of the coated pigment.

The coating can be carried out, for example, by adsorption of a liquid surfactant on the surface of the solid particles by simple mixing, with stirring, of the particles and of said surfactant, optionally hot, prior to the incorporation of the particles into the other ingredients of the make-up or care composition.

The coating can be carried out for example by chemical reaction of a surfactant with the surface of the solid particles of pigment and creation of a covalent bond between the surfactant and the particles. This method is described in particular in US Pat. No. 4,578,266.

Chemical surface treatment can consist of diluting the surfactant in a volatile solvent, dispersing the pigments in this mixture, and then slowly evaporating the volatile solvent, so that the surfactant deposits on the surface. pigments.

When the pigment comprises a lipophilic or hydrophobic coating, the latter is preferably present in the fatty phase of the composition according to the invention.

According to a particular embodiment of the invention, the pigments can be coated according to the invention with at least one compound chosen from silicone surfactants; fluorinated surfactants; fluoro-silicone surfactants; metallic soaps; N-acylated amino acids or their salts; lecithin and its derivatives; isopropyl trisostearyl titanate; isostearyl sebacate; natural vegetable or animal waxes; polar synthetic waxes; fatty esters; phospholipids; and their mixtures.

According to a particular embodiment of the invention, the pigments can be coated with a hydrophilic compound.

Said hydrophilic compound making it possible to surface-treat a pigment in order to optimize its dispersion in the aqueous phase is more particularly chosen from biological polymers, carbohydrates, polysaccharides, polyacrylates or derivatives of polyethylene glycol.

As examples of biological polymers, mention may be made of polymers based on monomers of the carbohydrate type.

More particularly, mention may be made of biosaccharide gum; chitosan and their derivatives, such as butoxy chitosan, carboxymethyl chitosan, carboxybutylchitosan, chitosan gluconate, chitosan adipate, chitosan glycolate, chitosan lactate, etc.; chitins and their derivatives, such as carboxymethyl chitin, chitin glycolate; cellulose and its derivatives such as cellulose acetate; microcrystalline cellulose; sodium hyaluronate; soluble proteoglycans; galacto-arabinans; glycosaminoglycans; glycogen; Sclerotium gum; dextran; starch and its derivatives such as distarch phosphate; and their mixtures.

According to a particular mode, the coloring matter is an organic pigment, synthetic, natural or of natural origin.

By "organic pigment", we mean any pigment that meets the definition of the Ullmann encyclopedia in the organic pigment chapter. The organic pigment, which is therefore insoluble in the medium in which it is found, can in particular be chosen from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, of the metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene , diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophthalone.

The organic pigment(s) may in particular be chosen from carmine, carbon black, aniline black, melanin, azo yellow, quinacridone, phthalocyanine blue, sorghum red, the blue pigments codified in the Color Index under the references CI 69800, 69825, 73000, 74100, 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 20040, 21100, 21108, 47000, the green pigments codified in the Color Index under the references CI 61565, 74260, orange pigments coded in the Color Index under the references CI 11725, 71105, red pigments coded in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 15800, 26100, 58000, 73360 , 73915, 75470, and pigments obtained by oxidative polymerization of indole, phenolic derivatives as described in patent FR 2 679 771.

The pigments can also be in the form of composite pigments as described in patent EP 1 184 426. These composite pigments can be composed in particular of particles comprising an inorganic core covered at least partially with an organic pigment and at least one binder ensuring the fixing of the organic pigments on the core.

The pigment can also be a lake. By lacquer, we mean the insolubilized dyes adsorbed on insoluble particles, the assembly thus obtained remaining insoluble during use. Therefore, such compounds are therefore not considered to be colorants.

The inorganic substrates on which the dyes are adsorbed are for example alumina, silica, calcium and sodium borosilicate or calcium and aluminum borosilicate, and aluminum.

As far as organic dyes are concerned, any type of dye is suitable, nonionic or ionic, cationic or anionic. Preferably, non-anionic dyes are used.

According to a particular mode of the invention, the coloring material is a dye different from the aforementioned acid dyes, water-soluble or 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.

By “liposoluble 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 the oily phase and capable of coloring.

Among the natural water-soluble natural dyes, mention may be made of anthocyanins, belonging to the family of ortho-diphenols. These compounds are more particularly derived from fruits such as grapes, blackberries and plums or vegetables such as red cabbage, red radish or purple sweet potato. They are thus essentially at the origin of the mauve, red, blue and purple colors of flowers, fruits, leaves, seeds and roots.

Mention may also be made of betanin (beetroot), coppery chlorophyllin, methylene blue, caramel, riboflavin, flavonoids and tannins extracted from native or fermented plants, juglone, lawsone, extracts of fermented soybeans, algae, fungi, microorganisms, flavylium salts not substituted in position 3 as described in patent EP 1 172 091, extracts of Gesneria fulgens, Blechum procerum, Saxifraga.

By way of illustration of natural fat-soluble dyes, mention may be made in particular of carotenes such as β-carotene, α-carotene, lycopene; quinoline yellow; xanthophylls such as astaxanthin, antheraxanthin, citranaxanthin, cryptoxanthin, canthaxanthin1, diatomoxanthin flavoxanthin, fucoxanthin, lutein, rhodoxanthin rubixanthin, siphonaxanthin, violaxanthin, zeaxanthin; annatto; turmeric; quinizarin (Ceres Green BB, D&C Green No. 6, CI 61565, 1,4-Di-p-Toluidinoanthraquinone, Green No. 202, Quinzaine Green SS) and chlorophylls.

If the process is implemented in the presence of additional dyestuffs, their content is less than 10% by weight, more particularly less than 8% by weight, and even more preferably less than 5% by weight, relative to the total weight of the composition in which they are present.

FIRST COMPOSITION

The first composition used in the process according to the invention is an aqueous composition.

By aqueous composition is meant a composition comprising at least 5% by weight of water and more preferably at least 20% by weight of water, relative to the total weight of the first composition.

In accordance with a preferred embodiment of the invention, the first composition comprises from 40 to 95% by weight, and more precisely from 50 to 95% by weight, of water, relative to the total weight of the first composition.

The first composition may comprise at least one oily phase. The first composition may optionally be in the form of an oil-in-water emulsion (continuous aqueous phase and dispersed oily phase).

More particularly, if the first composition comprises it, the oily phase content does not exceed 50% by weight, more particularly does not exceed 20% by weight, relative to the weight of the first composition, and preferably the first composition comprises less 2% by weight, relative to the weight of the first composition.

Preferably, the first aqueous composition is in the form of an aqueous solution. More particularly, the composition is in a form comprising only a liquid phase or comprising less than 2% by weight of oily phase.

The pH of the first composition is between 2 and 8, more particularly between 2 and 7.

Advantageously, the aqueous phase comprises at least one buffering agent. The buffering agent is more particularly chosen from organic acids, mineral acids, as well as their salts, having a buffering activity in the pH range mentioned above.

By way of example of organic acids, mention may be made, inter alia, of citric acid, succinic acid, tartaric acid, lactic acid, fumaric acid, malic acid, maleic acid, oxalic acid, as well as mixtures thereof.

By way of mineral acids, mention may in particular be made of phosphoric, sulfuric and nitric acids.

By way of example of salts of these acids, the salts of alkali metals, such as sodium, potassium, ammoniums and salts of alkanolamines, such as salts of triethanolamine, are suitable.

SOLVENT S WATER SOLUBLE S

The composition in accordance with the invention may comprise at least one water-soluble solvent.

By “water-soluble solvent”, is meant in the present invention a compound that is liquid at ambient temperature and miscible with water (miscibility in water greater than 50% by weight at 25° C. and atmospheric pressure (1.013×10 ⁵ Pa)).

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

Among the water-soluble solvents that can be used, mention may be made in particular of monoalcohols, preferably saturated, having from 1 to 5 carbon atoms, such as in particular ethanol and isopropanol, as well as mixtures thereof. Preferably, the water-soluble solvent is chosen from mono-alcohols having 1 to 5 carbon atoms, as well as their mixtures.

Among the water-soluble solvents, mention may also be made of polyols which are liquid at 25° C. and atmospheric pressure (1.013×10 ⁵ Pa).

The term “polyol” denotes any organic molecule comprising at least two hydroxyl groups (or free hydroxyl groups).

More particularly, the liquid polyol(s) can be chosen from C ₂ -C ₈ compounds, more particularly C ₃ -C ₆ compounds, saturated or not, linear or branched, comprising at least two hydroxyl functions, preferably comprising 2 with 6 hydroxyl groups.

Advantageously, said polyol can be chosen from ethylene glycol, pentaerythritol, trimethylolpropane, propylene glycol, dipropylene glycol, 1,3 propanediol, butylene glycol, 1,3-butylene glycol, isoprene glycol, pentylene glycol, hexylene glycol, glycerol, ethylhexyl glycerol, diglycerol, and mixtures thereof.

Preferably, the polyol is chosen from glycerol, propylene glycol, 1,3-butylene glycol, dipropylene glycol, dibutylene glycol, diglycerol, and mixtures thereof; even more advantageously, glycerol.

Among the water-soluble solvents, mention may finally be made of benzyl alcohol; C ₂ -C ₅ alkylene carbonates, preferably ethylene carbonate, propylene carbonate; as well as mixtures thereof.

Preferably, the first composition comprises at least one water-soluble solvent chosen from benzyl alcohol, C ₂ -C ₅ alkylene carbonates, preferably ethylene carbonate, propylene carbonate, and mixtures thereof.

Preferably, if the composition comprises at least one water-soluble solvent, their content varies from 5 to 50% by weight, relative to the total weight of the aqueous composition.

THICKENING S HYDROPHILIC S

The first composition can comprise at least one hydrophilic thickener.

More particularly, the thickener can be chosen from:
- polyacrylic or polymethacrylic acids, copolymers of (meth)acrylic acid and acrylamide, or their salts, in particular of ammonium or of an alkali metal such as sodium;
- acryloyldimethyl taurate copolymers, in particular with the following INCI name hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer; Ammonium Acryloyldimethyltaurate / VP Copolymer, Ammonium Acryloyldimethyltaurate / Carboxyethyl Acrylate Crosspolymer;
- cellulose polymers, in particular hydroxyalkyl (C ₁ -C ₃ ) cellulose, chosen from hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxymethylcellulose, ethylhydroxyethylcellulose; carboxymethylcellulose, as well as quaternized derivatives of cellulose;
- vinyl polymers, such as polyvinylpyrrolidones; copolymers of methylvinyl ether and malic anhydride; the 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: galactomannans and their derivatives, such as Konjac gum, Gellan gum, Locust bean gum, Fenugreek gum, Karaya gum, Tragacanth, gum arabic, acacia gum, guar gum, hydroxypropylguar, hydroxypropylguar modified with sodium methylcarboxylate groups, xanthan gum;
- alginates and carrageenans;
- and mixtures thereof.

According to a preferred embodiment, the hydrophilic thickener is chosen from polyacrylic acids or their salts, acryloyldimethyl taurate copolymers and their salts, in particular the compounds with the INCI name hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer; polyvinyl alcohol, guar derivatives such as hydroxypropyl guar, cellulose derivatives such as hydroxyethylcellulose…, or their mixtures.

Preferably, when the first composition contains it, the content of hydrophilic thickener is between 0.01 and 3% by weight, preferably between 0.05 and 2% by weight, and advantageously 0.1 to 1.5% by weight, relative to the weight of the first composition.

SECOND COMPOSITION

The process according to the invention is implemented from a second composition comprising at least one oil.

The second composition can be in the form of a liquid or solid (stick) composition, and preferably in a liquid form.

OILS

The second composition more particularly comprises at least one oil, volatile or non-volatile, hydrocarbon-based, silicone-based or fluorinated.

By “oil” is meant a liquid fatty substance at 25° C. and atmospheric pressure (1.013.10 ⁵ Pa).

By “non-volatile oil”, is meant an oil whose vapor pressure at 25° C. and atmospheric pressure is non-zero and less than 2.66 Pa, more particularly less than 0.13 Pa. By way of example, the vapor pressure can be measured using the static method or the effusion method by isothermal thermogravimetry, depending on the vapor pressure of the oil (OECD 104 standard).

By "volatile oil" is meant an oil having a vapor pressure greater than or equal to 2.66 Pa, at ambient temperature (25° C.) and atmospheric pressure, ranging in particular from 2.66 Pa to 40,000 Pa, in particular ranging to 13,000 Pa, and preferably to 1,300 Pa.

The term "hydrocarbon oil" means an oil containing mainly hydrogen and carbon atoms and optionally one or more functions chosen from hydroxyl, ester, ether, carboxylic functions. A hydrocarbon oil therefore does not contain any silicon or fluorine atoms.

The term “silicone oil” denotes an oil comprising at least one silicon atom, and in particular at least one Si—O group, and more particularly an organopolysiloxane.

The term “fluorinated oil” denotes an oil comprising at least one fluorine atom.

Non-volatile silicone oils

The non-volatile silicone oil can in particular be chosen from the non-volatile silicones with the following INCI names: dimethicone, dimethiconol, trimethyl pentaphenyl trisiloxane, tetramethyl tetraphenyl trisiloxane, diphenyl dimethicone, trimethylsiloxyphenyl dimethicone, phenyltrimethicone, diphenylsiloxy phenyl trimethicone; as well as mixtures thereof.

Non-volatile fluorinated oils

The fluorinated oil can in particular be chosen from fluorinated polyethers, as well as from fluorosilicone oils, fluorinated silicones as described in document EP-A-847752.

Non-volatile hydrocarbon oils

The composition can comprise at least one non-volatile hydrocarbon-based polar or apolar oil.

“Apolar hydrocarbon-based oil” denotes an oil comprising only carbon and hydrogen atoms, preferably non-aromatic.

As examples of such oils, mention may be made of paraffin oil, squalane, isoeicosane, non-volatile mixtures of linear, saturated hydrocarbons, polybutenes, hydrogenated or not, polyisobutenes, hydrogenated or not, polydecenes, hydrogenated or not, decene/butene copolymers, polybutene/polyisobutene copolymers, as well as mixtures thereof.

By “polar hydrocarbon-based oil” is meant mainly hydrogen and carbon atoms and optionally one or more functions chosen from hydroxyl, ester, ether, carboxylic functions.

The polar hydrocarbon oils can be chosen from:
- fatty alcohols, saturated, unsaturated, linear or branched, C ₁₀ -C ₂₆ , preferably mono-alcohols. Advantageously, the C ₁₀ -C ₂₆ alcohols are fatty alcohols, preferably branched alcohols when they comprise at least 16 carbon atoms. Preferably, the fatty alcohol comprises from 10 to 24 carbon atoms, and more preferentially from 12 to 22 carbon atoms, such as in particular lauryl, isostearyl or oleic alcohol, 2-butyloctanol, 2-undecyl pentadecanol, l 2-hexyldecyl alcohol, isocetyl alcohol, octyldodecanol and mixtures thereof;
- triglycerides consisting of esters of fatty acids and glycerol, in particular the fatty acids of which may have chain lengths varying from C ₄ to C ₃₆ , and in particular from C ₁₈ to C ₃₆ , these oils possibly being linear or branched, saturated or unsaturated. By way of examples, mention may in particular be made of heptanoic or octanoic triglycerides, caprylic/capric acid triglycerides; vegetable oils such as wheat germ, sunflower, grapeseed, sesame, corn, apricot, castor, shea, avocado, olive, soybean, sweet almond oils , palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, squash, blackcurrant, evening primrose, millet, barley, quinoa, rye , safflower, bancoulier, passionflower, muscat rose; the liquid fraction of shea butter, and the liquid fraction of cocoa butter; as well as mixtures thereof;
- linear aliphatic hydrocarbon esters of formula RCOOR' in which RCOO represents a carboxylic acid residue comprising from 2 to 40 carbon atoms, and R' represents a hydrocarbon chain containing from 1 to 40 carbon atoms, the aliphatic hydrocarbon esters of alkylene glycol, in particular ethylene glycol or propylene glycol; the total number of carbon atoms being advantageously at least 10. By way of example of such esters, mention may be made, for example, of cetostearyl octanoate, isopropyl myristate, isopropyl palmitate, stearate or isopropyl isostearate, ethyl palmitate, 2-ethyl-hexyl palmitate, isostearyl isostearate, octyl stearate, isostearyl heptanoate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate, 2-hexyl ethyl palmitate, alkyl benzoate, polyethylene glycol diheptanoate, 2-d diethyl propylene glycol hexanoate and mixtures thereof, hexyl laurate, esters of neopentanoic acid such as isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate, octyl-2-docecyl neopentanoate, isononanoic acid esters such as isononyl isononanoate, isononanoate isot ridecyl, octyl isononanoate, oleyl erucate; lauroyl isopropyl sarcosinate, diisopropyl sebacate, isocetyl stearate, isodecyl neopentanoate, isostearyl behenate, myristyl myristate;
- hydroxylated esters such as polyglycerol-2 triisostearate;
- aromatic esters such as tridecyl trimellitate, C ₁₂ -C ₁₅ alcohol benzoate, 2-phenyl ethyl ester of benzoic acid, butyl octyl salicylate;
- linear fatty acid esters having a total carbon number ranging from 35 to 70, such as pentaerythrityl tetrapelargonate;
- esters of fatty alcohol or branched fatty acids C ₂₄ -C ₂₈ such as triisoarachidyl citrate, pentaerythrityl tetraisononanoate, glyceryl triisostearate, glyceryl tri-2-decyl tetradecanoate, pentaerythrityl tetraisostearate, polyglyceryl-2 tetraisostearate or else pentaerythrityl tetradecyl-2 tetradecanoate;
- polyesters obtained by condensation of dimer and/or trimer of unsaturated fatty acid and of diol such as those of INCI name dilinoleic acid/butanediol copolymer, dilinoleic acid/propanediol copolymer; the polyesters obtained by condensation of a fatty acid dimer and of a diol dimer, such as the dimer dilinoleyl dimer dilinoleate;
- synthetic ethers having 10 to 40 carbon atoms such as dicaprylyl ether;
- di-alkyl carbonates, the 2 alkyl chains possibly being identical or different, such as dicaprylyl carbonate;
- vinylpyrrolidone copolymers such as the vinylpyrrolidone/1-hexadecene copolymer (INCI name);
- their mixtures.

Volatile silicone and hydrocarbon oils

Among suitable volatile silicone oils, mention may be made of linear volatile silicone oils, such as octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and mixtures thereof. Mention may also be made of cyclic volatile silicone oils, such as octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane and mixtures thereof.

As regards volatile hydrocarbon-based oils, mention may in particular be made of C ₈ -C ₁₆ alkane, linear or branched, and more particularly branched, such as isododecane, isodecane, isohexadecane, and mixtures thereof.

Preferably, the composition comprises at least one non-volatile oil, more particularly chosen from silicone, phenyl or non-phenyl oils, from polar or apolar hydrocarbon-based oils, as well as mixtures thereof.

According to another embodiment, the composition comprises at least one volatile oil, preferably hydrocarbon-based.

The oil(s) content of the second composition advantageously varies from 30% to 90% by weight, more particularly from 50% to 90% by weight, relative to the weight of the second composition.

FILM-FORMING POLYMERS

In accordance with a particularly advantageous embodiment of the present invention, the second composition comprises at least one film-forming agent chosen from silicone polyamides; vinyl polymers comprising at least one unit derived from carbosiloxane dendrimer; film-forming ethylenic block copolymers; alkylcelluloses and preferably ethylcellulose; silicone resins; and their mixtures.

Silicone polyamides :

Among the silicone polyamides, mention may be made of the polyorganosiloxanes described in the documents US5874069, US5919441, US6051216 and US5981680. Preferably, the silicone polyamide is the polymer whose INCI name is Nylon-611/dimethicone copolymer, a product marketed under the reference DC 2-8179 by Dow Corning.

Vinyl polymers with a carbosiloxane dendrimer pattern :

As regards the vinyl polymers comprising at least one unit derived from carbosiloxane dendrimer, the latter have a hydrocarbon skeleton derived from at least one (meth)acrylic unit and at least one side chain comprising a unit derived from carbosiloxane dendrimer having a structure carbosiloxane dendrimer.

The term "carbosiloxane dendrimer structure" means a molecular structure possessing branched groups having high molecular masses, said structure having a high regularity in the radial direction starting from the bond to the backbone. Such polymers are in particular described in the documents EP0963751, WO03/045337 (for fluorinated polymers). The vinyl polymers grafted with at least one unit derived from carbosiloxane dendrimer particularly suitable for the present invention are the polymers whose INCI name is Acrylates/polytrimethylsiloxy methacrylate copolymer, and in particular sold under the names FA 4002 ID Silicone Acrylate, FA 4001 CM Silicone Acrylate , by the Dow Corning Company. Said polymers are marketed as a mixture in isododecane or in cyclopentasiloxane respectively.

Ethylene block copolymers :

As regards the film-forming ethylenic block copolymers, the copolymers comprising at least a first block having a glass transition temperature (Tg) greater than or equal to 40° C. and being derived in whole or in part from one or more first monomers, are suitable, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40°C, and at least one second block having a glass transition temperature less than or equal to 20°C and being derived from whole or in part of one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20°C, said first block and said second block being linked together by a random intermediate segment comprising at least one of said first constituent monomers of the first block and at least one of said second monomers constituent eras of the second block, and said block copolymer having a polydispersity index I greater than 2. Such copolymers are described in particular in the documents EP1882709, EP1411069. By way of example, it is possible to use copolymers whose INCI name is Acrylic acid/isobutyl acrylate/isobornyl acrylate copolymer. This copolymer is found mixed with isododecane, in particular in the Mexomere PAS product.

Alkylcelluloses :

The alkylcelluloses suitable for carrying out the present invention comprise at least one C ₂ -C ₆ alkyl residue, and are preferably chosen from ethylcellulose, propylcellulose, and even more preferably ethylcellulose.

Alkylcelluloses are alkyl ethers of cellulose, comprising a chain consisting of β-anhydroglucose units linked together by acetal bonds, each of the anhydroglucose units of which has three replaceable hydroxyl groups. The total substitution of the three hydroxyl groups would lead for each unit to a degree of substitution of 3, in other words to a content of alkoxy groups, in particular ethoxy groups, of 54.88%.

The ethylcellulose polymers, which are particularly suitable for the present invention, are polymers having a degree of substitution in ethoxy groups, ranging from 2.5 to 2.6 per anhydroglucose unit, in other words comprising a content of ethoxy groups ranging from 44% to 50%.

The average molar mass of the ethylcellulose is preferably chosen so that the viscosity of a 5% solution by weight in an 80/20 mixture (toluene/ethanol) at 25° C. ranges from 4 to 300 mPa .s, preferably from 5 to 200 mPa.s, for example from 5 to 150 mPa.s. (ASTM D 914 standard)

Ethylcellulose can be used in powder form or in latex form.

It is for example marketed under the trade names “ETHOCEL Standard” from Dow Chemicals, with in particular “ETHOCEL Standard 7 FP Premium” and “ETHOCEL standard 100 FP Premium”. Other commercially available products, such as those marketed by Ashland, Inc., under the names Aqualon Ethylcellulose type-K, type-N and type-T, preferably type-N, such as N7, N100, are particularly suitable. to the realization of the invention. Ethylcellulose in the form of an aqueous dispersion, Aquacoat ECD-30 marketed by FMC, could also be suitable.

Silicone resins :

More generally, the term "resin" means a compound whose structure is three-dimensional. Thus, for example, within the meaning of the present invention, a polydimethylsiloxane is not a silicone resin, within the meaning of the present invention. It should also be noted that the film-forming silicone resins are not silicone fillers such as, for example, the polymethylsilsesquioxane particles, marketed under the name Tospearl®, by Momentive Performance Materials.

The nomenclature of silicone resins (also called siloxane resins or silicone resin) is known as "MDTQ", the resin being described according to the different monomeric siloxane units it comprises, each of the letters "MDTQ" characterizing a type of unit.

The letter “M” represents the Monofunctional unit of formula R ₁ R ₂ R ₃ SiO _1/2 , the silicon atom being linked to a single oxygen atom in the polymer comprising this unit.

The letter "D" means a difunctional unit R ₁ R ₂ SiO _2/2 in which the silicon atom is connected to two oxygen atoms

The letter “T” represents a trifunctional unit of formula R ₁ SiO _3/2 .

Such resins are described for example in “Encyclopedia of Polymer Science and Enginering, vol. 15, John and Wiley and Sons, New York, (1989), p. 265-270, and US 2,676,182, US 3,627,851, US 3,772,247, US 5,248,739 or even US 5,082,706, US 5,319,040, US 5,302, 685 and US 4,935,484.

In the units M, D, T defined above, R _i , namely R ₁ , R ₂ and R ₃ , which are identical or different, represent a hydrocarbon radical (in particular alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or alternatively a hydroxyl group.

Finally, the letter “Q” signifies a SiO _4/2 tetrafunctional unit in which the silicon atom is bonded to four oxygen atoms which are themselves bonded to the rest of the polymer.

Various silicone resins with different properties can be obtained from these different units, the properties of these polymers varying according to the type of monomers (or units), the nature and the number of the radical(s) Ri, the length of the polymer chain, the degree of branching and the size of the pendant chains.

The silicone resin can be used in the form of a powder, in a form dissolved in a solvent, in a form conveyed in a liquid or even in a form emulsified in water. It should be noted that in the latter case, the silicone resin is preferably in a conveyed form, advantageously dissolved in a solvent, then emulsified.

As regards the silicone resins conveyed in a solvent, the latter is usually chosen from apolar hydrocarbon-based oils or silicone oils, volatile or non-volatile and preferably volatile.

As silicone resins which can be used in the compositions according to the invention, it is possible to use, for example, silicone resins of the MQ type, of the T type or of the MQT type.

MQ Resins :

As an example of silicone resins of the MQ type, mention may be made of the alkylsiloxysilicates of formula [(R ₁ ) ₃ SiO _1/2 ] _x (SiO _4/2 ) _y (MQ units) in which x and y are integers ranging from 50 to 80, and such that the group R ₁ represents a radical as defined above, and is preferably an alkyl group having from 1 to 8 carbon atoms, or a hydroxyl group, preferably a methyl group.

As examples of solid silicone resins of MQ type of trimethylsiloxysilicate type, mention may be made of those marketed under the reference SR1000 by the company Momentive Performances Materials, under the reference MQ 1600 by Dow Corning, under the reference Belsil TMS 803 by the company Wacker. Mention may also be made of products comprising a mixture of silicone resin with a volatile oil, in particular hydrocarbon-based, such as for example isododecane, such as in particular the product Silsoft 74, Silshine 151 from Momentive Performances Materials, or the products X-21-5595 and X-21-5616 from Shin Etsu. Also suitable are mixtures of trimethylsiloxysilicate with a dimethicone, such as for example those marketed under the names KF-7312K, KF-7312L, X-21-5249L and X-21-5250L by the company Shin Etsu or Dow Corning 593 Fluid by the Dow Corning Company,

As silicone resins comprising MQ siloxysilicate units, mention may also be made of phenylalkylsiloxysilicate resins, such as phenylpropyl dimethyl siloxysilicate (Silshine 151 marketed by the company Momentive Performances Materials). The preparation of such resins is described in particular in patent US5817302.

T-resins :

As examples of T-type silicone resins, mention may be made of polysilsesquioxanes of formula (RSiO _3/2 ) _x (T units) in which x is greater than 100 and such that the group R is an alkyl group having 1 to 10 carbon atoms, said polysilsesquioxanes possibly further comprising terminal Si—OH groups.

Mention may also be made of polymethylsilsesquioxanes which are polysilsesquioxanes in which none of the methyl radicals is substituted by another group. Such polymethylsilsesquioxanes are described for example in document US 5,246,694.

Preferably, it is possible to use polymethylsilsesquioxane resins in which R represents a methyl group, such as for example those marketed by the company Wacker under the reference Resin MK such as Belsil PMS MK: polymer comprising repeating units CH ₃ SiO _3/2 ( T units), which may also comprise up to 1% by weight of (CH ₃ ) ₂ SiO _2/2 units (D units) and having an average molecular weight of approximately 10,000 g/mol. Also suitable are the products marketed by the company SHIN-ETSU under the references KR-220L which are composed of T units of formula CH ₃ SiO _3/2 and have terminal Si-OH (silanol) groups, under the reference KR- 242A which comprise 98% T units and 2% dimethyl D units and have Si-OH terminal groups or under the reference KR-251 comprising 88% T units and 12% dimethyl D units and have Si-OH terminal groups. It is also possible to use the products of the company Dow Corning referenced Dow Corning 670 Fluid, Dow Corning 680 Fluid, comprising a mixture in the cyclopentasiloxane and in the isododecane respectively, of the polypropylsilsesquioxane resin (INCI name). Finally, it is possible to use mixtures of MQ resin and of T resin, such as for example the products marketed under the name Dow Corning MQ-1640 Flake Resin by the company Dow Corning comprising a mixture of trimethylsiloxysilicate and polypropylsilsesquioxane.

MQT resins :

As a resin comprising MQT units, those cited in document US Pat. No. 5,110,890 are known in particular.

A preferred form of MQT type resins are MQT-propyl (also called MQTPr) resins. Such resins which can be used in the compositions according to the invention are in particular those described and prepared in application WO 2005/075542, the content of which is incorporated here by reference.

The MQ-T-propyl resin preferably comprises the units: (i) (R1₃SiO_1/2)_To ; (ii) (R2₂SiO_2/2)_b ; (iii) (R3SiO_3/2)_vsand (iv) (SiO_4/2)_dwith R1, R2 and R3 independently representing a hydrocarbon radical (in particular alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or even a hydroxyl group and preferably an alkyl radical having from 1 to 8 carbon or a phenyl group; a, b, c and d being mole fractions; a being between 0.05 and 0.5; b being between zero and 0.3; c being greater than zero; d being between 0.05 and 0.6; a+b+c+d=1; provided that more than 40 mole % of the R3 groups of the siloxane resin are propyl groups.

Preferably, the siloxane resin comprises the units (i) (R1 ₃ SiO _1/2 ) _a ; (R3SiO _3/2 ) _c and (SiO _4/2 ) _d with R ₁ and R ₃ independently representing an alkyl group having from 1 to 8 carbon atoms, R ₁ preferably being a methyl group and R ₃ preferably being a propyl group; a being between 0.05 and 0.5, preferably between 0.15 and 0.4; c being greater than zero, preferably between 0.15 and 0.4; d being between 0.05 and 0.6, preferably between 0.2 and 0.6, or else between 0.2 and 0.55; a + b + c + d = 1, and a, b, c and d being molar fractions; provided that more than 40% by mole of the R ₃ groups of the siloxane resin are propyl groups.

The siloxane resins which can be used according to the invention can be obtained by a process comprising the reaction of:
A) an MQ resin comprising at least 80% by mole of (R1 ₃ SiO _1/2 ) _a and (SiO _4/2 ) _d units with R1 representing an alkyl group having from 1 to 8 carbon atoms, an aryl group , a carbinol group or an amino group; a and d being greater than zero; the a/d ratio being between 0.5 and 1.5; and of
B) a propyl T resin comprising at least 80% by mole of (R3SiO _3/2 ) _c units with R3 representing an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group ; c being greater than zero; provided that at least 40% by moles of the R3 groups are propyl groups; where the A/B mass ratio is between 95:5 and 15:85, preferably the A/B mass ratio is 30:70.

Advantageously, the A/B mass ratio is between 95:5 and 15:85. Preferably, the A/B ratio is less than or equal to 70:30. These preferred ratios have proven to allow for comfortable deposits.

Preferably, the composition according to the invention comprises, as silicone resin, at least one trimethylsiloxysilicate, polymethylsilsesquioxane, polypropylsilsesquioxane resin, as well as mixtures thereof.

Preferably, the film-forming polymer(s) are chosen from silicone polyamides, silicone resins, alone or as a mixture, and more particularly Nylon-611/dimethicone copolymer; trimethylsiloxysilicate, polymethylsilsesquioxane and polypropylsilsesquioxane resins, as well as mixtures thereof.

If it comprises any, the second composition has a content of film-forming polymer(s) (expressed as active material of the film-forming polymer) varying from 1 to 50% by weight, more particularly from 2 to 20% by weight, even more particularly from 5 to 20% by weight, relative to the total weight of the second composition.

LIPOPHILIC THICKENERS

The composition according to the invention may comprise at least one mineral thickener chosen more particularly from clays, silicas, or mixtures thereof, and/or also at least one organic thickener chosen more particularly from dextrin esters.

Lipophilic clays

The clays can be natural or synthetic and they are rendered lipophilic by treatment with an alkyl ammonium salt such as a C ₁₀ to C ₂₂ ammonium chloride, for example di-stearyl di-methyl ammonium chloride.

They can be chosen from bentonites, in particular hectorites and montmorillonites, beidellites, saponites, nontronites, sepiolites, biotites, attapulgites, vermiculites and zeolites.

Preferably, they are chosen from hectorites.

Preferably, use is made as lipophilic clays of hectorites modified with a C ₁₀ to C ₂₂ ammonium chloride, such as hectorite modified with di-stearyl di-methyl ammonium chloride such as, for example, that marketed under the name Bentone 38V® by the company Elementis or the bentone gel in isododecane marketed under the name Bentone Gel ISD ^V® (Isododecane 87%/Disteardimonium Hectorite 10%/Propylene carbonate 3%) by the company Elementis.

Hydrophobic silicas

The composition according to the invention may also comprise, as a lipophilic thickener, a fumed silica or particles of silica airgel.

The s ilia s pyrogenic s

Particularly suitable for the invention, fumed silica treated hydrophobic surface. It is in fact possible to chemically modify the surface of the silica, by chemical reaction generating a reduction in the number of silanol groups present on the surface of the silica. It is possible in particular to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained.

The hydrophobic groups can be:
- trimethylsiloxyl groups, which are obtained in particular by treating fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are called “Silica silylate” according to the CTFA ( ^8th edition, 2000). They are for example marketed under the references Aerosil R812® by the company Degussa, CAB-O-SIL TS-530® by the company Cabot.
- dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained in particular by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are called “Silica dimethyl silylate” according to the CTFA (8th edition, 2000). They are for example marketed under the references Aerosil R972®, and Aerosil R974® by the company Degussa, CAB-O-SIL TS-610® and CAB-O-SIL TS-720® by the company Cabot.

Silica aerogels

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 different drying methods are described in detail in Brinker CJ., and Scherer GW, Sol-Gel Science: New York: Academic Press, 1990.

The hydrophobic silica airgel particles usually have a specific surface area per unit mass (S _M ) 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, and 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, preferably further from 5 to 25 µm, better from 5 to 20 µm and even better from better from 5 to 15 µm.

According to one embodiment, the hydrophobic silica airgel particles used in the present invention 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 method (BRUNAUER – EMMET – TELLER) 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 hydrophobic silica airgel particles used in the present invention have a specific surface area per unit mass (S _M ) ranging from 600 to 800 m ² /g and a size expressed as volume-average diameter (D[0.5]) ranging from 5 to 20 μm and even better still from 5 to 15 μm.

The aerogels are hydrophobic silica aerogels, preferably of 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.

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

Preferably, hydrophobic silica airgel particles modified at the surface with trimethylsilyl groups will be used.

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

Mention may also be made of the aerogels marketed by the company Cabot under the references AEROGEL TLD 201, AEROGEL OGD 201, AEROGEL TLD 203, ENOVA® AEROGEL MT 1100, ENOVA AEROGEL MT 1200.

The airgel marketed under the name VM-2270 (INCI name Silica silylate), by the company Dow Corning, will preferably be used, the particles of which have an average size ranging from 5-15 microns and a specific surface area per unit of mass ranging from 600 to 800 m ² /g.

Dextrin esters

The composition may also comprise at least one dextrin ester, more particularly an ester of dextrin and of a C ₈ -C ₃₀ fatty acid.

More particularly the ester of dextrin and fatty acid, corresponds to the formula (I):

in which the radicals R1, R2 and R3, which are identical or different, are chosen from hydrogen or an acyl group (R-CO-) in which the radical R is a hydrocarbon-based group, linear or branched, saturated or unsaturated, possessing 6 to 30, in particular 8 to 22, or even 12-18, carbon atoms, provided that at least one of said radicals R1, R2 or R3 is different from hydrogen; n is an integer between 3 and 150, in particular 10 and 100, and preferably 15-40.

Preferably, the three radicals R1, R2 and R3 are different from hydrogen, which leads to dextrin esters having the following formula (II):

in which the radicals R'1, R'2 and R'3, which are identical or different, represent a hydrocarbon group, linear or branched, saturated or unsaturated, possessing 6 to 30, in particular 8 to 22, more particularly 12-18 atoms of carbon; n is an integer between 3 and 150, in particular 10 and 100, and preferably 15-40.

In particular the radicals -OCOR'1, -OCOR'2 and/or -OCOR'3 can be chosen from the radicals caprylic, capric, lauric, myristic, palmitic, stearic, arachic, behenic, isobutyric, isovaleric, ethyl-2 butyric, éthylméthylacétique, isoheptanoïque, éthyl-2 hexanoïque, isononanoïque, isodécanoïque, isotridécanoïque, isomyristique, isopalmitique, isostéarique, isoaracique, isohexanoïque, decenoïque, dodécenoïque, tetradecenoïque, myristoléïque, hexadécénoïque, palmitoléïque, oléïque, élaidique, asclepinique, gondoléïque, eicosènoïque, sorbique, linoléïque , linolenic, punicic, stearidonic, arachidonic, stearolic, and mixtures thereof.

Preferably, the dextrin ester is chosen from dextrin palmitate, dextrin myristate. Some of these dextrin esters are commercially available, in particular under the name RHEOPEARL from the company Chiba floor Milling. Co.

When the composition comprises them, the content of lipophilic thickening agent(s) represents from 0.01 and 5% by weight, preferably between 0.05 and 3% by weight, and advantageously 0.1 to 2% by weight, relative to the total weight of the composition.

SOLID FAT COMPOUNDS

Raincoats

The second composition according to the invention may optionally comprise at least one silicone wax, or a hydrocarbon wax, polar or apolar.

The wax considered in the context of the present invention is generally a lipophilic compound that is solid at room temperature (25° C.), with a reversible solid/liquid state change, having a melting point in particular greater than or equal to 30°C, more particularly above 45°C. Advantageously, the melting point is less than or equal to 90°C, more particularly less than or equal to 80°C, and preferably less than or equal to 70°C.

The melting point of a solid fatty substance can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name “DSC Q100” by the company TA Instruments with the software “TA Universal Analysis”.

The measurement protocol is as follows:
A sample of solid fatty substance of approximately 5 mg is placed in an "airtight aluminum capsule" crucible.
The sample is subjected to an initial rise in temperature ranging from 20°C to 120°C, at a heating rate of 2°C / minute up to 80°C, then left at isotherm of 100°C for 20 minutes , then cooled from 120°C to – 0°C at a cooling rate of 2°C / minute, and finally subjected to a second temperature rise ranging from 0°C to 20°C at a heating rate of 2 °C/min.
The melting temperature value of the solid fatty substance is the value of the top of the most endothermic peak of the observed melting curve, representing the variation of the difference in power absorbed as a function of temperature.

Polar hydrocarbon waxes :

More particularly, the polar wax is chosen from hydrocarbon-based ester waxes, hydrocarbon-based alcohol waxes, silicone waxes, as well as mixtures thereof.

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.

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. The additional alcohol wax in particular does not comprise an ester function.

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

Ester waxes

It is possible in particular to use as ester wax, the waxes 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, which can contain a heteroatom in particular oxygen, and whose the melting point temperature varies from 30 to 120°C, preferably from 30 to 100°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 - _C40 . 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 mixtures of C14-C18 carboxylic acid esters and alcohols such as the products "Cetyl Ester Wax 814" from the company KOSTER KEUNEN, "SP Crodamol MS MBAL", "Crodamol MS PA" from the company CRODA, “Miraceti” from company LASERSON. 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 a C ₄ -C ₃₀ alkyl group (alkyl group comprising from 4 to 30 carbon atoms) and R ⁴ represents a linear or branched C ₄ -C ₃₀ aliphatic group (alkyl group comprising from 4 to 30 carbon atoms) which may or may not contain one or more unsaturations. Preferably, the C ₄ -C ₃₀ aliphatic group is linear and unsaturated.
iv) waxes obtained by catalytic hydrogenation of animal or vegetable oils having in particular fatty chains, linear or branched, C ₈ -C ₃₂ , for example such as hydrogenated jojoba oil, hydrogenated 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 the company 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 of animal or vegetable origin, such as beeswax, synthetic beeswax, carnauba wax, candelilla wax, lanolin wax, rice bran wax, wax of 'Ouricury, Alfa wax, berry wax, shellac wax, cork fiber wax, sugarcane wax, Japan wax, sumac wax, montan wax, waxes of Orange and Lemon, laurel wax, hydrogenated Jojoba wax, sunflower wax, in particular refined.
vi) Mention may also be made of hydrocarbon-based, polyoxyalkylenated or polyglycerolated waxes, natural or synthetic, of animal or vegetable origin; the number of oxyalkylenated (C2-C4) units can vary from 2 to 100, the number of glycerolated units can vary from 1 to 20. Examples include polyoxyethylenated beeswax, such as PEG- 6 beeswax, peg-8 beeswax; polyoxyethylenated carnauba waxes, such as PEG-12 carnauba; lanolin waxes, hydrogenated or not, polyoxyethenized or polyoxypropylene, such as PEG-30 lanolin, PEG-75 lanolin; PPG-5 lanolin wax glyceride; polyglycerolated beeswax, in particular polyglyceryl-3 Beewax, the Acacia Decurrens/Jojoba/Sunflower Seed Wax/Polyglyceryl-3 Esters mixture, polyglycerolated vegetable waxes such as mimosa, jojoba, sunflower waxes, and mixtures thereof (Acacia Decurrens/Jojoba/Sunflower Seed Wax Polyglyceryl-3 Esters.
vii) 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.
viii) as well as mixtures thereof.

Alcohol waxes

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° C. and 90° C. Examples of alcohol wax include stearic alcohol, cetyl alcohol, myristic alcohol, palmitic alcohol, behenic alcohol, erucic alcohol, arachidyl alcohol, or mixtures thereof.

Apolar hydrocarbon waxes s:

The composition may optionally comprise at least one additional wax chosen from apolar hydrocarbon waxes.

By “ non-polar hydrocarbon-based wax ”, within the meaning of the present invention, is meant a wax comprising only carbon or hydrogen atoms in its structure. In other words, such a wax is free of other atoms, in particular of heteroatoms such as for example nitrogen, oxygen, silicon.

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, waxes obtained by the synthesis of Fischer-Tropsch, microwaxes, in particular polyethylene.

Silicone waxes:

Mention may be made, as silicone wax, for example of mixtures comprising a compound of the C30-45 Alkyldimethylsilyl Polypropylsilsesquioxane type (INCI name), for example the product Dow Corning SW-8005 C30 Resin Wax marketed by the company Dow Corning. Mention may also be made of mixtures comprising a compound of the C30-45 Alkyl Methicone type (INCI name), such as for example the product Dow Corning® AMS-C30 Cosmetic Wax. We can also mention silicone beeswax.

The second composition may optionally comprise a content of wax(es), preferably polar(s), preferably hydrocarbon(s), is between 1 and 20% by weight, more particularly from 2 to 10% by weight, relative to the weight of the composition.

PASTY COMPOUNDS

The second composition according to the invention may optionally comprise at least one pasty fatty compound at room temperature.

By "pasty fatty substances" within the meaning of the invention, we mean fatty substances having a melting point ranging from 20 to 55° C., preferably 25 to 45° C., and/or a viscosity at 40° C. ranging from 0.1 to 40 Pa.s (1 to 400 poise), preferably 0.5 to 25 Pa.s, measured with Contraves TV or Rhéomat 80, equipped with a spindle rotating at 60 Hz.

A person skilled in the art can choose the spindle for measuring the viscosity, from spindles MS-r3 and MS-r4, on the basis of his general knowledge, so as to be able to carry out the measurement of the pasty compound tested.

Preferably, these fatty substances are hydrocarbon compounds, optionally of the polymeric type; they can also be chosen from silicone compounds; they can also be in the form of a mixture of hydrocarbon and/or silicone compounds.

In the case of a mixture of different pasty fatty substances, the pasty hydrocarbon compounds are preferably used (mainly containing carbon and hydrogen atoms and optionally oxygen atoms, more particularly in the form of ester groups), in majority proportion.

Among the pasty compounds capable of being used in the composition according to the invention, mention may be made of lanolins and lanolin derivatives such as acetylated lanolins or oxypropylene lanolins or isopropyl lanolate, having a viscosity of 18 to 21 Pa .s, preferably 19 to 20.5 Pa.s, and/or a melting point of 30 to 55°C and mixtures thereof. It is also possible to use fatty acid or alcohol esters, in particular those having 20 to 65 carbon atoms (melting point of the order of 20 to 35° C. and/or viscosity at 40° C. ranging from 0. 1 to 40 Pa.s) such as tri-isostearyl or cetyl citrate; arachidyl propionate; polyvinyl laurate; cholesterol esters such as triglycerides of vegetable origin such as partially or totally hydrogenated vegetable oils, butters of vegetable origin, viscous polyesters such as poly(12-hydroxystearic) acid and mixtures thereof.

The esters of an oligomeric glycerol, in particular the esters of diglycerol, in particular the condensates of adipic acid and of glycerol, for which part of the hydroxyl groups of the glycerols have reacted with a mixture of fatty acids such as stearic acid, capric acid, stearic acid, isostearic acid and 12-hydroxystearic acid, such as those sold in particular under the brand name Softisan 649 by the company Sasol; or alternatively diol dimer and diacid dimer esters, where appropriate, esterified on their alcohol(s) or free acid(s) function(s) by acid or alcohol radicals, in particular dilinoleate dimer esters ; such as the products marketed under the Plandool brand (bis-behenyl/isostearyl/phytosteryl dimerdilinoleyl dimerdilinoleate (Plandool G), phytosteryl/isosteryl/cetyl/stearyl/behenyl dimerdilinoleate (Plandool H or Plandool S)).

Mention may also be made of pasty silicone fatty substances such as polydimethylsiloxanes (PDMS) having pendant chains of the alkyl or alkoxy type having from 8 to 24 carbon atoms, and a melting point of 20-55° C., such as stearyl dimethicones in particular those sold by the company Dow Corning under the trade names of DC2503 and DC25514, and mixtures thereof.

The second composition according to the invention may optionally comprise a content of pasty compound(s), preferably polar compound(s), preferably hydrocarbon compound(s), of between 1 and 20% by weight, more particularly from 3 to 15% by weight, relative to the weight of the composition.

Water

The second composition according to the invention may or may not comprise water.

According to a first embodiment of the invention, the second composition is in the form of a composition whose water content is less than 5% by weight, more particularly less than 2% by weight, even more particularly less than 1% by weight, relative to the weight of the second composition, and preferably in the form of an anhydrous composition.

According to a second embodiment of the invention, the second composition is in the form of an emulsion. Preferably, the continuous phase of the emulsion is the oily phase (water-in-oil emulsion). In this case, the amount of aqueous phase is preferably greater than 10% by weight, or even greater than 20% by weight, and more preferably ranging from 20 to 50% by weight, relative to the total weight of the second composition.

The pH of the aqueous phase of the second composition is more particularly between 2 and 8, more particularly between 2 and 7.

Advantageously, the aqueous phase comprises at least one buffering agent. The buffering agent can in particular be chosen from organic acids, mineral acids, as well as their salts, having a buffering activity in the pH range mentioned above.

As examples of organic acids, mention may be made, inter alia, of citric acid, succinic acid, tartaric acid, lactic acid, fumaric acid, malic acid, maleic acid, oxalic acid, as well as mixtures thereof.

By way of mineral acids, mention may in particular be made of phosphoric, sulfuric and nitric acids.

By way of example of salts of these acids, the salts of alkali metals, such as sodium, potassium, ammoniums and salts of alkanolamines, such as salts of triethanolamine, are suitable.

The second composition in accordance with the invention may also comprise at least one water-soluble solvent chosen more particularly from C ₁ -C ₅ mono-alcohols such as in particular ethanol and isopropanol, as well as their mixtures. The water-soluble solvent can also be chosen from polyols that are liquid at 25° C. and atmospheric pressure (1.013.10 ⁵ Pa), in particular C ₂ -C ₈ compounds, more particularly C ₃ -C ₆ compounds, saturated or not, linear or branched, comprising at least two hydroxyl functions, preferably comprising from 2 to 6 hydroxyl groups. Preferably, said polyol is chosen from glycerol, propylene glycol, 1,3-butylene glycol, dipropylene glycol, dibutylene glycol, diglycerol, and mixtures thereof; even more advantageously, glycerol. Among the water-soluble solvents, mention may finally be made of benzyl alcohol; C ₂ -C ₅ alkylene carbonates, preferably ethylene carbonate, propylene carbonate; as well as mixtures thereof.

Preferably, in particular if the second composition comprises water, it comprises at least one water-soluble solvent chosen from benzyl alcohol, C ₂ -C ₅ alkylene carbonates, preferably ethylene carbonate, propylene carbonate, or mixtures thereof.

Preferably, if the second composition comprises at least one water-soluble solvent, its content varies from 1 to 20% by weight, relative to the total weight of the second composition.

When the second composition is in the form of an emulsion, it may comprise one or more emulsifying surfactants.

Within the meaning of the present invention, the term “emulsifying surfactant” is understood to mean an amphiphilic surfactant compound, that is to say having two parts of different polarity. In general, one is lipophilic (soluble or dispersed in an oily phase. The other is hydrophilic (soluble or dispersible in water). Emulsifying surfactants are characterized by the value of their HLB (Hydrophile Lipophile balance or hydrophilic balance -lipophilic), the HLB being the ratio between the hydrophilic part and the lipophilic part in the molecule. The term HLB is well known to those skilled in the art and is described for example in "The HLB system. A time-saving guide to Emulsifier Selection" (published by ICI Americas Inc.; 1984). For emulsifying surfactants, the HLB generally ranges from 3 to 8 for the preparation of water-in-oil emulsions. The HLB of the surfactant(s) used according to the invention can be determined by the GRIFFIN method or the DAVIES method.

Optional Cosmetic Ingredients

The first and/or the second composition according to the invention can also comprise any usual cosmetic ingredient, which can be chosen in particular from perfumes, preservatives, neutralizers, sunscreens, sweeteners, vitamins, free radical scavengers and sequestrants, and their mixtures.

It goes without saying that those skilled in the art will take care to select the possible additional ingredients and/or the quantity of these in such a way that the advantageous properties of the composition according to the invention are not, or are not substantially, degraded.

COSMETICS KITS

The present invention also relates to cosmetic kits for implementing a process for making up human keratin materials, in particular the lips, according to the invention.

Thus, according to a first variant, the kit comprises:
- a first aqueous composition comprising at least one amino acid containing at least one additional cationizable function, its C ₁ -C ₃ esters or the corresponding oligopeptides;
a second composition, in the form of an emulsion or in the form of a composition comprising less than 5% by weight of water relative to the weight of the composition, comprising at least one oil and at least one acid dye.

According to a second variant, the kit that it comprises:
- a first aqueous composition comprising at least one acid dye,
- a second composition comprising at least one oil, in the form of an emulsion or in the form of a composition comprising less than 5% by weight of water, relative to the weight of the composition, and preferably in the form of a emulsion, and at least one amino acid containing at least one additional cationizable function, its C ₁ -C ₃ esters or the corresponding oligopeptides.

The first and second compositions used in the process according to the invention are each packaged in a container or compartment, said container being closed by a closure element.

The container may be in any suitable form. It may in particular be in the form of a bottle, a tube, a jar or a case.

The closure element can be in the form of a removable cap, a lid, a lid, in particular of the type comprising a body fixed to the container and a cap hinged to the body. It can also be in the form of an element ensuring the selective closure of the container, in particular a pump, a valve, or a valve.

The container can be associated with an applicator, in particular in the form of a brush comprising an arrangement of bristles held by a twisted wire. Such a twisted brush is described in particular in US Patent 4,887,622. It can also be in the form of a comb comprising a plurality of application elements, obtained in particular by molding. Such combs are described for example in patent FR 2 796 529. The applicator can be in the form of a brush, as described for example in patent FR 2 722 380. The applicator can be in the form of a block of foam or elastomer. The applicator can be free (sponge) or attached to a rod carried by the closure element, as described for example in US Pat. No. 5,492,426. The applicator can be attached to the container, as described for example in patent FR 2 761 959.

The product can be contained directly in the container, or indirectly.

The closing element can be coupled to the container by screwing. Alternatively, the coupling between the closure element and the container is done other than by screwing, in particular via a bayonet mechanism, by snap-fastening, or by tightening. By “snap-on” is meant in particular any system involving the crossing of a bead or a bead of material by elastic deformation of a portion, in particular of the closure element, then by return to the elastically unconstrained position of said portion after crossing the bead or bead.

The container may be at least partly made of thermoplastic material. Examples of thermoplastic materials include polypropylene or polyethylene.

The container may have rigid walls or deformable walls, in particular in the form of a tube or a tube bottle.

The container may include means to cause or facilitate dispensing of the composition. By way of example, the container may have deformable walls so as to cause the composition to come out in response to an overpressure inside the container, which overpressure is caused by elastic (or inelastic) crushing of the walls of the container .

The container can be equipped with a wiper placed near the opening of the container. Such a wiper makes it possible to wipe the applicator and possibly the rod to which it may be attached. Such a wiper is described for example in patent FR 2 792 618.

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

The expressions “between… and…” and “ranging from… to…” must be understood to include limits, unless the contrary is specified.

In addition, the sum of the amounts of the ingredients of the composition represents 100% by weight of the composition.

The invention is illustrated in more detail by the examples presented below.

Unless otherwise indicated, the quantities indicated are expressed in percentage by weight.

The following examples are presented by way of non-limiting illustration of the invention.

Examples

Example 1

The following first composition is prepared:

Ingredients Quantity
(% by weight of raw material) Water 88 Phenoxyethanol 0.5 Arginine ethyl ester 10 Hydroxypropyl guar (Jaguar HP 105, Solvay) 1.5

The following second composition is prepared:

Ingredients (INCI) Quantity
(% by weight of raw material) Trimethylsiloxysilicate (SR 1000, Momentive Performance Materials) 18.5 Silica silylate (DOWSIL VM-2270 AEROGEL FINE PARTICLES, Dow Corning) 0.5 Propylene carbonate 2.0 C30-45 alkyldimethylsilyl polypropylsilsesquioxane (DOWSIL SW-8005 C30 RESIN WAX, Dow Corning) 2.1 Nylon-611/dimethicone copolymer
(DOWSIL 2-8179 GELLANT; Dow Corning) 10.3 Dimethicone (and) dimethicone crosspolymer (DOWSIL EL-9140DM SILICONE ELASTOMER BLEND, Dow Corning) 37.6 Dimethicone (DOWSIL SH 200 C FLUID 350 CST, Dow Corning) 10.5 Isododecane qsp 100 RED 27 0.2 Ethanol 5.0

Process for preparing the composition
1. The silicone oil, the silicone wax, the Nylon-611/dimethicone polymer, the trimethylsiloxysilicate resin, the isododecane and the propylene carbonate are mixed with Rayneri stirring at 80°C.
2. Once the mixture is homogeneous, the silicone elastomer and the silica are added, with stirring at 80°C.
3. After homogenization, the resulting mixture is allowed to cool to room temperature.
4. In parallel, the dye is mixed in alcohol at room temperature with magnetic stirring until dissolved.
5. The resulting mixture is then added to that of step 3 under Rayneri stirring at ambient temperature.
6. Once the mixture is homogeneous, it is packaged.

Application method:

1. Preparation of the lips

The lips are scrubbed using a scrub composition Sucres de Soin Gommage Eclat from L'Oréal Paris. Then 2 hours after the treatment, the lips are photographed and their coloring is measured (Chromasphere Chromalys Samba-Shiva with SAMBA polarimetric camera; definition 410x410 pixels)

2.P lip treatment process and measurement

The first composition is applied and left to dry for 15 minutes.
The second composition is then applied and left to dry for 15 minutes.
A photograph of the lips thus made up is taken and their coloration is measured.
A second photograph is taken 24 hours after the application, the subject having taken his meals normally, the first having taken place at least 6 hours after the end of the method according to the invention; however, the subject did not re-make up, make-up over (ie: with another make-up composition), or remove make-up from his lips in the meantime.
A third photograph is taken 44 hours and a fourth 68 hours, after the end of the process, the subject having taken his meals, but not having made up or removed make-up from his lips after the treatment process according to the invention, and throughout the duration of the assessment.

Results

The analysis of the photographs shows that the lips retain after 44 hours, homogeneous coloring. After 68 hours, the analysis of the photographs shows that there is still a slight homogeneous coloring of the lips.

For comparison, the application on lips pretreated according to step 1, with simply the second composition, shows that after 24 hours only a slight coloring of the lips remains, which is, moreover, not distributed homogeneously.

Example 2

The following first composition is prepared:

Ingredients Quantity
(% by weight of raw material) Water 88 Phenoxyethanol 0.5 Histidine ethyl ester 10 Hydroxypropyl guar (Jaguar HP 105, Solvay) 1.5

The following second composition is prepared:

Ingredients (INCI) Quantity
(% by weight of raw material) Trimethylsiloxysilicate (SR 1000, Momentive Performance Materials) 18.5 Silica silylate (DOWSIL VM-2270 AEROGEL FINE PARTICLES, Dow Corning) 0.5 Propylene carbonate 2.0 C30-45 alkyldimethylsilyl polypropylsilsesquioxane (DOWSIL SW-8005 C30 RESIN WAX, Dow Corning) 2.1 Nylon-611/dimethicone copolymer
(DOWSIL 2-8179 GELLANT; Dow Corning) 10.3 Dimethicone (and) dimethicone crosspolymer (DOWSIL EL-9140DM SILICONE ELASTOMER BLEND, Dow Corning) 37.6 Dimethicone (DOWSIL SH 200 C FLUID 350 CST, Dow Corning) 10.5 Isododecane qsp 100 RED 21 0.2 Ethanol 5.0

Process for preparing the composition
1. The silicone oil, the silicone wax, the Nylon-611/dimethicone polymer, the trimethylsiloxysilicate resin, the isododecane and the propylene carbonate are mixed with Rayneri stirring at 80°C.
2. Once the mixture is homogeneous, the silicone elastomer and the silica are added, with stirring at 80°C.
3. After homogenization, the resulting mixture is allowed to cool to room temperature.
4. In parallel, the dye is mixed in alcohol at room temperature with magnetic stirring until dissolved.
5. The resulting mixture is then added to that of step 3 under Rayneri stirring at ambient temperature.
6. Once the mixture is homogeneous, it is packaged.

Application method:

1. Preparation of the lips

The lips are scrubbed using a scrub composition Sucres de Soin Gommage Eclat from L'Oréal Paris. Then 2 hours after the treatment, the lips are photographed and their coloration is measured (Chromalys Samba-Shiva Chromasphere with SAMBA polarimetric camera; definition 410×410 pixels).

2.P lip treatment process and measurement

The first composition is applied and left to dry for 15 minutes.
The second composition is then applied and left to dry for 15 minutes.
A photograph of the lips thus made up is taken and their coloration is measured.
A second photograph is taken 24 hours after the application, the subject having taken his meals normally, the first of them having taken place at least 6 hours after the end of the method according to the invention; however, the subject did not re-make up, make-up over (ie: with another make-up composition), or remove make-up from his lips in the meantime.
A third photograph is taken 44 hours and a fourth 68 hours, after the end of the process, the subject having taken his meals, but not having made up or removed make-up from his lips after the treatment process according to the invention, and throughout the duration of the assessment.

Results

The analysis of the photographs shows that the lips retain after 44 hours, homogeneous coloring. After 68 hours, the analysis of the photographs shows that there is still a slight homogeneous coloring of the lips.

For comparison, the application on lips pretreated according to step 1, with simply the second composition, shows that after 24 hours only a slight coloring of the lips remains, which is also not homogeneous.

Claims (20)

Process for making up human keratin materials, in particular the lips, consisting in successively applying a first aqueous composition, then a second composition comprising at least one oil; one of the compositions comprising at least one amino acid containing at least one additional cationizable function, its C ₁ -C ₃ esters or the corresponding oligopeptides; and the other composition comprising at least one acid dye. Process according to Claim 1, characterized in that a first aqueous composition is applied comprising at least one amino acid containing at least one additional cationizable function, its C ₁ -C ₃ esters or the corresponding oligopeptides; then a second composition comprising at least one oil and at least one acid dye, the second composition comprising less than 5% by weight of water relative to the weight of said composition, or being in the form of an emulsion, more particularly water in oil. Process according to Claim 1, characterized in that a first aqueous composition comprising at least one acid dye is applied, then a second composition comprising at least one oil and at least one amino acid, the second composition comprising less than 5% by weight of water relative to the weight of said composition, or being in the form of an emulsion, more particularly water in oil; preferably the second composition is in the form of a water-in-oil emulsion. Process according to any one of the preceding claims, characterized in that the second composition is applied directly after the application of the first composition, once the deposit of the latter has dried. Process according to any one of the preceding claims, characterized in that the amino acid is chosen from natural amino acids such as arginine, histidine, lysine, asparagine, or synthetic such as ornithine, alone or in mixtures, or oligopeptides such as alaline-lysine, as well as their ethyl esters or their addition salts with a mineral acid, and preferably the amino acid is chosen from arginine, ethyl ester of arginine , lysine, lysine ethyl ester, histidine, histidine ethyl ester, as well as the corresponding hydrochlorides. Process according to any one of the preceding claims, characterized in that the content of amino acid(s) containing at least one additional cationizable function, its/their C ₁ -C ₃ esters or the corresponding oligopeptides, varies from 1 to 20% by weight, more particularly from 2.5 to 15% by weight, and even more preferably from 5 to 15% by weight, relative to the weight of the composition comprising it(s). Process according to any one of the preceding claims, characterized in that the acid dye is chosen from azo, xanthene, anthraquinone, triarylmethane, azine, quinolin, indigoid acid dyes and mixtures thereof, and preferably from azo, xanthene, as well as mixtures thereof. Process according to any one of the preceding claims, characterized in that the acid dye or dyes are chosen from the following species, alone or in mixtures: Acid Black 1 (CI 20470), Acid Black 2 (CI 50420), Acid Red 14 (IC 14720); Acid Red 88 (CI 15620); Acid Red 27 (CI 16185); Acid Red 18 (CI 16255); Acid Red 41 (CI 16290); Acid Red 33 (CI 17200); Acid Red 1 (CI 18050); Acid Red 155 (CI 18130); Acid Red 180 (CI 18736); Acid Red 163 (CI 24790); Acid Red 73 (CI 27290); Acid Orange 6 (CI 14270); Acid Orange 7 (CI 15510); Orange GGN (CI 15980); Acid Orange 10 (CI 16230); Acid Orange 24 (CI 20170); Acid Yellow 9 monosodium salt (CI 13015); Acid Yellow 11 (CI 18820); Acid Yellow 17 (CI 18965) for azo dyes; and from Acid Violet 9 (CI 45190); Acid Red 52 (CI 45100); Acid Red 50 (CI 45220); Acid Red 87 (CI 45380); Acid Red 98 (CI 45405); D&C Red 27 or 28 (CI 45410); Acid Red 95 (CI 45425); Acid Red 51 (CI 45430); Acid Orange 11 (CI 45370); Acid Yellow 73 (CI 45350) for xanthene dyes; as well as their combinations, and preferably, the acid dye or dyes are chosen from xanthenic dyes of the “red” type. Process according to any one of the preceding claims, characterized in that the content of acid dye(s) varies from 0.1 to 5% by weight, more particularly from 0.1 to 2% by weight, and even more advantageously from 0.1 to 1% by weight, relative to the weight of the composition comprising it or them. Process according to any one of the preceding claims, characterized in that the first aqueous composition comprises at least one hydrophilic thickening agent. Process according to any one of the preceding claims, characterized in that the first aqueous composition comprises at least 5% by weight of water, more particularly at least 20% by weight of water, and preferably from 40 to 95% by weight, more precisely from 50 to 95% by weight, of water, relative to the total weight of the first composition. Process according to any one of the preceding claims, characterized in that the second composition comprises at least one non-volatile oil chosen from silicone, phenyl or non-phenyl oils, from polar or apolar hydrocarbon-based oils, as well as mixtures thereof. Process according to any one of the preceding claims, characterized in that the oil content of the second composition varies from 30% to 90% by weight, more particularly from 50% to 90% by weight, relative to the weight of the second composition. Process according to any one of the preceding claims, characterized in that the second composition comprises at least one film-forming agent chosen from silicone polyamides; vinyl polymers comprising at least one unit derived from carbosiloxane dendrimer; film-forming ethylenic block copolymers; alkylcelluloses and preferably ethylcellulose; silicone resins; and mixtures thereof, and preferably chosen from silicone polyamides, silicone resins and mixtures thereof. Process according to any one of the preceding claims, characterized in that the second composition is in the form of a composition whose water content is less than 5% by weight, more particularly less than 2% by weight, even more particularly less than 1% by weight, relative to the weight of the second composition. Process according to any one of Claims 1 to 15, characterized in that the second composition is in the form of an emulsion, preferably a water-in-oil emulsion. Process according to any one of the preceding claims, characterized in that the first composition and/or the second composition comprise at least one solvent chosen from benzyl alcohol; C ₂ -C ₅ alkylene carbonates, preferably ethylene carbonate, propylene carbonate; as well as mixtures thereof. Process according to any one of the preceding claims, characterized in that a preliminary stage of preparation of the human keratin materials is carried out, consisting in cleansing, removing make-up, optionally performing a scrubbing stage in the case of an application to the skin and /or the lips. Cosmetic kit for implementing a process for making up human keratin materials, in particular the lips, according to any one of the preceding claims, characterized in that it comprises:
- a first aqueous composition comprising at least one amino acid containing at least one additional cationizable function, its C ₁ -C ₃ esters or the corresponding oligopeptides,
- a second composition, in the form of an emulsion or in the form of a composition comprising less than 5% by weight of water relative to the weight of said composition, comprising at least one oil and at least one acid dye. Cosmetic kit for implementing a process for making up human keratin materials, in particular the lips, according to any one of Claims 1 to 18, characterized in that it comprises:
- a first aqueous composition comprising at least one acid dye,
a second composition, in the form of a composition comprising less than 5% by weight of water relative to the weight of said composition, or in the form of an emulsion, preferably a water-in-oil emulsion, comprising at least one oil and at least one amino acid containing at least one additional cationizable function, its C ₁ -C ₃ esters or the corresponding oligopeptides.