WO2024261074A1 - Composition with chitosan and a modified polysaccharide - Google Patents

Abstract

The present invention relates to a cosmetic composition, especially for making up and/or caring for the skin and/or lips and/or lashes and/ or hair comprising, in a physiologically acceptable aqueous medium: • a) at least 0.01% by weight relative to the total weight of the composition of native chitosan having a molecular weight strictly greater than 3000 Daltons, this amount being strictly less than 15% by weight, • b) at least one modified polysaccharide, and • c) from 5% to 25% by weight relative to the total weight of the composition of at least one pigment colouring material.

Description

COMPOSITION WITH CHITOSAN AND A MODIFIED POLYSACCHARIDE

The present invention relates to a cosmetic composition, especially for making up and/or caring for the skin and/or lips and/or lashes and/or hair comprising, in a physiologically acceptable aqueous medium: a) at least 0.01 % by weight relative to the total weight of the composition of native chitosan having a molecular weight strictly greater than 3000 Daltons, this amount being strictly less than 15% by weight, and b) at least one modified polysaccharide.

The present invention also relates to a method for making up and/or caring for the skin and/or the keratinous appendages, wherein the composition according to the invention is applied to the skin and/or the keratinous appendages.

There are many cosmetic compositions for which endurance properties of the deposited film, after application to the keratin materials, are desired. Examples include lipsticks, foundations, mascaras or nail polishes. In order to achieve such a result, it is possible to associate particular raw materials, especially film-forming agents. Furthermore, it is often sought to obtain covering compositions.

The formulator is therefore looking for raw materials and/or systems for obtaining easily formulable, preferably fluid, chitosan-based compositions the deposit of which has good optical properties, for example, coverage, matity, and has good endurance and the resistance of which to, for example, dry mechanical wear, oil or water, is improved. There is also a need for such compositions, to further have good application and/or application comfort, as well as good texture, that is, especially with a controlled and acceptable viscosity.

In addition, formulating cosmetic products that are environmentally friendly, that is, designed and developed with environmental issues in mind, is becoming a major concern to help address the global challenges.

It is therefore essential to provide more sustainable compositions and/or preparation processes and/or ingredients enabling these environmental issues to be addressed. Within this context, it is important to develop new cosmetic compositions with a better carbon footprint, especially by promoting the use of renewable raw materials and/or with a good index of naturalness and/or natural origin and more particularly of plant origin, while reducing the use of compounds of petrochemical origin.

These problems can be solved by implementing cosmetic compositions described hereafter, such compositions having good formulability, good cosmetic properties, especially good resistance of makeup properties, such as coverage, to dry friction, water, oils and/or sebum, as well as good sensory properties. One purpose of the present invention in particular is to provide emulsions comprising chitosan and having good dry resistance to water and/or oil.

After application, these compositions leave a covering and homogeneous filmforming deposit, which has good wear resistance. The coloured films formed are adhesive and cohesive, and have improved dry resistance to water and/or oil.

These compositions also comprise sustainable ingredients, enabling environmental issues to be addressed.

One object of the present invention is therefore a cosmetic composition, especially for making up and/or caring for the skin and/or lips, in particular the skin and/or lashes and/or hair, comprising, in a physiologically acceptable aqueous medium: a) at least 0.01 % by weight relative to the total weight of the composition of native chitosan having a molecular weight strictly greater than 3000 Daltons, this amount being strictly less than 15% by weight, and b) at least one modified polysaccharide.

It also relates to a method for making up and/or caring for the skin and/or the keratinous appendages, wherein the composition according to the invention is applied to the skin and/or the keratinous appendages.

The composition is preferably in the form of an emulsion, more preferably a direct (oil-in-water) or invert (water-in-oil) emulsion.

According to one embodiment, the composition according to the invention is in the form of an oil-in-water emulsion, in particular having a weight ratio oil phase/water phase between 5:95 and 80:20, preferably between 8:92 and 65:35, preferably between 10:90 and 60:40, preferably between 12:88 and 50:50, preferably between 15:85 and 40:60.

According to one embodiment, the composition according to the invention is in the form of a water-in-oil emulsion, in particular having a weight ratio oil phase/water phase between 90:10 and 20:80, preferably between 80:20 and 30:70, preferably between 70:30 and 40:60, preferably between 65:35 and 45:55.

The composition according to the invention may also be in the form of an aqueous dispersion or solution or an aqueous gel.

By “physiologically acceptable”, it is meant a medium compatible with keratin materials.

Preferably, the composition according to the invention comprises, relative to the total weight of the composition, 10% by weight or less, preferably 5% by weight or less, preferably 0.1 to 10% by weight, of silicone.

By silicone, it is meant any silicone compound.

Preferably, the composition according to the invention is substantially free of silicone other than a film-forming or tackifying silicone polymer, preferably other than a silicone resin or a silicone acrylate copolymer, preferably other than an MQ resin or acrylates/polytrimethylsiloxy-methacrylate copolymer.

By “substantially free of silicone other than a silicone resin, preferably other than a film-forming or tackifying silicone polymer, preferably a silicone resin or a silicone acrylate copolymer, preferably other than an MQ resin or acrylates/polytrimethylsiloxy- methacrylate copolymer”, it is meant that the composition comprises less than 1% by weight relative to the total weight of the composition, preferably less than 0.5% by weight, preferably less than 0.3% by weight, preferentially less than 0.1% by weight of silicone other than a film forming or tackifying silicone polymer, preferably a silicone resin or a silicone acrylate copolymer, preferably other than an MQ resin or acrylates/polytrimethylsiloxy-methacrylate copolymer. Preferably, the composition is completely free of silicone other than a film-forming or tackifying silicone polymer, preferably a silicone resin or a silicone acrylate copolymer, preferably other than an MQ resin or acrylates/polytrimethylsiloxy-methacrylate copolymer. By silicone other than a film-forming or tackifying silicone polymer, preferably other than a silicone resin or a silicone acrylate copolymer, preferably other than an MQ resin or acrylates/polytrimethylsiloxy-methacrylate copolymer, it is meant any silicone compound that is not a film-forming or tackifying silicone polymer, preferably that is not a silicone resin or a silicone acrylate copolymer, preferably that is not an MQ resin or an acrylates/polytrimethylsiloxy-methacrylate copolymer.

By the term “resin”, it is meant a compound with a three-dimensional structure. Thus, for the purposes of the present invention, a polydimethylsiloxane is not a silicone resin.

The nomenclature of silicone resins is known as “MDTQ”, the resin being described according to the different siloxane monomeric units it comprises, each of the letters “MDTQ” characterising a type of unit.

The letter “M” represents the Monofunctional unit of formula R1 R2R3SiOi/2, the silicon atom being bound to a single oxygen atom in the polymer comprising this unit.

The letter “D” means a Difunctional unit R1 R2SiO2/2 in which the silicon atom is bound to two oxygen atoms.

The letter “T” represents a Trifunctional unit of formula R1 SiOs/2.

In the units M, D, T previously defined, Ri, namely, R1 , R2 and R3, identical or different, represent a hydrocarbon radical (especially alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or even a hydroxyl group.

Finally, the letter “Q” means a Tetrafunctional unit SiO4/2 in which the silicon atom is bound to four oxygen atoms themselves bound to the remainder of the polymer.

Such resins are described for example in "Encyclopaedia of Polymer Science and Engineering, 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 US 5,082,706, US 5,319,040, US 5.302, 685 and US 4,935,484.

MQ type silicone resins, are for example alkylsiloxysilicates of formula [(R1 )3SiO1/2]x(SiO4/2)y (MQ units) in which x and y are integers ranging from 50 to 80, and such that the group R1 represents a radical as defined previously, and preferably is an alkyl group having from 1 to 8 carbon atoms, or a hydroxyl group, preferably a methyl group. A distinction is made in particular between trimethylsiloxysilicate or phenylalkylsiloxysilicate resins such as phenylpropyldimethylsiloxysilicate.

Silicone polymers include siloxanes having an organo-function group, such as polyalkylsiloxanes, where at least one alkyl radical is other than methyl, for example organopolysiloxanes having the INCI name Stearyl Dimethicone, Cetyl Dimethicone or C26-28 Alkyl Dimethicone, or, for example, polyarylsiloxanes and polyarylalkylsiloxanes, for example organopolysiloxanes having the INCI name Phenyl Trimethicone, Trimethylsiloxyphenyl Dimethicone or Dimethylphenyl Dimethicone, or, for example, organopolysiloxanes having an organo-function radical such as an aminopropyl, aminopropyl-aminoethyl, aminopropyl-aminoisobutyl radical, for example organopolysiloxanes having the INCI name Amodimethicone, or, for example, organopolysiloxanes having a polyethylene glycol or polyalkylene glycol radical, for example organopolysiloxanes having the INCI name PEG-12 Dimethicone, PEG/PPG- 25,25-Dimethicone or Cetyl PEG/PPG-15/15 Butyl ether Dimethicone.

Silicone acrylate copolymers are polymers comprising a siloxane group and a hydrocarbon group. For example, adequate polymers include polymers comprising a hydrocarbon backbone such as, for example, a backbone selected from vinyl polymers, methacrylic polymers and/or acrylic polymers and at least one chain selected from siloxane pendant groups and polymers comprising a backbone of siloxane groups and at least one pendant hydrocarbon chain such as, for example, a vinyl, methacrylic and/or acrylic pendant group.

The silicone acrylate copolymer may be selected from polymers derived from non-polar silicone copolymers comprising repeating units of at least one polar (meth)acrylate unit and vinyl copolymers grafted with at least one non-polar silicone chain. Non-limiting examples of such copolymers are acrylates/dimethicone copolymers such as those commercially available from Shin-Etsu, for example, products sold under the brand names KP-545 (cyclopentasiloxane (and) acrylates/dimethicone copolymer), KP-543 (butyl acetate (and) acrylates/dimethicone copolymer), KP-549 (methyl trimethicone (and) acrylates/dimethicone copolymer), KP-550 (INCI name: isododecane (and) acrylate/dimethicone copolymer), KP-561 (acrylates/stearyl acrylate/dimethicone acrylates copolymer), KP-562 (acrylates/behenyl acrylate/dimethicone acrylates copolymer), and mixtures thereof. Additional examples include acrylate/dimethicone copolymers sold by Dow Corning under the brand names FA 4001 CM SILICONE ACRYLATE (cyclopentasiloxane (and) acrylates/polytrimethylsiloxymethacrylate copolymer), FA 4002 ID SILICONE ACRYLATE (isododecane (and) acrylates/polytrimethylsiloxymethacrylate Copolymer), and FA 4004 ID SILICONE ACRYLATE (isododecane (and) acrylates/polytrimethylsiloxymethacrylate Copolymer), and mixtures thereof.

According to one embodiment, the composition according to the invention is substantially free of silicone. By “substantially free of silicone”, it is meant that the composition comprises less than 1 % by weight relative to the total weight of the composition, preferably less than 0.5% by weight, preferably less than 0.3% by weight, preferentially less than 0.1% by weight of silicone. Preferably, the composition is completely free of silicone. According to this embodiment, by silicone, it is meant any silicone compound, including film-forming or tackifying silicone polymers.

Preferably, the composition according to the invention comprises, relative to the total weight of the composition, less than 20% by weight, preferably less than 10% by weight, preferably less than 5% by weight of natural resin. Preferably, the composition according to the invention is substantially free of natural resin. By “substantially free of natural resin,” it is meant that the composition comprises less than 1% by weight relative to the total weight of the composition, preferably less than 0.5% by weight, preferably less than 0.3% by weight, preferably less than 0.1 % by weight of natural resin. Preferably, the composition is completely free of natural resin.

By natural resin, it is meant especially an extract of candelilla wax.

Chitosan

The composition according to the invention comprises at least 0.01% by weight relative to the total weight of the composition of at least one native chitosan having a molecular weight strictly greater than 3000 Daltons (3 kDa).

The amount of native chitosan is also strictly less than 15% by weight relative to the total weight of the composition.

Preferably, the native chitosan has a molecular weight greater than or equal to 10 kDa, preferably greater than or equal to 15 kDa, preferably greater than or equal to 20 kDa. Preferably, the native chitosan has a molecular weight between 10 kDa and 2 MDa, preferably between 15 kDa and 1 .5 MDa, preferably between 20 kDa and 300 kDa, preferably between 20 kDa and 200 kDa. One Dalton is equivalent to 1 g/mol.

Chitosan is very rarely found in nature. It is reported only in the exoskeletons of certain insects such as queen termites and in the cell walls of a particular class of fungi, zygomycetes.

Chitosan is obtained by deacetylation of chitin. Chitin is a polysaccharide composed of several N-acetyl-D-glucosamine units bound to each other by a p-type bond (1 .4).

The ideal chemical structure of chitosan is a chain of p-D-glucosamine monomers bound by a glycosidic bond (1^4). By “chitosan” according to the invention, it is meant any copolymer formed of N-acetyl- D-glucosamine and D-glucosamine constituent units, the degree of acetylation of which is less than 90%. Chitosan consists of glucosamine sugar units (deacetylated units) and N- acetyl-D-glucosamine units (acetylated units) bound to each other by p-type bonds (1 .4) and constitutes a polymer of the Poly(N-acetyl-D-glucosamine)-poly(D-glucosamine) type.

Preferably, the degree of acetylation of chitosan is less than or equal to 80%, preferably less than or equal to 70%, preferably less than or equal to 60%, preferably less than or equal to 50%, preferably less than or equal to 35%, preferably less than or equal to 25%, preferably less than or equal to 15%.

The degree of acetylation is the percentage of acetylated units relative to the total number of units, it can be determined by Fourier Transform Infrared (FT-IR) spectroscopy or by a strong base titration.

The chitosan of the invention is preferably a polysaccharide prepared from a fungal origin. In particular, it is extracted and purified from safe and abundant food or biotechnological fungal sources such as Agaricus bisporus or Aspergillus niger.

The chitosan of the invention is preferably derived from the mycelium of an Ascomycete fungus, and in particular from Aspergillus niger and/or a Basidiomycete fungus, and in particular Lentinula edodes (shiitake) and/or Agaricus bisporus. Preferably, the fungus is Aspergillus niger.

Chitosan may be of GMO origin, but preferably is of non-GMO origin.

The chitosan according to the invention is native, that is, it is unmodified. In particular, it does not contain any chemical modification.

A method for preparing chitosan is that described in application WO03068824.

Preferably, the chitosan used in the invention is in powder form. It is especially marketed by Kitozyme under the name Kiosmetine or Kionutrime.

Chitosan is preferably present in an amount ranging from 0.01% to 14% by weight, preferably from 0.1 % to 14% by weight, preferably from 0.1% to 12% by weight, preferably from 0.2% to 7% by weight, preferably from 0.25% to 5%, preferably from 0.3 to 3% by weight, or even more preferably from 0.5 to 2% by weight relative to the total weight of the composition. Modified polysaccharide

The composition of the invention comprises one or more modified polysaccharide(s), said polysaccharide not being selected from chitosans and derivatives thereof.

The polysaccharide modified according to the invention is indeed other than chitosan and derivatives thereof.

A “sugar” is a monosaccharide, or polysaccharide radical or an O-protected sugar derivative such as an ester of sugar and (C1 -C6)alkylcarboxylic acid such as acetic acid, a sugar with amine group(s) and (C1 -C4)alkylated derivatives, such as methylated derivatives as methyl glucose. Mention may be made, as a sugar radical, of sucrose, glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose.

By “polysaccharide”, it is meant a poly-osidic sugar which is a polymer made of several oses bound to each other by O-osidic bonds, said polymers being made of monosaccharide units (also called mono-osidic) as defined previously, said monosaccharide units comprising at least 5 carbon atoms, preferably 6, in particular the mono-osidic units are bound to each other in 1 .4 or 1 .6 alpha or beta anomers, each osidic unit which may be of configuration L or D, as well as salts thereof and solvates thereof such as the hydrates of said monosaccharides; they are more particularly polymers formed of a certain number of oses (or monosaccharides) having as general formula: -[Cx(H2O)y)]w- or -[(CH2O)x]w-, with x being an integer greater than or equal to 5, preferably x being greater than or equal to 6, in particular x being inclusively between 5 and 7, preferably x = 6, and y being an integer representing x - 1 , and w being an integer greater than or equal to 2, particularly inclusively between 3 and 3000, more particularly between 5 and 2500, preferentially between 10 and 2300, particularly inclusively between 15 and 1000, more particularly between 20 and 500, preferentially between 25 and 200.

The polysaccharide(s) useful for the invention are cationic, non-ionic, anionic or amphoteric polymers, preferably cationic, non-ionic or anionic, better non-ionic, modified by the presence of at least one cyclic or non-cyclic, linear or branched, saturated or unsaturated, aromatic or not, hydrocarbon aliphatic chain, comprising from 2 to 30 carbon atoms, possibly substituted by one or more atoms or groups a), f), g), h), i), j), I) as defined hereafter and/or p) (di)alkylamino and/or possibly interrupted by one or more heteroatoms or groups a') to c') as defined below: a) halogen such as chlorine or bromine, f) (thio)carboxamide -C(O)-N(Ra)2 or -C(S)- N(Ra)2, g) cyano, h) iso(thio)cyanate, i) (hetero)aryl such as phenyl or furyl, and j) (hetero)cycloalkyl such as anhydride, epoxide or dithiolane, I) R-X with R representing a group selected from a) cycloalkyl such as cyclohexyl, ) heterocycloalkyl such as preferably monosaccharide sugar such as glucose, y) (hetero)aryl such as phenyl, 5) active cosmetic, and X representing a') O, S, N(Ra) or Si(Rb)(Rc), b') S(O)r, or (thio)carbonyl, c') or combinations of a') with b') such as (thio)ester, (thio)amide, (thio)urea, sulfonamide; Ra representing a hydrogen atom, or a (C1 -C4)alkyl, or aryl(C1 -C4)alkyl group such as benzyl, preferably Ra represents a hydrogen atom; Rb and Rc, identical or different, represent a (C1 -C4)alkyl or (C1 - C4)alkoxy group, particularly a single substituent; and/or a') heteroatoms such as O, S, N(Ra), and Si(Rb)(Rc), b') S(O)r, (thio)carbonyl, c') or associations of a') with b') such as (thio)ester, (thio)amide, (thio)urea, sulfonamide with r being 1 or 2, Ra being as defined previously, preferably Ra representing a hydrogen atom, Rb and Rc, being as defined previously.

The “polysaccharides" are as defined above; furthermore, the ose units - [C_x(H₂O)y)] w- or -[(CH₂O)_X]W-, are possibly modified by substitution, oxidation, dehydration and/or reduction.

As ose units of the polysaccharide(s) useful to the invention, mention may be made of glucose; galactose; arabinose; rhamnose; mannose; xylose; fucose; anhydrogalactose; galacturonic acid; glucuronic acid; mannuronic acid; galactose sulphate; anhydrogalactose sulphate and fructose.

Mention may in particular be made of polysaccharides modified from native gums such as those derived from exudates of trees or shrubs, algae, seeds or tubers, fungi, bacteria, animal organisms, plants, which have been modified physically, by chemical or enzymatic reactions.

Native gums can be selected from:

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

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

- karaya gum (polymer derived from galacturonic acid, galactose, rhamnose and glucuronic acid); - tragacanth gum (polymer of galacturonic acid, galactose, fucose, xylose and arabinose);

- agar (polymer derived from galactose and anhydrogalactose);

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

- carrageenans and furcelleranes (polymers of galactose sulphate and anhydrogalactose sulphate);

- guar gum (polymer of mannose and galactose);

- carob gum (polymer of mannose and galactose);

- fenugreek gum (polymer of mannose and galactose);

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

- konjac gum (polymer of glucose and mannose);

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

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

- scleroglucan gum (polymer of glucose);

- cellulose (polymer of glucose);

- starch (polymer of glucose);

- dextrin

- inulin and

- pectin.

In particular, the modified polysaccharides are derived from gum arabic; ghatti gum; karaya gum; tragacanth gum; agar; alginates; carrageenans and furcellerans; guar gum; carob gum; fenugreek gum; tamarind gum; konjac gum; xanthan gum or dehydroxanthan gum; gellan gum; scleroglucan gum; cellulose; starch; dextrin, pullulan, linulin; and pectin; preferably selected from cellulose; starch; dextrin or pullulan, more preferably cellulose.

The starch molecules used in the present invention may have as botanical origin cereals or even tubers. Thus, the starches are for example selected from maize, rice, manioc, barley, potato, wheat, sorghum, pea starches.

Starches may be modified chemically or physically, especially by one or more of the following reactions: pregelatinization, oxidation, crosslinking, esterification, etherification, amidification, heat treatments. According to one embodiment of the invention, the modified polysaccharide(s) are non-ionic.

These polymers can be modified physically or chemically. As physical treatment, mention may be especially of temperature. As chemical treatments, mention may be made of the esterification, etherification, amidification, oxidation, metastasis, addition reactions. These treatments make it possible to lead to polymers which may especially be non-ionic, anionic or amphoteric.

Preferably, these chemical or physical treatments are applied to guar gums, carob gums, starches or celluloses.

The starch molecules may be derived from all plant starch sources such as, in particular, maize, potato, oats, rice, tapioca, sorghum, barley or wheat that have been modified to bind at least one cyclic or non-cyclic, linear or branched, saturated or unsaturated, aromatic or not, hydrocarbon aliphatic chain, comprising from 6 to 30 carbon atoms possibly substituted by one or more atoms or groups a), f), g), h), i), j), I) as defined above; and/or p) (di)alkylamino and/or possibly interrupted by one or more heteroatoms or groups a') to c') as defined above. The hydrolysates of the above-mentioned starches may also be used. The modified starch is preferably derived from potato starch.

According to one embodiment, the modified polysaccharides are polysaccharide ethers called alkyl polysaccharides the alkyl radical of which comprises between 2 and 30, preferably between 2 and 10, more preferably between 2 and 6 carbon atoms.

Preferably, the alkyl polysaccharides according to the invention are derived from cellulose or guar or mixtures thereof.

According to one embodiment, the modified polysaccharides are alkylcelluloses the linear or branched alkyl residue of which comprises between 1 and 10 carbon atoms, in particular between 2 and 6 carbon atoms, preferably between 2 and 3 carbon atoms. Alkylcellulose is an alkyl cellulose ether comprising a chain consisting of p- anhydroglucose units bound to each other by acetal bonds. Each anhydroglucose unit has three replaceable hydroxyl groups, all or part of which may react according to the following reaction:

Cell-OM + R-Hal => Cell-OR + MHal with Hal representing a halogen such as Cl, with M representing a cationic counterion such as alkali metal Na or K, or alkali earth metal, preferably an alkali metal such as Na, Cell representing a polysaccharide radical such as cellulose, where R represents a linear or branched alkyl group, comprising from 1 to 10 carbon atoms, preferably between 2 and 3 carbon atoms such as methyl or ethyl, and MHal the salt generated such as sodium chloride.

Advantageously, the alkylcellulose is selected from ethylcellulose and propylcellulose. According to a particularly preferred embodiment, the alkylcellulose is ethylcellulose. It is an ethyl cellulose ether.

The total substitution of the three hydroxyl groups would lead, for each anhydroglucose unit, to a degree of substitution of 3, in other words, to an alkoxy group content of between 40% and 60%, especially around 55% (54.88%).

The ethylcellulose polymers used in a composition according to the invention are preferably polymers having a degree of substitution in ethoxy groups ranging from 2.5 to 2.6 per anhydroglucose unit, in other words, comprising an ethoxy group content ranging from 44 to 50%.

According to a particular embodiment of the invention, the modified polysaccharide of the invention is an ethylcellulose in powder form. For example, it is marketed under the trade names ETHOCEL Standard by Dow Chemicals, including ETHOCEL Standard 7 FP Premium and ETHOCEL Standard 100 FP Premium. Other commercially available products, such as those marketed by Ashland, Inc., under the designations Aquaion Ethylcellulose type-K, type-N and type-T, preferably type-N, such as N7, N100, are particularly suitable for the embodiment of the invention.

According to another embodiment, the polysaccharide ethers are alkylguars, that is, guar gums modified by hydroxy hydrogen substitution with a linear or branched alkyl group, comprising between 1 to 10 carbon atoms, in particular between 2 and 6 carbon atoms, preferably between 2 and 3 carbon atoms such as 2 carbon atoms. The alkylguar polymers used in a composition according to the invention are preferably ethylguar.

Ethylguar is known under the INCI name: Ci -C5 alkyl galactomannan.

More particularly, it has a degree of substitution of 2 to 3, and especially of 2.5 to 2.8.

The alkylated guar gums (with Ci-Ce alkyl group), including ethylguar, as well as their preparation method, are especially described in patent application EP 708114 and document RD9537807 (1995 October).

According to one embodiment, the modified polysaccharides are polysaccharide esters, in particular esters obtained by reaction between at least one polysaccharide such as dextrin with at least one saturated or unsaturated linear or branched acid and including from 2 to 30 carbon atoms, especially from 10 to 30 carbon atoms.

According to a particular embodiment, the modified polysaccharides of the invention are selected from cellulose or derivatives thereof such as hydroxy(Ci- C5)alkylcelluloses, starch and inulin, said polysaccharides including at least one Cs- C30 fatty chain, such as alkyl, arylalkyl, alkylaryl groups or mixtures thereof where the linear or branched, preferably linear, Cs-Cso alkyl groups are preferred.

According to a particular embodiment of the invention, the modified polysaccharide(s) are selected from polysaccharide mono- or polyalkyl esters.

Among the saccharide or polysaccharide mono- or polyalkyl esters suitable for the implementation of the invention, mention may be made of dextrin or inulin alkyls or polyalkyl esters.

It may especially be a dextrin mono- or polyester (the dextrin being derived from starch) and at least one fatty acid (such as R-C(O)-OH) and especially meeting the following formula (I):

[Chem 1 ]

in which:

• n is an integer greater than or equal to 2, preferably ranging from 3 to 200, especially ranging from 20 to 150, and in particular ranging from 25 to 50,

• Ri, R2 and R3, identical or different, are selected from hydrogen or an acyl group (R-C(O)-) in which the radical R is a linear or branched, saturated or unsaturated hydrocarbon group, having from 7 to 29, in particular from 7 to 21 , especially from 11 to 19, more particularly from 13 to 17, or even 15, carbon atoms, it being understood that at least one of said radicals R1, R2 or R₃ is other than hydrogen.

In particular, R1, R₂ and R3 represent a hydrogen atom or an acyl group (R- C(O)-) in which R is a hydrocarbon radical as defined previously, provided that at least two of said radicals R1, R₂ or R₃ are other than hydrogen.

All of the radicals R1, R₂ and R₃ may represent an identical or different acyl group (R-C(O)), and the acyl groups are especially identical.

In particular, n previously set out advantageously varies from 25 to 50, is especially equal to 38 in the general formula of the saccharide ester usable in the present invention.

Especially when the radicals R1, R₂ and/or R₃, identical or different, represent an acyl group (R-C(O)), derived from carboxylic fatty acid R-C(O)OH, preferably selected from caprylic, capric, lauric, myristic, palmitic, stearic, arachidic, behenic, isobutyric, isovaleric, ethyl-2 butyric, ethylmethylacetic, isoheptanoic, ethyl-2 hexanoic, isononanoic, isodecanoic, isotridecanoic, isomyristic, isopalmitic, isostearic, isoaracic, isohexanoic, decenoic, dodecenoic, tetradecenoic, myristoleic, hexadecenoic, palmitoleic, oleic, elaidic, asclepinic, gondoleic, eicosenoic, sorbic, linoleic, linolenic, punicic, stearidonic, arachidonic, stearolic acids, and mixtures thereof.

Preferably, at least one dextrin palmitate is used as dextrin and fatty acid ester. This can be used alone or in combination with other esters.

Advantageously, the dextrin and fatty acid ester has a degree of substitution less than or equal to 2.5 based on a glucose unit, especially varying from 1 .5 to 2.5, preferably from 2 to 2.5. The weight average molecular weight of the dextrin ester may in particular be from 10,000 to 150,000, especially from 12,000 to 100,000 or even from 15,000 to 80,000. Preferably, the modified polysaccharide(s) of the invention are dextrin esters, and preferably are dextrin palmitates.

Dextrin esters, in particular dextrin palmitates, are commercially available under the name RHEOPEARL KL2®, MKL2®, TL® or KL® from the company Chiba Flour.

According to one embodiment, the modified polysaccharide is a modified dextrin, preferably a dextrin ester, more particularly a C12-C24 saturated or unsaturated, linear or branched dextrin and fatty acid ester.

Preferably, the dextrin ester is selected from C14-C24 saturated or unsaturated, linear or branched fatty acid esters such as myristic acid, palmitic acid, or a mixture thereof. According to one embodiment, the dextrin ester is selected from Palmitate dextrins such as RHEOPEARL KL2® and RHEOPEARL TL2® marketed by CHIBA FLOUR, myristate dextrin such as that marketed under the reference RHEOPEARL MKL2® by CHIBA FLOUR, palmitate/ethylhexanoate dextrin marketed under the reference RHEOPEARL TT2®, palmitate/hexyldecanoate dextrin marketed under the reference RHEOPEARL WX or mixtures thereof.

According to a preferred embodiment, the modified polysaccharide denotes dextrin palmitate.

According to one embodiment, the modified polysaccharide is a modified inulin, preferably an inulin ester, more particularly a saturated or unsaturated, linear or branched C12-C24 inulin and fatty acid ester.

Preferably, the inulin ester is selected from saturated or unsaturated, linear or branched C14-C24 fatty acid esters such as myristic acid, palmitic acid, stearic acid, preferably stearic acid, and mixtures thereof.

According to one embodiment, the inulin ester is a stearoyl inulin such as the references REOPEARL ISK2® and RHEOPEARL ISL2® marketed by CHIBA FLOUR or mixtures thereof.

According to one embodiment, the modified polysaccharide is a modified cellulose, preferably a cellulose ester, more particularly a saturated or unsaturated, linear or branched C2-C24 cellulose and acid ester. Preferably, the cellulose ester is selected from saturated or unsaturated, linear or branched C2-C10, preferably C2-C6, in particular C2-C4 acid esters such as acetic acid, butyric acid or a mixture thereof.

According to one embodiment, the cellulose ester is a cellulose acetate butyrate such as the reference EASTMAN CELLULOSE ACETATE BUTYRATE® marketed by EASTMAN CHEMICAL.

Among the polysaccharide esters, mention may also be made of pullulan esters. Pullulan is a polysaccharide consisting of maltotriose units.

According to one embodiment, the modified polysaccharides are polysaccharide esters. By polysaccharide esters, it is meant polysaccharides at least one of the hydroxy radicals of which is esterified by an acid to form ester groups -O- C(O)-R or -C(O)-OR in which R denotes a saturated or unsaturated radical of 2 to 30 carbon atoms, especially 11 to 19 carbon atoms, preferably 12 to 17 carbon atoms such as 13 carbon atoms.

Advantageously, the polysaccharide ester is myristoyl pullulan.

According to another embodiment, the modified polysaccharide(s) of the invention are cationic. Preferably, these chemical or physical treatments to obtain at least one cationic group are applied to guar gums, carob gums, starches and celluloses.

The cationic groups may be of the primary, secondary, tertiary or quaternary amine type, preferably quaternary, and comprise a C6-C30 aliphatic chain.

According to a particular embodiment of the invention, the modified polysaccharide(s) are selected from quaternised (poly)hydroxyethylcelluloses modified by groups including at least one aliphatic (or fatty) chain, such as alkyl, arylalkyl, alkylaryl groups having at least 8 carbon atoms, or mixtures thereof. The alkyl radicals carried by the quaternised celluloses or hydroxyethylcelluloses preferably comprise from 8 to 30 carbon atoms. The aryl radicals preferably denote the phenyl, benzyl, naphthyl or anthryl groups. Examples of quaternised alkylhydroxyethyl-celluloses with C8-C30 fatty chains, may include the QUATRISOFT LM 200®, QUATRISOFT LM-X 529-18-A®, QUATRISOFT LM-X 529-18-B® (C12 alkyl) and QUATRISOFT LM-X 529-8® (C18 alkyl) products sold by the company Dow Corning, the CRODACEL QM®, CRODACEL QL® (C12 alkyl) and CRODACEL QS® (C alkyl) products sold by the company CRODA and the SOFTCAT SL 100® product sold by the company Dow Corning.

The non-ionic guar gums usable according to the invention may be modified by C1-C20 (poly)hydroxylakylammonium groups, preferably Ci-Ce (poly)hydroxyalkyl, mention may especially be made, by way of example, of the hydroxymethyltrimmonium, hydroxyethyltrimmonium, hydroxypropyltrimmonium and hydroxybutyltrimmonium halide groups, preferably hydroxypropyltrimmonium halide, preferably chloride.

Such cationic guar gums modified by hydroxyalkylammonium groups are for example sold by the company Solvay under the trade names Cationic Jaguar® C-14S Guar Hydroxypropyltrimonium Chloride F Jaguar® C-13S Guar Hydroxypropyltrimonium Chloride F Jaguar® C-17 Guar Hydroxypropyltrimonium Chloride Jaguar® Excel Guar Hydroxypropyltrimonium Chloride Jaguar® C-500 STD Guar Hydroxypropyltrimonium Chloride Jaguar® C-162 Hydroxypropyl Guar Hydroxypropyltrimonium Chloride Jaguar® Optima Guar Hydroxypropyltrimonium Chloride Jaguar® LS Hydroxypropyl Guar Hydroxypropyltrimonium Chloride.

The total amount of the modified polysaccharide(s) present in the composition according to the invention is preferably in the range of 0.05% to 20% by weight, more preferably from 0.1% to 15% by weight, even more preferably from 0.2 to 12% by weight, and according to a particularly preferred embodiment from 0.5% to 10% by weight, preferably from 1% to 5% by weight relative to the total weight of the composition.

Preferably, the weight ratio of the total amount of the modified polysaccharide(s) to the total amount of chitosan(s), present in the composition, ranges from 0.05 to 200, more preferably from 0.1 to 100, more preferably from 0.2 to 50, or even better from 0.5 to 40, preferably from 0.5 to 20, preferably from 0.8 to 10, and even more preferably from 1 to 8, preferably from 1.1 to 5.

Pigment colouring materials

The composition according to the invention can further comprise at least one pigment colouring material. This colouring material is selected from powdery colouring materials such as mineral pigments, nacres, organic pigments. By “pigments”, it is meant white or coloured, mineral or organic particles, insoluble in an aqueous medium, intended to colour the resulting composition and/or deposition.

The colouring materials may be present, in the composition, in a content ranging from 0.5% to 70% by weight, preferably from 1% to 60% by weight, preferably from 1% to 50% by weight, preferably from 2% to 40% by weight, relative to the weight of the composition, preferably from 4% to 30% by weight, preferably from 5% to 25% by weight, preferably from 6% to 20% by weight, preferably from 8% to 18% by weight.

Mineral pigments

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

By “mineral pigment”, it is meant any pigment that meets the definition of the Ullmann encyclopaedia in the inorganic pigment chapter. 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 aluminium powder and copper powder. The following mineral pigments can also be used: Ta2O5, Ti3O5, Ti2O3, TiO, ZrO2 in mixture with TiO2, ZrO2, Nb2O5, CeO2, ZnS.

The size of the pigment useful within the context of the present invention is generally greater than 5 nm, preferably greater than 10 nm, preferably greater than 20 nm, preferably greater than 100 nm and may be up to 10 pm, preferably from 200 nm to 5 pm, and more preferably from 300 nm to 1 pm. According to a particular embodiment of the invention, the pigments have a size characterised by a D[50] greater than 100 nm and which may be up to 10 pm, preferably from 200 nm to 5 pm, and more preferably from 300 nm to 1 pm. The sizes are measured by static light scattering using a commercial granulometer of the MasterSizer 3000® type from Malvern, for measuring the particle size distribution of all particles over a wide range ranging from 0.01 pm to 1000 pm. Data are processed on the basis of the conventional Mie scattering theory. This theory is best suited for size distributions ranging from sub-micron to multi-micron, it allows an “effective” particle diameter to be determined. This theory is described in particular in Van de Hulst, H.C., “Light Scattering by Small Particles”, Chapters 9 and 10, Wiley, New York, 1957. D[50] represents the maximum size of 50% by volume of particles. Within the scope of the present invention, the mineral pigments are more particularly iron oxide and/or titanium dioxide. By way of example, mention may be made more particularly of titanium dioxides and iron oxides, coated with aluminium stearoyl glutamate, for example marketed under the reference NAI® by the company MIYOSHI KASEL

As mineral pigments usable in the invention, mention may also be made of nacres.

By “nacres”, it is meant coloured particles of any shape, iridescent or not, especially produced by certain molluscs in their shells or synthesised and which exhibit a colour effect by optical interference.

Nacres may be selected from pearlescent pigments, such as mica titanium covered with iron oxide, mica titanium covered with bismuth oxychloride, mica titanium covered with chromium oxide, mica titanium covered with an organic colorant, as well as bismuth oxychloride-based pearlescent pigments. They may also be mica particles on the surface of which at least two successive layers of metal oxides and/or organic colouring materials are superimposed. Mention may also be made, as examples of nacres, of natural mica covered with titanium oxide, iron oxide, natural pigment or bismuth oxychloride. Among the nacres available on the market, mention may be made of nacres TIMICA®, FLAMENCO® and DUOCHROME® (mica-based) marketed by the company ENGELHARD, TIMIRON® nacres marketed by the company MERCK, mica-based nacres PRESTIGE® marketed by the company ECKART and synthetic mica-based nacres SUNSHINE® marketed by the company SUN CHEMICAL.

Nacres may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or copper colour or tinge. By way of illustration of the nacres that may be implemented within the scope of the present invention, mention may be made, in particular, of gold-coloured nacres, especially, marketed by the company ENGELHARD, under the name of Brillant gold 212G® (Timica), Gold 222C® (Cloisonne), Sparkle Gold® (Timica), Gold 4504® (Chromalite) and Monarch Gold 233X® (Cloisonne); bronze nacres, especially, marketed by the company MERCK under the name Bronze fine® (17384) (Colorona) and Bronze® (17353) (Colorona) and by the company ENGELHARD under the name Super bronze (Cloisonne); orange nacres, especially, marketed by the company ENGELHARD under the name Orange 363C® (Cloisonne) and Orange MCR 101® (Cosmica) and by the company MERCK under the name Passion Orange® (Colorona) and Matte Orange (17449) ® (Microna); brown tint nacres, especially, marketed by the company ENGELHARD under the name Nu-Antique Copper 340XB® (Cloisonne) and Brown CL4509® (Chromalite); copper-tinged nacres, especially, marketed by the company ENGELHARD under the name Copper 340A® (Timica); red-tinged nacres, especially, marketed by the company MERCK under the name Sienna Fine® (17386) (Colorona); yellow-tinged nacres, especially, marketed by the company ENGELHARD under the name Yellow (4502) ® (Chromalite); gold-tinged red nacres, especially, marketed by the company ENGELHARD under the name Sunstone G012® (Gemtone); pink nacres, especially, marketed by the company ENGELHARD under the name Tan Opale G005® (Gemtone); gold-tinged black nacres, especially, marketed by the company ENGELHARD under the name Nu Antique Bronze 240 AB® (Timica), blue nacres, especially, marketed by the company MERCK under the name Matte Blue® (17433) (Microna), silver-tinged white nacres, especially, marketed by the company MERCK under the name Xirona Silver® and rose-orange green-gold nacres, especially, marketed by MERCK under the name Indian Summer® (Xirona) and mixtures thereof.

Among the pigments usable according to the invention, mention may also be made of those with an optical effect different from a simple conventional tint effect, that is, unified and stabilised as produced by the conventional colouring materials, such as, for example, monochromatic pigments. For purposes of the invention, “stabilised” means without any effect of colour variability with the angle of observation or in response to a change in temperature. For example, this material may be selected from metallic glint particles, goniochromatic colouring agents, diffractive pigments, thermochromic agents, optical brightening agents, as well as fibres, especially interferential fibres. Of course, these different materials can be associated in such a way as to provide the simultaneous appearance of two effects, or even a new effect in accordance with the invention.

The metallic glint particles usable in the invention are in particular selected from:

- particles of at least one metal and/or at least one metal derivative,

- particles including an organic or mineral substrate, monomaterial or multimaterial, at least partially covered by at least one metallic glint layer comprising at least one metal and/or at least one metal derivative, and

- mixtures of said particles.

Among the metals that may be present in said particles, mention may be made, for example, of Ag, Au, Cu, Al, Ni, Sn, Mg, Cr, Mo, Ti, Zr, Pt, Va, Rb, W, Zn, Ge, Te, Se and mixtures or alloys thereof. Ag, Au, Cu, Al, Zn, Ni, Mo, Cr, and mixtures or alloys thereof (for example, bronzes and brasses) are preferred metals. Metal derivatives refer to compounds derived from metals, including oxides, fluorides, chlorides and sulphides

By way of illustration of these particles, mention may be made of aluminium particles, such as those marketed under the names STARBRITE 1200 EAC® by the company SIBERLINE and METALURE® by the company ECKART.

Mention may also be made of copper metal powders or alloy mixtures, such as references 2844 marketed by the company RADIUM BRONZE, metal pigments, such as aluminium or bronze, such as those marketed under the names ROTOSAFE 700® of the company ECKART, silica-coated aluminium particles marketed under the name VISIONAIRE BRIGHT SILVER® of the company ECKART, and metal alloy particles, such as silica-coated bronze powders (copper and zinc alloy) marketed under the name Visionary Bright Natural Gold® by the company Eckart.

These may otherwise be particles including a glass substrate such as those marketed by the company NIPPON SHEET GLASS under the name MICROGLASS METASHINE®.

The goniochromatic colouring agent may be selected, for example, from interferential multilayer structures and liquid crystal colouring agents.

Examples of symmetrical interferential multilayer structures usable in compositions made according to the invention are, for example, the following structures: AI/SiO2/AI/SiO2/AI, pigments having this structure being marketed by the company DUPONT DE NEMOURS; Cr/MgF2/AI/MgF2/Cr, pigments having this structure being marketed under the name CHROMAFLAIR® by the company FLEX; MoS2/Si02/AI/Si02/MoS2; Fe2Os/SiO2/AI/SiO2/Fe2O3, and Fe2O3/SiO2/Fe2Os/SiO2/Fe2O3, pigments having these structures being marketed under the name SICOPEARL® by the company BASF; MoS2/Si02/mica-oxide/Si02MoS2; Fe203/Si02/mica-oxide/Si02/Fe203; TiO2/SiO2/TiO2 and TiO2/Al2Os/TiO2; SnO/TiO2/SiO2/TiO2/SnO; Fe2O3/SiO2/Fe2Os; SnO/mica/TiO2 /SiO2/TiO2/mica/SnO, pigments having these structures being marketed under the name XIRONA® by the company MERCK (Darmstadt). By way of example, these pigments may be the pigments of silica/titanium oxide/tin oxide structure marketed under the name XIRONA MAGIC® by the company MERCK, the pigments of silica/brown iron oxide structure marketed under the name XIRONA INDIAN SUMMER® by the company MERCK, and the pigments of silica/titanium oxide/mica/tin oxide structure marketed under the name XIRONA CARRIBEAN BLUE® by the company MERCK. Mention may also be made of the INFINITE COLOURS pigments from the company SHISEIDO. Depending on the thickness and nature of the different layers, different effects are achieved. For example, the structure Fe2O3/SiO2/AI/SiO2/Fe2O3 changes from gold- green to grey-red for SiC>2 layers from 320 to 350 nm; from red to gold for SIC>2 layers from 380 to 400 nm; from purple to green for SIC>2 layers from 410 to 420 nm; from copper to red for SIC>2 layers from 430 to 440 nm.

Mention may be made, as examples of pigments with a polymeric multilayer structure, of those marketed by the company 3M under the name COLOUR GLITTER®.

As liquid crystal goniochromatic particles, for example, those sold by the company CHENIX, as well as those marketed under the name HELICONE® HC by the company WACKER, may be used.

Hydrophobic coated pigments

According to a particular embodiment of the invention, the compositions according to the invention comprise at least one pigment coated with at least one lipophilic or hydrophobic compound and especially as detailed hereafter.

This type of pigment is particularly advantageous insofar as it can be considered in significant amounts together with a significant amount of water. Besides, since they are treated with a hydrophobic compound, they exhibit a predominant affinity for the gelled oil phase which can then carry them.

Of course, the compositions according to the invention may also contain uncoated pigments.

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

For the purposes of the invention, the coating of a pigment according to the invention generally refers to the total or partial surface treatment of the pigment by a surfactant, absorbed, adsorbed or grafted onto said pigment.

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

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

According to one alternative, the surface treatment consists in coating the pigments.

The coating may 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 may be carried out, for example, by adsorption of a liquid surfactant to the surface of the solid particles by simply mixing under stirring the particles and said surfactant, possibly hot mixing, prior to the incorporation of the particles into the other ingredients of the makeup or care composition.

The coating can for example be carried out by chemical reaction of a surfactant with the surface of the solid pigment particles and creation of a covalent bond between the surfactant and the particles. This method is described in particular in US patent 4,578,266.

Chemical surface treatment may consist in diluting the surfactant in a volatile solvent, dispersing the pigments in this mixture, and then slowly evaporating the volatile solvent, such that the surfactant is deposited onto the surface of the pigments.

Lipophilic or hydrophobic treatment agent

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 may be coated according to the invention with at least one compound selected from silicone surfactants; fluoro surfactants; fluorosilicone surfactants; metal soaps; N-acylated amino acids or salts thereof; lecithin and derivatives thereof; isopropyl triisostearyl titanate; isostearyl sebacetate; natural plant or animal waxes; synthetic polar waxes; fatty esters; phospholipids; and mixtures thereof.

Silicone surfactant

According to a particular embodiment, the pigments may be totally or partially surface-treated with a compound of a silicone nature.

Silicone surfactants may be selected from organopolysiloxanes, silane derivatives, silicone-acrylate copolymers, silicone resins, and mixtures thereof.

By organopolysiloxane compound, it is meant a compound having a structure comprising an alternation of silicone atoms and oxygen atoms and comprising organic radicals bound to silicon atoms. Non-elastomeric organopolysiloxane

Mention may especially be made, as non-elastomeric organopolysiloxanes, of polydimethylsiloxanes, polymethylhydrogenosiloxanes and polyalkoxydimethylsiloxanes.

The alkoxy group may be represented by the radical R-O- such that R represents methyl, ethyl, propyl, butyl or octyl, 2-phenylethyl, 2-phenylpropyl or 3,3,3- trifluoropropyl radicals, aryl radicals such as phenyl, tolyl, xylyl, or substituted aryl radicals such as phenylethyl.

One method for surface treating pigments with a polymethylhydrogenosiloxane consists in dispersing the pigments in an organic solvent, then adding the silicone compound. By heating the mixture, covalent bonds are created between the silicone compound and the surface of the pigment.

According to a preferred embodiment, the silicone surfactant may be a non- elastomeric organopolysiloxane, especially selected from polydimethylsiloxanes.

Alkylsilanes and alkoxysilanes

Alkoxy functional silanes are especially described by Witucki in A silane primer, Chemistry and applications of alkoxysilanes, Journal of Coatings Technology, 65, 822, pages 57-60, 1993.

Alkoxysilanes such as alkyltriethoxysilanes and alkyltrimethoxysilanes marketed under references Milquet A-137® (OSI Specialities) and Prosil 9202® (PCR) may be used for coating the pigments.

The use of alkylpolysiloxanes having a reactive terminal group such as alkoxy, hydroxy, halogen, amino or imino are described in the application

JP H07-196946. They are also suitable for treating pigments.

Silicone acrylate polymers

Grafted silicone-acrylic polymers having a silicone backbone as described in US patents 5,725,882, US 5,209,924, US 4,972,037, US 4,981 ,903, US 4,981 ,902, US 5,468,477, and in US patents 5,219,560 and EP 0,388,582, may be used.

Other silicone-acrylate polymers may be silicone polymers having in their structure the following unit of formula (II):

in which the Gi radicals, identical or different, represent hydrogen or a C1-C10 alkyl radical or even a phenyl radical; the G2 radicals, identical or different, represent a C1-C10 alkylene group; G3 represents a polymeric residue resulting from the (homo)polymerization of at least one ethylenically unsaturated anionic monomer; G4 represents a polymeric residue resulting from the (homo)polymerization of at least one ethylenically unsaturated hydrophobic monomer; m and n are equal to 0 or 1 ; a is an integer ranging from 0 to 50; b is an integer which may be between 10 and 350, c is an integer ranging from 0 to 50, with the proviso that one of the parameters a and c is other than 0.

Preferably, the above unit of formula (I) has at least one, and even more preferably all, of the following characteristics:

- the G1 radicals denote an alkyl radical, preferably the methyl radical;

- n is non-zero, and the G2 radicals represent a divalent C1-C3 radical, preferably a propylene radical;

- G3 represents a polymeric radical resulting from the (homo)polymerization of at least one monomer of the ethylenically unsaturated carboxylic acid type, preferably acrylic acid and/or methacrylic acid;

- G4 represents a polymeric radical resulting from the (homo)polymerization of at least one monomer of the (Ci Cio)alkyl (meth)acrylate type, preferably of the isobutyl or methyl (meth)acrylate type.

Examples of silicone polymers having the formula (I) are in particular polydimethylsiloxanes (PDMS) on which, via a thiopropylene-type connecting member, mixed polymer units of the poly(meth)acrylic acid type and of the methyl poly(meth)acrylate type are grafted.

Other examples of silicone polymers having the formula (I) are in particular polydimethylsiloxanes (PDMS) to which polymer units of the isobutyl poly(meth)acrylate type are grafted, via a connecting member of the thiopropylene type.

Silicone resins

The silicone surfactant may be selected from silicone resins such as those previously defined.

Fluoro surfactant

The pigments may be totally or partially surface-treated with a compound of a fluoro nature. Fluoro surfactants may be selected from perfluoroalkyl phosphates, perfluoropolyethers, polytetrafluoropolyethylenes (PTFE), perfluoroalkanes, perfluoroalkyl silazanes, hexafluoropropylene polyoxides, polyorganosiloxanes comprising perfluoroalkyl perfluoropolyether groups.

By perfluoroalkyl radical, it is meant an alkyl radical in which all hydrogen atoms have been replaced by fluorine atoms.

The perfluoropolyethers are especially described in patent application EP 0,486,135, and sold under the trade names FOMBLIN by the company MONTEFLUOS.

Perfluoroalkyl phosphates are in particular described in application JP H05- 86984. Perfluoroalkyl phosphate-diethanol amine marketed by Asahi Glass under the reference Asahi Guard AG530® may be used.

Among the linear perfluoroalkanes, mention may be made of perfluorocycloalkanes, perfluoro(alkylcycloalkanes), perfluoropolycycloalkanes, aromatic perfluoro hydrocarbons (perfluoroarenes) and hydrocarbon perfluoroorganic compounds including at least one heteroatom.

Among the perfluoroalkanes, mention may be made of the series of linear alkanes such as perfluorooctane, perfluorononane or perfluorodecane.

Among the perfluorocycloalkanes and perfluoro(alkylcycloalkanes), mention may be made of perfluorodecaline sold under the name FLUTEC PP5 GMP by the company RHODIA, perfluoro(methyldecaline), perfluoro(C3-C5)alkyl-cyclohexanes) such as perfluoro(butylcyclohexane).

Among the perfluoropolycycloalkanes, mention may be made of bicyclo[3.3.1 ]nonane derivatives such as perfluorotrimethylbicyclo[3.3.1 ]nonane, adamantane derivatives such as perfluorodimethyladamantane and hydrogenated phenanthrene perfluoro derivatives such as tetracosafluoro- tetradecahydrophenanthrene.

Among the perfluoroarenes, mention may be made of perfluoro derivatives of naphthalene such as perfluoronaphthalene and perfluoromethyl-1 -naphthalene.

By way of example of commercial references of pigments treated with a fluoro compound, mention may be made of:

- yellow iron oxide/perfluoroalkyl phosphate sold under the reference PF 5 Yellow 601® by the company Daito Kasei;

- red iron oxide/perfluoroalkyl phosphate sold under the reference PF 5 Red R 516L® by the company Daito Kasei; - black iron oxide/perfluoroalkyl phosphate sold under the reference PF 5 Black BL 100® by the company Daito Kasel;

- titanium dioxide/perfluoroalkyl phosphate sold under the reference PF 5 TiO2 CR 50® by the company Daito Kasei;

- yellow iron oxide/perfluoropolymethylisopropylether sold under the reference Iron Oxide Yellow BF-25-3® by the company Toshiki;

- DC Red 7/perfluoropolymethylisopropylether sold under the reference D&C Red 7 FHC® by the company Cardre Inc.; and

- DC Red 6/PTFE sold under the reference T 9506® by the company Warner- Jenkinson.

Fluorosilicone surfactant

The pigments may be totally or partially surface-treated with a compound of a fluoro-silicone nature.

The fluorosilicone compound may be selected from perfluoroalkyl dimethicones, perfluoroalkyl silanes, and perfluoroalkyltrialkoxysilanes.

Mention may be made, as perfluoroalkyl silanes, of the LP-IT® and LP-4T® products marketed by Shin-Etsu Silicone.

As an example of commercial references of pigment treated with a fluorosilicone compound, mention may be made of titanium dioxide/fluorosilicone sold under the reference Fluorosil Titanium Dioxide 100TA® by the company Advanced Dermaceuticals International Inc.

Other lipophilic surfactants

The hydrophobic treatment agent may also be selected from

(i) metal soaps such as aluminium dimyristate, and aluminium salt of hydrogenated tallow glutamate;

As metal soaps, mention may especially be made of metal soaps of fatty acids having from 12 to 22 carbon atoms, and in particular those having from 12 to 18 carbon atoms.

The metal of the metal soap may especially be zinc or magnesium.

As metal soap, zinc laurate, magnesium stearate, magnesium myristate, zinc stearate, and mixtures thereof may be used.

The hydrophobic treatment agent may also be selected from ii) fatty acids such as lauric acid, myristic acid, stearic acid, palmitic acid. The hydrophobic treatment agent may also be selected from ill) N-acylated amino acids or salts thereof which may comprise an acyl group having from 8 to 22 carbon atoms, such as for example a 2-ethyl hexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl, cocoyl group.

The amino acid may be for example lysine, glutamic acid or alanine.

The salts of these compounds may be aluminium, magnesium, calcium, zirconium, zinc, sodium, potassium salts.

Thus, according to a particularly preferred embodiment, an N-acylated amino acid derivative can especially be a glutamic acid derivative and/or a salt thereof, and more particularly a stearoyl glutamate, such as for example aluminium stearoyl glutamate.

The hydrophobic treatment agent may also be selected from iv) lecithin and derivatives thereof.

The hydrophobic treatment agent may also be v) isopropyl triisostearyl titanate.

As examples of pigments treated with isopropyl titanium triisostearate (ITT), mention may be made of those sold under the trade reference BWB0-I2® (Iron oxide CI77499 and isopropyl titanium triisostearate), BWY0-I2® (Iron oxide CI77492 and isopropyl titanium triisostearate), and BWR0-I2® (Iron oxide CI77491 and isopropyl titanium triisostearate) by the company KOBO.

The hydrophobic treatment agent may also be vi) isostearyl sebacate.

The hydrophobic treatment agent may also be selected from vii) natural plant or animal waxes or synthetic polar waxes;

The hydrophobic treatment agent may also be selected from viii) fatty esters, in particular jojoba esters;

The hydrophobic treatment agent may also be selected from ix) phospholipids.

The waxes indicated in the compounds previously mentioned may be those generally used in the cosmetic field, as defined below.

They may especially be hydrocarbon, silicone and/or fluoro, possibly comprising ester or hydroxyl functions. They can also be of natural or synthetic origin.

By polar wax, it is meant a wax containing chemical compounds including at least one polar group. The polar groups are well known to those skilled in the art; they may be, for example, alcohol, ester, carboxylic acid groups. Polyethylene waxes, paraffin waxes, microcrystalline waxes, ozokerite and Fisher-Tropsch waxes are not polar waxes.

In particular, the polar waxes have an average Hansen solubility parameter ba at 25°C such as ba > 0 (J/cm³)^1/2 and better ba > 1 (J/cm³)^1/2: [Math 1 ]

where bp and bh are respectively the polar and interaction-type contributions specific to Hansen solubility parameters.

The definition of solvents in the three-dimensional solubility space according to HANSEN is described in article by C. M. HANSEN, The three-dimensional solubility parameters J. Paint Technol. 39, 105 (1967):

- bh characterises the specific interaction forces (hydrogen bonds, acid/base, donor/acceptor type, etc.);

- bp characterises DEBYE interaction forces between permanent dipoles as well as KEESOM interaction forces between induced dipoles and permanent dipoles.

The parameters bp and bh are expressed in (J/cm³)^1/2.

A polar wax is especially made of molecules including, in addition to carbon and hydrogen atoms in their chemical structure, heteroatoms (such as O, N, P).

By way of illustrating and not limiting purposes of these polar waxes, mention may especially be made of natural polar waxes, such as beeswax, lanolin wax, orange wax, lemon wax, and Chinese insect waxes, rice bran wax, Carnauba wax, Candellila wax, Ouricury wax, cork fibre wax, sugar cane wax, Japan wax, and sumac wax, montan wax.

According to a particular embodiment, the pigments may be coated with at least one compound selected from silicone surfactants; fluoro surfactants; N-acylated amino acids or salts thereof; isopropyl triisostearyl titanate; natural plant or animal waxes; fatty esters; and mixtures thereof.

According to a particularly preferred embodiment, the pigments can be coated by an N-acylated amino acid and/or a salt thereof, in particular by a derivative of glutamic acid and/or a salt thereof, or by a fatty ester, in particular by a jojoba ester.

According to a more particularly preferred embodiment, the pigments can be coated with an N-acylated amino acid and/or a salt thereof, in particular with a glutamic acid derivative and/or a salt thereof, especially a stearoyl glutamate, such as for example aluminium stearoyl glutamate.

As examples of coated pigments according to the invention, mention may be made more particularly of titanium dioxides and iron oxide, coated with aluminium stearoyl glutamate, for example marketed under reference NAI by MIYOSHI KASEL Pigments not coated with a hydrophobic compound

As stated previously, a composition may further contain pigments not coated with a lipophilic or hydrophobic compound.

These other pigments may be coated with a hydrophilic compound or not coated.

These pigments may be mineral pigments especially as defined previously.

These pigments may also be organic pigments.

By organic pigment, it is meant any pigment that meets the definition of the Ullmann encyclopaedia in the chapter on organic pigment. The organic pigment may especially be selected from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophtalone compounds.

The organic pigment(s) may be selected for example from carmine, carbon black, aniline black, melanin, azo yellow, quinacridone, phthalocyanine blue, sorghum red, blue pigments coded in the Colour Index under references Cl 42090, 69800, 69825, 73000, 74100, 74160, yellow pigments coded in the Colour Index under references Cl 11680, 11710, 15985, 19140, 20040, 21 100, 21108, 47000, 47005, green pigments coded in the Colour Index under references Cl 61565, 61570, 74260, orange pigments coded in the Colour Index under references Cl 1 1725, 15510, 45370, 71105, red pigments coded in the Colour Index under references Cl 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, and pigments obtained by oxidising polymerization of indolic, phenolics derivatives as described in patent FR 2,679,771.

These pigments may also be in the form of composite pigments as described in patent EP1 184426. These composite pigments may in particular be composed of particles having an inorganic core covered at least partially with an organic pigment and at least one binder ensuring attachment of the organic pigments to the core.

The pigment may also be a lake. By lake, it is meant insolubilised colorants adsorbed on insoluble particles, the whole thus obtained remaining insoluble during use.

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

Among the organic colorants, mention may be made of cochineal carmine. Products known under the following names may also be mentioned: D&C Red 21 (Cl 45,380), D&C Orange 5 (Cl 45,370), D&C Red 27 (Cl 45,410), D&C Orange 10 (Cl 45,425), D&C Red 3 (Cl 45,430), D&C Red 4 (Cl 15,510), D&C Red 33 (Cl 17,200), D&C Yellow 5 (Cl 19,140), D&C Yellow 6 (Cl 15,985), D&C Green (Cl 61 ,570), D&C Yellow 1 O (Cl 77,002), D&C Green 3 (Cl 42,053), D&C Blue 1 (Cl 42,090).

As examples of lakes, mention may be made of the product known as D&C Red 7 (Cl 15,850:1 ).

Nature of the hydrophilic coating

As stated previously, these other pigments may be coated with a hydrophilic compound.

Said hydrophilic compound allowing surface treatment of a pigment to optimise its dispersion in the gelled aqueous phase is more particularly selected from biologic polymers, carbohydrates, polysaccharides, polyacrylates or polyethylene glycol derivatives.

As examples of biologic polymers, mention may be made of carbohydrate-type monomers-based polymers.

More particularly, mention may be made of biosaccharide gum; chitosans and derivatives thereof, such as butoxychitosan, carboxymethyl chitosan, carboxybutyl chitosan, chitosan gluconate, chitosan adipate, chitosan glycolate, chitosan lactate, etc.; chitins and derivatives thereof, such as carboxymethyl chitin, chitin glycolate; cellulose and derivatives thereof such as cellulose acetate; microcrystalline cellulose; distarch phosphate; sodium hyaluronate; soluble proteoglycans; galacto-arabinanes; glycosaminoglycans; glycogen; sclerotium gum; dextran; starch and derivatives thereof; and mixtures thereof.

As examples of carbohydrates, mention may especially be made of polyhydroxyaldehydes or polyhydroxyketones, of general formula: Cx(H₂O)_y in which x and y can range from 1 to 1 ,000,000.

Carbohydrates may be monosaccharides, disaccharides or polysaccharides.

As examples of carbohydrates, mention may be made of amylodextrins, betaglucans, cyclodextrins, modified maize starch, glycogen, hyaluronic acid, hydroxypropylcylodextrin, lactose, maltitol, guanosine, glyceryl starch, Triticum Vulgare starch, trehalose, sucrose and derivatives thereof, raffinose, sodium chondroitin sulphate.

C1-C20 alkylene glycols or C1-C20 alkylene glycol ethers, alone or used in combination with tri-Ci-C2o-alkylsilanes can also be used as surface treatment agents. Mention may be made, as examples of pigments surface-treated with PEG alkyl ether alkoxy silane, such as, for example, pigments treated with PEG-8-methyl ether triethoxysilane marketed by the company KOBO under the name pigments SW.

Silicones such as dimethicones having hydrophilic groups, also known under the name dimethicones copolyols or alkyl dimethicones copolyols, may also be suitable for the invention as a surface treatment agent. In particular, such dimethicones may comprise as repeat units, C1-C20 alkylene oxides, such as ethylenic or propylenic.

By way of example, mention may be made of the pigment treated with PEG-12- Dimethicone, marketed by the company SENSIENT CORPORATION, under the name LCW AQ® Pigment.

The amount of pigments coated with at least one hydrophilic compound and/or of uncoated pigments is especially conditioned by the intended purpose of the cosmetic composition in question, and its adjustment is of course a matter for the composition formulator.

According to a particular embodiment, the composition further comprises at least one pigment selected from titanium dioxides and/or iron oxides, in particular coated with a hydrophobic surface treatment agent, in particular by an N-acylated amino acid and/or a salt thereof, in particular by a glutamic acid derivative and/or a salt thereof, in particular a stearoyl glutamate, such as for example aluminium stearoyl glutamate.

According to a particular embodiment, the composition according to the invention comprises at least one uncoated or coated pigment, preferably at least one coated pigment.

Alpha hydroxy acid (AHA)

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

By alpha hydroxy acid, it is meant, according to the present invention, a carboxylic acid having at least one hydroxy function occupying an alpha position on said acid (carbon adjacent to a carboxylic acid function). This acid may be present in the final composition in the form of free acid and/or in the form of one of its associated salts (salts with an organic base or an alkali, especially), depending in particular on the final pH imposed on the composition. The a-hydroxy acids (alpha hydroxy acids or AHAs) are for example selected from lactic acid, citric acid, methyl lactic acid, glucuronic acid, glycolic acid, pyruvic acid, 2-hydroxy- butanoic acid, 2-hydroxypentanoic acid, 2-hydroxyhexanoic acid, 2-hydroxyheptanoic acid, 2-hydroxyoctanoic acid, 2-hydroxynonanoic acid, 2-hydroxydecanoic acid, 2- hydroxyundecanoic acid, 2-hydroxydodecanoic acid, 2-hydroxytetradecanoic acid, 2- hydroxy-hexadecanoic acid, 2-hydroxyoctadecanoic acid, 2-hydroxytetracosanoic acid, 2-hydroxyeicosanoic acid; mandelic acid; phenylactic acid; gluconic acid; galacturonic acid; aleuritic acid; ribonic acid; tartronic acid; tartaric acid; malic acid; fumaric acid; salts thereof and mixtures thereof.

According to a preferred embodiment, the alpha hydroxy acid is selected from lactic acid, citric acid, malic acid, tartaric acid, and salts thereof. More particularly, the alpha hydroxy acid is selected from lactic acid, citric acid, salts thereof, and mixtures thereof.

The alpha hydroxy acid(s) may be present in an amount ranging from 0.001 to 10% by weight, from 0.005 to 5% by weight, preferably from 0.01 to 3% by weight relative to the total weight of the composition.

Surfactant

The composition may also comprise at least one surfactant, preferably nonionic, cationic or anionic, preferably a non-ionic surfactant.

Preferably, the non-ionic surfactant may be selected from non-ionic surfactants known from prior art, especially from fatty acid and polyglycerol esters, sugar esters, poloxamers, polysorbates, and mixtures thereof.

Preferably, the non-ionic surfactant is selected from fatty acid and polyglycerol esters and sugar esters, preferably from fatty acid and polyglycerol esters.

When present, the non-ionic surfactant(s) are present in a content of between 0.01% and 15% by weight, preferably in a content of between 0.05% and 10% by weight, preferably between 0.1% and 8% by weight, preferably between 1% and 7% by weight relative to the total weight of the composition.

Physiologically acceptable aqueous medium

The composition according to the invention comprises a physiologically acceptable aqueous medium. Said medium comprises water. The water used may be sterile demineralized water and/or floral water such as rose water, cornflower water, chamomile water or lime water, and/or natural thermal or mineral water such as VITTEL water, LUCAS water or LA ROCHE POSAY water.

The composition preferably comprises at least 5% by weight by weight of water relative to the total weight of the composition, preferably at least 10% by weight, preferably at least 20% by weight, preferably at least 25% by weight, preferably at least 30% by weight, preferably at least 35% by weight, preferably at least 40% by weight, preferably at least 50% by weight, more preferably at least 60% by weight, even more preferably at least 70% by weight, advantageously at least 80% by weight.

The composition preferably comprises from 5% to 95% by weight of water relative to the total weight of the composition, more preferably from 10% to 85%, even more preferably from 20% to 80%, even more preferably from 25% to 75%, even more preferably from 28% to 70%, even more preferably from 30% to 65%, even more preferably from 35% to 60%.

The aqueous phase may also comprise at least one organic solvent miscible in water at 25°C.

Preferably, the water-miscible organic solvent is selected from alcohols, polyols, and mixtures thereof.

Among the alcohols, mention may be made of C1-C10 alcohols, more preferably C1-C5 alcohols, such as ethanol, isopropanol, propanol and butanol.

The polyol is preferably selected from polyols having from 2 to 20 carbon atoms, more preferably from 2 to 6 carbon atoms, such as glycerol, diglycerol, propylene glycol, isoprene glycol, dipropylene glycol, butylene glycol, hexylene glycol, 1 ,2- propanediol, 1 ,3-propanediol, pentylene glycol, polyethylene glycols having from 2 to 200 ethylene oxide units, and mixtures thereof.

Advantageously, the composition according to the invention comprises ethanol.

The composition may comprise from 0.1% to 25% by weight of water-miscible organic solvent, relative to the total weight of the composition, more preferably from 0.5% to 20% by weight, more preferably from 1% to 15% by weight, more preferably from 1 .5% to 10% by weight, even more preferably from 2% to 5% by weight. Preferably, the weight ratio of the polyol(s), if present, to chitosan (that is, weight ratio polyol(s):chitosan) is between 0.1 and 6. Preferably, it is between 0.1 and 5, preferably between 0.2 and 5, preferably between 0.2 and 4.5, preferably between 0.5 and 2.

Oil phase

The composition according to the invention preferably also comprises at least one oil phase. When the composition used according to the invention comprises an oil phase, it preferably contains at least one oil, especially a cosmetic oil. It may further contain other fats.

By “oil”, it is meant a non-aqueous compound, liquid at 25°C and atmospheric pressure (1 .013.10⁵ Pa), non-miscible in water.

By “non-miscible”, it is meant that mixing the same amount of water and oil, after stirring, does not lead to a stable solution comprising only one phase, under the aforementioned temperature and pressure conditions. The observation is carried out by eye or by means of a phase contrast microscope as required, on 100 g of mixture obtained after sufficient Rayneri stirring to make a vortex appear within the mixture (as an indication 200 to 1000 rpm); the resulting mixture being left at rest, in a closed vial, for 24 hours at room temperature before observation.

As oils usable in the composition of the invention, mention may be made, for example:

- hydrocarbon oils of animal origin, such as perhydrosqualene;

- hydrocarbon oils of plant origin, such as liquid triglycerides of fatty acids having from 4 to 10 carbon atoms such as triglycerides of heptanoic or octanoic acids or, for example, sunflower, maize, soy, pumpkin, grape seed, sesame, hazelnut, apricot, macadamia, arara, sunflower, castor, avocado oils, triglycerides of caprylic/capric acids such as those sold by the company Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel, jojoba oil, shea butter oil;

- the synthesis esters and ethers, in particular of fatty acids, such as the oils of formulas R1 COOR2 and R1 OR2 wherein R1 represents the remainder of a fatty acid having from 8 to 29 carbon atoms, and R2 represents a hydrocarbon chain, branched or not, containing from 3 to 30 carbon atoms, such as for example Purcellin oil, isononyl isononanoate, isopropyl myristate, ethyl-2-hexyl palmitate, octyl-2-dodecyl stearate, octyl-2-dodecyl erucate, isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octylhydroxystearate, octyldodecyl hydroxystearate, diisostearylmalate, triisocetyl citrate, heptanoates, octanoates, decanoates of fatty alcohols; polyol esters such as propylene glycol dioctanoate, neopentylglycol diheptanoate, and diethyleneglycol diisononanoate; and pentaerythritol esters such as pentaerythrityl tetraisostearate or dipentaerythrityl pentaisononanoate;

- linear or branched hydrocarbons, of mineral or synthetic origin, such as paraffin oils, volatile or not, and derivatives thereof, branched-chain hydrocarbon oils comprising from 10 to 20 carbon atoms such as isohexadecane, isododecane, isoparaffins and mixtures thereof, vaseline, polydecenes, polyisobutenes, hydrogenated polyisobutenes such as, for example, Parleam® marketed by the company NIPPON OIL FATS, PANALANE H-300 E marketed by the company AMOCO, VISEAL 20000 marketed by the company SYNTEAL, REWOPAL PIB 1000 marketed by the company WITCO, or PARLEAM LITE marketed by NOF Corporation, branched alkanes alone or in mixture, such as the mixture of undecane and tridecane marketed under the name Cetiol UT by BASF, or alkanes of plant origin, in particular coconut, such as those marketed under the name VEGELIGHT SILK by BIOSYNTHIS, or the mixture of C13-15 alkanes marketed under the name NEOSSANCE HEMISQUALANE CN by AMYRIS;

- partially hydrocarbon and/or silicone fluoro oils as those described in document JP-A-2-295912; or

- mixtures thereof.

The composition may comprise from 5% to 90% by weight of oil phase, relative to the total weight of the composition, preferably from 7% to 80% by weight, more preferably from 10% to 60% by weight, advantageously from 15% to 40% by weight.

According to a preferred embodiment, the oil phase contains at least one nonvolatile oil, the content by weight of which is less than or equal to 50%, preferentially less than or equal to 35%, preferentially less than or equal to 20%, preferentially less than or equal to 15%, preferentially less than or equal to 10%, and preferentially less than or equal to 7% relative to the total weight of the composition.

Advantageously, the weight ratio of the non-volatile oil to the modified polysaccharide is between 0.1 and 10, preferentially between 0.1 and 5, preferentially between 0.3 and 3, preferentially between 0.5 and 2. By “non-volatile oil”, it is meant an oil remaining on the keratin materials at room temperature and atmospheric pressure for at least several hours and especially having a vapour pressure of less than 10-3 mm Hg (0.13 Pa).

The oils may be selected from the above-mentioned oils.

According to one embodiment, the composition according to the invention further comprises a volatile oil and/or a volatile alcohol.

By “volatile oil”, it is meant any oil likely to evaporate on contact with the skin, at ambient temperature and atmospheric pressure. The volatile oils of the invention are volatile cosmetic oils, liquid at room temperature, having a non-zero vapour pressure, at room temperature and atmospheric pressure, in particular ranging from 0.13 Pa to 40,000 Pa (0.001 to 300 mm Hg) and preferably ranging from 1.3 to 1300 Pa (0.01 to 10 mm Hg).

The volatile oil may be selected from hydrocarbon volatile oils, silicone volatile oils, fluoro volatile oils, and mixtures thereof, preferably from hydrocarbon volatile oils.

Volatile hydrocarbon oils may be selected from hydrocarbon oils having from 8 to 16 carbon atoms, and especially branched C8-C16 alkanes such as petroleum- derived C8-C16 isoalkanes (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and for example oils sold under the trade names Isopar® or Permethyl®.

In particular, the composition according to the invention may comprise isododecane, cyclopentasiloxane; isohexadecane, or a mixture thereof.

The composition according to the invention may comprise a volatile oil in a content ranging from 1 to 60% by weight relative to the total weight of the composition, preferably from 5 to 50% by weight, more preferably ranging from 10 to 40% by weight, and more preferably still from 15 to 25% by weight.

By volatile alcohol, it is meant a C1 -C4 alcohol, such as for example ethanol, isopropanol, butanol, n-propanol.

The composition according to the invention may comprise a volatile alcohol in a content ranging from 0.1% to 25% by weight of water-miscible organic solvent, relative to the total weight of the composition, preferentially from 0.5% to 20% by weight, more preferably from 1 % to 15% by weight, even more preferably from 1.5% to 10% by weight, advantageously from 2% to 5% by weight. pH of the composition The composition according to the invention has a pH of less than or equal to 7, preferably less than or equal to 6.5, preferably less than or equal to 6.3. Advantageously, the pH of the composition is between 3 and 6.3, preferably between 4 and 6.3.

Preferably, the cosmetic composition according to the invention comprises at least one base and/or at least one acid. The base and acid according to the invention are known and conventionally used in the cosmetic field.

The base and/or acid are especially used to adjust the final pH of the composition between 3 and 6.3.

The acid may for example be citric acid.

The base may be selected from mineral bases such as for example alkali metal hydroxides, sodium hydroxide, potassium hydroxide.

Preferably, the base of the composition is an alkali metal hydroxide, preferably sodium hydroxide or potassium hydroxide.

The composition according to the invention may comprise at least one base in an active material content ranging from 0.5% to 10% by weight, relative to the total weight of the composition, especially from 1% to 5% by weight, preferably ranging from 1% to 4% by weight.

The composition according to the invention can be obtained conventionally by those skilled in the art.

The following examples illustrate the invention. Unless otherwise stated, percentages are given by weight relative to the total weight of the composition (%w/w).

EXAMPLES: PREPARATIONS OF COMPOSITIONS ACCORDING TO THE INVENTION AND COMPARISONS WITH COMPARATIVE COMPOSITIONS

Compositions B, D, and E according to the invention, comparative compositions A, C, and F-G, were prepared by mixing the ingredients of Table 1 . Compositions B and D according to the invention contain chitosan, dextrin palmitate, and pigments.

Comparative compositions A and C contain chitosan and pigments, but no dextrin palmitate.

Compositions A and B are invert emulsions, while compositions C to G are direct emulsions.

- Protocol for spreading the compositions in a film

Spreading of products is performed on a spreading bench (Elcometer 4340 Applicator) allowing its speed and distance over which it is carried out, to be adjusted. The bench is equipped with a suction system connected to a pump so that the substrate on which the spreading is carried out does not move. Contrast charts with a black background and an unvarnished white background are used (1 byko-chart, uncoated N2A, code 2831 ). The spreading thickness is adjustable by means of the square spreader deposited onto the support so as to spread by levelling when the platform is switched on. Each slice of the spreader allows spreading with a different thickness ranging from 25 pm to 200 pm. The selected thickness is 25 pm to approximate an in v/vo film thickness. A weight of 960 g is added above the spreader during spreading. The spreading speed is set to 1 in/sec, that is, 2.54 cm/s. The films are dried for 24 h at room temperature and humidity (RH) (50% RH).

- Contrast ratio measurement protocol for coverage objectivation

Colour measurement is performed with the Konica Minolta CM-700d spectrophotometer. Contact measurement ensures that there is no light pollution.

Selected settings: 8 mm aperture; Uncertainty: 0.04; SCI/SCE measurement; Geometry d/8°.

The colour measurements on the two backgrounds (black background FN and white background FB) allow the coverage of a foundation to be characterised by calculating the “contrast ratio”, (CR%) that is, YFN/YFB x 100, where YFN and YFB are respectively the luminance values measured on the black background and the white background, the latter being all the higher the greater the coverage of the foundation.

- Dry, water and oil endurance test protocol

The water friction endurance test is carried out by colorimetric measurements on dry film before and after abrasion. Abrasion is performed by attaching a strip of tissue (Chicopee® Veraclean™ Polish Plus) wet if necessary (400 pL of water or oil in the tissue), to the 25 pm spreader slice. The 960 g weight is added over the spreader during abrasion. The bench speed is set to 2.54 cm/s.

Colour measurement before and after abrasion is performed using the same spectrophotometric method as explained previously.

In order to evaluate friction endurance, the “Contrast Ratio” is measured respectively before friction (CR Dry Deposition, %) and after abrasion (CR Dry Deposition Friction, %). The loss [(CR Dry Deposition Friction - CR Dry Deposition]/CR Dry Deposition]*! 00, as a percentage, quantifies the loss of coverage and indicates the friction endurance of the film: the lower this loss, the more resistant the film is to friction.

Each CR value therefore represents an average of 3 to 6 measurements.

Results in invert emulsion:

Compositions A and B are prepared as follows:

Preparation of the aqueous phase:

Under Rayneri deflocculator, sprinkle the chitosan over the water. Add the lactic acid and leave for 5 min at 300 rpm.

Meanwhile, in the final beaker, mix the isododecane, caprylic/capric triglycerides, polyglyceryl-6 polyricinoleate and resin under Rayneri deflocculator at 250 rpm.

Slowly add the aqueous phase to the final beaker by increasing the rotation speed to 500 rpm.

Add the dry pigments and then the alcohol.

The results are shown in Table 1 .

[Table 1]

* The pigments used in the compositions are a mixture of TiO2 pigments surface-treated with stearoyl glutamate and iron oxides treated with the disodium stearoyl glutamate/aluminium hydroxide pair (NAI-White A and NAI-BHP-10, NAI-YHP-10 and NAI-R-800HP-10 from Miyoshi Kasei)

The results show better water, oil, and dry endurance for the composition B according to the invention relative to the comparative composition A.

The results also show a possible coverage gain for the composition B of the invention relative to the comparative composition A.

Thus, the addition of dextrin palmitate in an invert formula containing 2% chitosan significantly improves the coverage and both dry and water endurance of this coverage.

Results in direct emulsion:

Compositions C to G are prepared as follows:

Aqueous phase (lactic acid, water, alcohol, surfactant and possibly chitosan)

- If chitosan is present:

- Disperse the chitosan in the water under Rayneri deflocculator.

- Add the lactic acid and stir for 30 min, the speed is adjusted so as to have a minimum vortex.

- Add polyglyceryl-10 laurate and alcohol and stir for 10 min.

- Add the pigments and stir for 10 min. - If chitosan is absent:

- Disperse the polyglyceryl-10 laurate in water under Rayneri deflocculator, the speed is adjusted so as to have a minimum vortex.

- Add alcohol.

- Add the pigments and stir for 10 min.

Fatty phase (caprylic/capric triglycerides, isododecane, pigments and possibly dextrin palmitate)

- Heat the fatty phase to 60°C on a magnetic heating plate so as to obtain a homogeneous mixture, then cool to room temperature.

Emulsification

- Add the fatty phase to the aqueous phase under Rayneri emulsifier and stir for 10 min, the speed is adjusted so as to have a minimum vortex.

The results are shown in Tables 2 and 3.

[Table 2]

* The pigments used in the compositions are a mixture of TiO2 pigments surface-treated with stearoyl glutamate and iron oxides treated with the disodium stearoyl glutamate/aluminium hydroxide pair (NAI-White A and NAI-BHP-10, NAI-YHP-10 and NAI-R-800HP-10 from Miyoshi Kasei)

Adding dextrin palmitate to a direct formula containing 2% chitosan significantly improves dry, water and oil endurance of coverage. [Table 3]

* The pigments used in the compositions are a mixture of TiO2 pigments surface-treated with stearoyl glutamate and iron oxides treated with the disodium stearoyl glutamate/aluminium hydroxide pair (NAI-White A and NAI-BHP-10, NAI-YHP-10 and NAI-R-800HP-10 from Miyoshi Kasei)

The viscosity of the formulas is measured as follows:

Viscosity evaluation protocol

The viscosity measurement is carried out on a DHR2 type rheometer from TA instrument using a sandblasted static part and a sandblasted planar mobile part for a gap of 1 mm and an experiment temperature of 25°C. The viscosity results in Pa.s are taken in a comparable and systematic manner for a shear of 0.1 s ^-1.

In these tests at total iso-mass content between dextrin palmitate and/or chitosan, the following effects can be observed:

- The formula with only dextrin palmitate (F) instantly phase separates;

- The formula with only chitosan (G) becomes uncontrollably viscous; and

- Only the formula containing both dextrin palmitate and chitosan according to the invention (E) is both formulable, and of controlled and acceptable viscosity.

Claims

1 . A cosmetic composition, especially for making up and/or caring for the skin and/or lips and/or lashes and/or hair comprising, in a physiologically acceptable aqueous medium: a) at least 0.01 % by weight relative to the total weight of the composition of native chitosan having a molecular weight strictly greater than 3000 Daltons, this amount being strictly less than 15% by weight, b) at least one modified polysaccharide, and from 5% to 25% by weight relative to the total weight of the composition of at least one pigment colouring material.

2. The composition according to claim 1 , wherein the native chitosan has a molecular weight greater than or equal to 10 kDa, preferably greater than or equal to 15 kDa, preferably greater than or equal to 20 kDa, preferably the native chitosan has a molecular weight of between 10 kDa and 2 MDa, preferably between 15 kDa and 1 .5 MDa, preferably between 20 kDa and 300 kDa, preferably between 20 kDa and 200 kDa.

3. The composition according to claim 1 or 2, wherein the native chitosan has a degree of acetylation of chitosan of less than or equal to 80%, preferably less than or equal to 70%, preferably less than or equal to 60%, preferably less than or equal to 50%, preferably less than or equal to 35%, preferably less than or equal to 25%, preferably less than or equal to 15%.

4. The composition according to one of the preceding claims, wherein the native chitosan is a polysaccharide prepared from a fungal origin, preferably derived from the mycelium of an Ascomycete-type fungus, and in particular from Aspergillus niger and/or a Basidiomycete fungus, and in particular Lentinula edodes and/or Agaricus bisporus, preferably the fungus is Aspergillus niger.

5. The composition according to one of the preceding claims, wherein the native chitosan is present in an amount ranging from 0.01% to 14% by weight, preferably from 0.1 % to 14% by weight, preferably from 0.1% to 12% by weight, preferably from 0.2% to 7% by weight, preferably from 0.25% to 5% by weight, preferably from 0.3 to 3% by weight, or even more preferably from 0.5 to 2% by weight relative to the total weight of the composition.

6. The composition according to any of the preceding claims, wherein the modified polysaccharide is selected from cationic, non-ionic, anionic or amphoteric, better non-ionic polysaccharides, modified by the presence of at least one cyclic or non-cyclic, linear or branched, saturated or unsaturated, aromatic or not, aliphatic hydrocarbon chain, comprising from 2 to 30 carbon atoms, possibly substituted with one or more atoms or groups a), f), g), h), i), j), I) as defined below and/or p) (di)alkylamino and/or possibly interrupted by one or more heteroatoms or groups a') to c') as defined below: a) halogen such as chlorine or bromine, f) (thio)carboxamide -C(O)-N(Ra)2 or -C(S)-N(Ra)2, g) cyano, h) iso(thio)cyanate, i) (hetero)aryl such as phenyl or furyl, and j) (hetero)cycloalkyl such as anhydride, epoxide or dithiolane, I) R-X with R representing a group selected from a) cycloalkyl such as cyclohexyl, p) heterocycloalkyl such as preferably monosaccharide sugar such as glucose, y) (hetero)aryl such as phenyl, 5) cosmetic active, and X representing a’) O, S, N(Ra), or Si(Rb)(Rc), b') S(O)r, or (thio)carbonyl, or c') the associations of a') with b') such as (thio)ester, (thio)amide, (thio)urea, sulfonamide; Ra representing a hydrogen atom, or a (C1 -C4)alkyl, or aryl(C1- C4)alkyl group such as benzyl, preferably Ra represents a hydrogen atom; Rb and Rc, identical or different, represent a (C1 -C4)alkyl or (C1 -C4)alkoxy group, particularly a single substituent; and/or a') heteroatoms such as O, S, N(Ra), and Si(Rb)(Rc), b') S(O)r, (thio)carbonyl, orc') associations of a') with b') such as (thio)ester, (thio)amide, (thio)urea, sulfonamide with r being 1 or 2, Ra being as defined previously, preferably Ra representing a hydrogen atom, Rb and Rc, being as defined previously; preferably, the modified polysaccharide is selected from modified polysaccharides derived from gum arabic; ghatti gum; karaya gum; tragacanth gum; agar; alginates; carrageenans and furcellerans; guar gum; carob gum; fenugreek gum; tamarind gum; konjac gum; xanthan gum or dehydroxanthan gum; gellan gum; scleroglucan gum; cellulose; starch; dextrin, pullulan, inulin; and pectin; preferably selected from cellulose; starch; dextrin, pullulan, inulin, more preferably cellulose.

7. The composition according to one of the preceding claims, wherein the modified polysaccharide is an alkylpolysaccharide the alkyl radical of which comprises between 2 and 30, preferably between 2 and 10, more preferably between 2 and 6 carbon atoms; preferably the modified polysaccharide is a cellulose or guar derivative; preferably the modified polysaccharide is an alkylcellulose the linear or branched alkyl residue of which comprises between 1 and 10 carbon atoms, in particular between 2 and 6 carbon atoms, preferably between 2 and 3 carbon atoms, or an alkylguar; preferably the modified polysaccharide is selected from ethylcellulose, propylcellulose and ethylguar, preferably ethylcellulose.

8. The composition according to one of claims 1 to 6, wherein the modified polysaccharide is selected from polysaccharide esters.

9. The composition according to one of claims 1 to 6 or 8, wherein the modified polysaccharide is selected from dextrin palmitate and pullulan myristoyl.

10. The composition according to one of the preceding claims, wherein the modified polysaccharide may be present in the composition according to the invention in a content ranging from 0.05% to 20% by weight, preferably from 0.1% to 15% by weight, preferably from 0.2% to 12% by weight, preferably from 0.5% to 10% by weight, preferably between 1% and 5% relative to the total weight of the composition.

1 1 . The composition according to one of the preceding claims, wherein the weight ratio of the total amount of the modified polysaccharide to the total amount of chitosan is between 0.05 to 200, more preferably from 0.1 to 100, more preferably from 0.2 to 50, or even better from 0.5 to 40, preferably from 0.5 to 20, preferably from 0.8 to 10, and even more preferably from 1 to 8, or even from 1.1 to 5.

12. The composition according to one of the preceding claims, wherein the pigment colouring material is a mineral pigment selected from titanium dioxide, iron oxides, zirconium or cerium oxides, zinc or chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue, metal powders such as aluminium powder and copper powder, nacres and monochromatic pigments.

13. The composition according to one of the preceding claims, wherein the pigment colouring material is an organic pigment selected from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophtalone compounds.

14. The composition according to one of one of the preceding claims, wherein the pigment colouring material is selected from titanium dioxide, iron oxides, zirconium or cerium oxides, zinc or chromium oxides, and mixtures thereof, preferably the pigment is selected from titanium dioxide, iron oxides, and mixtures thereof.

15. The composition according to one of the preceding claims, wherein the pigment colouring material is present in a content ranging from 6% to 20% by weight, preferably from 8% to 18% by weight relative to the weight of the composition.

16. The composition according to one of the preceding claims, comprising 10% by weight or less, preferably 5% by weight or less, of silicone, relative to the total weight of the composition.

17. The composition according to one of the preceding claims that is substantially free of silicone other than a film-forming or tackifying silicone polymer; preferably the composition comprises less than 1 % by weight relative of the total weight composition, preferably less than 0.5% by weight, preferably less than 0.3% by weight, preferentially 0.1% by weight of silicone other than a film-forming or tackifying silicone polymer, preferentially the composition according to the invention is substantially free of silicone, advantageously the composition is completely free of silicone.

18. The composition according to one of the preceding claims, wherein the physiologically acceptable aqueous medium comprises at least 5% by weight of water relative to the total weight of the composition, preferably at least 10% by weight, preferably at least 20% by weight, preferably at least 25%, preferably at least 30% by weight, preferably at least 35% by weight, preferably at least 40% by weight; preferably from 5% to 95% by weight of water relative to the total weight of the composition, more preferably from 10% to 85%, even more preferably from 20% to 80%, even more preferably from 25% to 75%, even more preferably from 28% to 70%, even more preferably from 30% to 65%, even more preferably from 35% to 60%; and possibly at least one organic solvent miscible in water at 25°C selected from alcohols, polyols and mixtures thereof, preferably the weight ratio of the polyol(s), if present, to chitosan is between 0.1 and 6, preferably between 0.1 and 5, preferably between 0.2 and 5, preferably between 0.2 and 4.5, preferably between 0.5 and 2.

19. The composition according to one of the preceding claims, comprising at least one alpha hydroxy acid, preferably selected from lactic acid, citric acid, methyllactic acid, glucuronic acid, glycolic acid, pyruvic acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid, 2-hydroxyhexanoic acid, 2-hydroxyheptanoic acid, 2- hydroxyoctanoic acid, 2-hydroxy-nonanoic acid, 2-hydroxydecanoic acid, 2- hydroxyundecanoic acid, 2-hydroxydodecanoic acid, 2-hydroxytetradecanoic acid, 2- hydroxy-hexadecanoic acid, 2-hydroxyoctadecanoic acid, 2-hydroxytetra-cosanoic acid, 2-hydroxyeicosanoic acid ; mandelic acid; phenyllactic acid; gluconic acid; galacturonic acid; aleuritic acid; ribonic acid; tartronic acid; tartaric acid; malic acid; fumaric acid; salts thereof and mixtures thereof.

20. The composition according to one of the preceding claims, which has a pH of less than or equal to 7, preferably less than or equal to 6.5, preferably less than or equal to 6.3, preferably between 3 and 6.3, preferably between 4 and 6.3.

21. The composition according to any of the preceding claims, further comprising at least one surfactant, preferably a non-ionic surfactant, preferably in a content by weight of between 0.01% and 15%, preferably in a content of between 0.05% and 10% by weight, preferably between 0.1 % and 5% by weight, preferably between 0.1 % and 2% by weight relative to the total weight of the composition.

22. The composition according to any of the preceding claims, comprising at least one non-volatile oil, preferably in a content by weight of less than or equal to 50%, preferentially less than or equal to 35%, preferentially less than or equal to 20%, preferentially less than or equal to 15%, preferentially less than or equal to 10% and preferentially less than or equal to 7% relative to the total weight of the composition and/or the weight ratio of the non-volatile oil to the modified polysaccharide of which is between 0.1 and 10, preferentially between 0.1 and 5, preferentially between 0.3 and 3, preferentially between 0.5 and 2.

23. The composition according to any of the preceding claims further comprising a volatile oil and/or a volatile alcohol.

24. A method for making up and/or caring for the skin and/or the keratinous appendages, wherein the composition according to any one of the preceding claims is applied to the skin and/or the keratinous appendages.