EP4731169A1 - Composition with chitosan and a natural resin - 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, in particular the skin, comprising, in a physiologically acceptable aqueous medium: a) at least 0.01% by weight relative to the total weight of native chitosan composition having a molecular weight strictly greater than 3,000 Daltons, this amount being strictly less than 15% by weight, and b) at least one natural resin. It also relates to a method for making up and/or caring for the skin and/or skin appendages, wherein the composition according to the invention is applied to the skin and/or the skin appendages.

Description

COMPOSITION WITH CHITOSAN AND A NATURAL RESIN

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 native chitosan composition having a molecular weight strictly greater than 3,000 Daltons, this amount being strictly less than 15% by weight, and b) at least one natural resin.

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

There are many cosmetic compositions for which holding properties of the deposited film, after application to the keratin materials, are desired. Mention may be made for example of lipsticks, foundations, mascaras or nail polishes. In order to achieve such a result, special raw materials, especially film-forming agents, can be combined.

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 whose deposition has good optical properties, e.g., coverage, matt finish, good hold and whose resistance, e.g., to mechanical wear dry or to water, is improved. There is also a need for such compositions to further present good sensoriality at application and/or comfort at application, as well as good texture, i.e. especially that have a controlled and acceptable viscosity.

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

It is therefore essential to propose more sustainable compositions and/or preparation methods and/or ingredients thus enabling these environmental challenges to be addressed. In 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 below, such compositions having good formulability, good cosmetic properties, especially good resistance of makeup properties, such as coverage or matt finish, under dry friction, to water, oils and/or sebum, as well as good sensoriality and texture. The present invention in particular aims to propose emulsions comprising chitosan and having good resistance to dryness, 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 resistance when dry and/or in the presence of a chemical aggressor such as water.

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

The 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 native chitosan composition having a molecular weight strictly greater than 3,000 Daltons, this amount being strictly less than 15% by weight, and b) at least one natural resin.

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

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

According to one embodiment, the composition according to the invention is in the form of an oil-in-water emulsion, in particular having an oil phase/water phase weight ratio 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 an oil phase/water phase weight ratio 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.

'Physiologically acceptable' means 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.

Silicone means any silicone compound.

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

'Substantially free of silicone different from a film-forming or tacking silicone polymer, preferably different from a silicone resin or a silicone acrylate copolymer, preferably different from an MQ resin or acrylates/polytrimethylsiloxy-methacrylate copolymer' means 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 silicone different from a film-forming or tacking silicone polymer, preferably a silicone resin or a silicone acrylate copolymer, preferably different from an MQ resin or acrylates/polytrimethylsiloxy- methacrylate copolymer. Preferably, the composition is completely free of silicone differenct from a film-forming or tacking silicone polymer, preferably a silicone resin or a silicone acrylate copolymer, preferably different from an MQ resin or acrylates/polytrimethylsiloxy-methacrylate copolymer. Silicone different from a filmforming or tacking silicone polymer, preferably a silicone resin or a silicone acrylate copolymer, preferably different from an MQ resin or an acrylates/polytrimethylsiloxy- methacrylate copolymer, means any silicone compound that is not a film-forming or tacking 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.

The term 'resin' means a compound with a three-dimensional structure. Thus, within the meaning 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 that 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 bonded to a single oxygen atom in the polymer comprising this unit.

The letter 'D' means a Difunctional unit R1 R2SiO2/2 wherein the silicon atom is bonded to two oxygen atoms.

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

In the previously defined units M, D, T, Ri, i.e. 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 SiO4/2 T etrafunctional unit wherein the silicon atom is bonded to four oxygen atoms themselves bonded 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'.

Siliconised resins of MQ type, are for example alkylsiloxysilicates of formula [(R1 )₃ SiOi/2]x (SiO4/2)_y (MQ units) wherein x and y are integers ranging from 50 to 80, and such that the grouping R1 represents a radical as defined previously, and preferably is an alkyl grouping 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 different from 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, suitable polymers include polymers comprising a hydrocarbon skeleton such as, for example, a skeleton selected from vinyl polymers, methacrylic polymers and/or acrylic polymers and at least one chain selected from siloxane pendant groups and polymers comprising a skeleton of siloxane groups and at least one hydrocarbon pendant 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. 'Substantially free of silicone' means 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. Preferably, the composition is completely free of silicone. According to this embodiment, silicone means any silicone compound, including filmforming or tacking silicone polymers. Preferably, the composition according to the invention comprises less than 20% by weight relative to the total weight of the pullulan composition, preferably less than 10% by weight, preferably less than 5% by weight.

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 3,000 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 (or chitosane) is very rarely found in nature. It is reported only in the exoskeletons of certain insects such as termite queens 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 bonded to each other by a p-type bond (1 .4).

The ideal chemical structure of chitosan is a chain of p-D-glucosamine monomers bonded by a glycoside bond (1^4).

'Chitosan' according to the invention means 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) bonded 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) 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 Le ntinula edodes (shiitake) and/or Agaricus bisporus. The fungus is preferably Aspergillus niger.

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

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

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

Preferably, the chitosan used in the invention is in powder form. In particular, it is marketed by Kitozyme under the name Kiosmetine or Kionutrime.

The 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. Natural resin

The composition according to the invention comprises at least one natural resin.

A resin is generally defined as a solid, highly viscous or liquid substance of plant or synthetic origin. Resins have several unique characteristics, such as:

- the ability to permanently cure, for example for synthetics under the influence of temperature and for natural ones under the influence of oxygen;

- their insolubility in water and above all their good tacky and adhesive properties.

ISO4618:2014(en) defines a resin as a 'generally amorphous macromolecular product with a consistency ranging from solid to liquid'.

Natural resins are almost exclusively of plant origin (fossil or harvested) and are secreted and exuded from plants for defence, protection and communication roles within their ecosystem. An exception is lacquer gum (or shellack) of animal origin, secreted by the insect Coccus lacca.

According to an embodiment, the natural resin is of plant or animal origin.

'Natural resin', and in particular 'plant resin', within the meaning of the invention, means any substance comprising a minimum content of terpenic compounds, i.e. at least 30% by weight of terpenic compounds over the total weight of the substance (or material) considered, as chemically defined below, said substance being derived directly or indirectly from secretion and exudate, mainly by plants (more rarely by animals), of a substance for defence, protection and communication roles with their ecosystem.

Advantageously, the natural resin according to the invention is not soluble in water at room temperature (unlike latex or gums, for example).

Natural resins are also considered to be natural adhesives that have the inherent ability to cure consistently and predictably by themselves without synthetic chemistry.

Preferably, the natural resin used in the composition according to the invention has an average molecular weight in number of less than or equal to 10,000 g/mol. The resin preferably has an average molecular weight in number of less than or equal to 10,000 g/mol, especially ranging from 250 to 10,000 g/mol preferably less than or equal to 5,000 g/mol, especially ranging from 250 to 5,000 g/mol, better, less than or equal to 2,000 g/mol especially ranging from 250 to 2,000 g/mol and even better less than or equal to 1 ,000 g/mol especially ranging from 250 to 1 ,000 g/mol. The mean molecular weights in number (Mn) are determined by liquid chromatography by gel permeation (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector).

Thermal properties

Advantageously, the resins according to the invention are characterised by having a softening point, which refers to the transition temperature from a pseudosolid state to a plastic state during heating.

Preferably, the resins of the invention have a softening point (or temperature) in the range of 20°C to 150°C, more preferably from 30°C to 100°C, even more preferably from 40°C to 90°C.

Softening point is the temperature at which a product reaches a certain degree of softening under standardised conditions. It refers to the transition temperature from a pseudo-solid state to a plastic state during heating. It is measurable by the bead-and-ring method (or TBA, bead-and-ring temperature) for resins according to ASTM E284.

According to their class, some of the resins according to the invention may also have a melting temperature, preferably less than 360°C, preferably less than 190°C, and even more preferably less than 90°C.

According to a preferred form of the invention, the resins do not have a melting temperature.

The melting point (or melting temperature) of a substance at a given pressure is the temperature at which the liquid and solid states of that substance can coexist at equilibrium.

Preferably, the resins of the invention have a glass transition temperature, the latter being preferably in the series from 0 to 200°C, more preferably from 10°C to 100°C, even more preferably from 20°C to 90°C and even more preferably from 30°C to 70°C.

The glass transition temperature (Tv: Tg for glass) of a material represents the temperature range through which the material changes from a rubbery state to a glassy, solid (rigid) state.

The thermal properties, in particular the Tf and Tg of the resins, can be measured by DSC (Differential Scanning Calorimetry), for example using a DSC 8000 device from Perkin Elmer, according to:

- Protocol 1: Determination of melting temperatures Tf and crystallisation Tc: Raw materials alone or solubilised/dispersed in solvents, stainless steel cups, scanning from 5°C to 90°C, scanning speed at 5°C.min-1 ;

- Protocol 2: Determination of the glass transition temperature T g : measurement in 2nd heating. Aluminium cups (40 pL) containing the raw materials are used, a temperature scan between -100°C and 150°C (with isotherms) is performed in order to observe the glass transition temperature. The temperature ramp applied is 10°C/min for glass transition temperatures (2 cycles).

Chemically, natural resins are complex mixtures of several classes of compounds whose presence and content define the class of the resin (oleoresin, balm, gum, etc.): essential oils, neutral and acidic constituents and polysaccharides (present exclusively in gums).

The characteristic components of the resins are the terpenic compounds they contain, preferably in a content of at least 30% by weight, on the resin weight.

'Terpenic compounds' means terpenes, hydrocarbons formed from isoprene of general formula (C5H8)n, and their numerous derivatives (alcohols, aldehydes, ketones, acids, etc.) comprising a terpene structure (Montpellier Academy. Resins: https://tice.ac-montpellier.fr/ABCDORGA/Famille/Terpenes.html).

Among the terpenic hydrocarbons, a distinction is made between: monoterpenes of crude formula C10H16 (n=2), sesquiterpenes of crude formula C15H24 (n=3), diterpenes (C20H32) (n=4), sesterterpenes (C25H40) (n=5), triterpenes (C30H48) (n=6), tetraterpenes (C40H64) (n=8) and other polyterpenes. Some have an acyclic structure; they include a number of double bonds corresponding to their raw formula: 3 for C10H16; 5 for C20H32; 7 for C30H48. Others have one or more cycles, i.e. a reduced number of double bonds; for example, for C10H16 one cycle and 2 double bonds or 2 cycles and one double bond.

Advantageously, the resins of the invention contain at least 30% of terpenic compounds, preferably at least 40% by weight of terpenic compounds, preferably at least 50% of terpenic compounds, and even more preferably at least 60% of terpenic compounds, or even more preferably at least 70% by weight of the total resin or resinous substance used as a starting material in the composition according to the invention.

Monoterpenic and sesquiterpenic compounds are mostly volatile compounds, for example essential oils. Polyterpene compounds derived from terpenes with n greater than or equal to 4 (such as derivatives of diterpenes and triterpenes) are resinous compounds of a rather solid nature.

According to a preferred embodiment of the invention, the resins comprise at least 10%, preferably at least 20% by weight, preferably at least 30% by weight, preferably at least 35% by weight, of polyterpenic compounds, i.e. deriving from terpenes with n greater than or equal to 4, over the total weight of the resin representing 100% by weight. Thus, resins with a solid fraction at room temperature (25°C) are preferred. Advantageously, said resins used according to the invention are not volatile. Advantageously, the polyterpenic compounds of the resins or resinous substances used in the composition of the invention are mostly (at more than 50% by weight over the total weight of polyterpenes) derived from diterpenes and/or triterpenes.

According to a preferred embodiment of the invention, the resins comprise less than 70% by weight of monoterpenic or sesquiterpenic compounds, i.e. deriving from terpenes with n less than 4, over the total weight of the resin representing 100%, preferably said resins comprise less than 60% by weight, preferably less than 50% by weight, preferably less than 30% by weight, preferably less than 15% by weight, of monoterpenic or sesquiterpenic compounds, deriving from terpenes with n less than 4, over the total weight of the resin representing 100%. Thus, it is preferable, for the compositions of the invention, to limit the use of the most volatile resins, because they are less effective in terms of cosmetic film retention.

Advantageously, the natural resin(s) according to the invention are selected from: a) acaroid resins, b) ambers, c) asphaltite and gilsonite, d) Peru balm, e) Tolu balm, f) Benjoin resins, g) Canada balm, h) copal resins (especially Kauri, Manila, West African Copals such as Congo, Angola or Cameroon Copals, East African Copals such as Zanzibar or Madagascar Copals, South American Copals such as from Brazil or Colombia), i) damars, j) elemites, k) incense, I) Galbanums, m) labdanums, n) putties, o) myrrh, p) Sandaraque, q) Lacquer gums, r) Styrax (Storax), s) Venice turpentine (Larch, Turpentine essence), t) Rosins, especially Rosin and rosinate and Tall oils, v) resins extracted from vegetable waxes; and mixtures of these resins.

Preferably, the natural resin(s) used according to the invention are selected from j), k), t) and v); it is understood that the resin(s) of the invention can be esterified, saltified, form adducts, be modified by phenols, and/or dimerised and/or further hydrogenated. j) Elemis

'Elemis' is the generic term for the group of recent natural resins derived from plants of the Burseraceae families (Canarium indicum). Each type is described according to its country of origin. According to a particular embodiment of the invention, the elemi resin used comes from the Philippines, especially elemi from Manila. To extract it, the trees are damaged and a pathological resin run-off appears, which solidifies over time. The elemis are yellowish to greenish, opaque, ointmentlike, slimy, sticky, and solidify into brownish resins sprinkled with crystals. Elemis are soluble in aromatic solvents, alcohols, esters and carbon sulphide; and less soluble in aliphatic solvents. Elemites have an acid number between 18 and 34, a saponification value between 25 and 60, and a softening point of approx. 80. Elemite balms contain up to 30% essential oils.

According to a preferred embodiment of the invention, the resin(s) of the invention are selected from the elemis, especially elemi derived from the family of Canarium Luzonicum in its pure form or in mixture with a latex, for example. Mention may be made of the elemi resin of Canarium Luzonicum marketed under the name RESINE ELEMI. k) Incense

Incense is found in the United Arab Emirates, Oman, Somalia, Ethiopia and East India. The incense resins are new and derived from Boswellia carterii tree incense. Incense resins from the Amazon are also found. The bark is intentionally damaged to obtain a milky extract that is recovered after drying. Preferably, the resin(s) of the invention are selected from incense, especially from the Amazon.

Incense resins are pale yellow, forming irregular rounded or globulous beads. They usually contain 20% to 40% by weight (approx. 33%) of boswellic acid (C32H52O4). Incenses have an acid number between 30% and 50% (indirect) and are moderately soluble in ethanol in alkaline media.

According to a particular embodiment of the invention, the resin(s) of the invention are selected from incense, especially Amazon incense resins marketed under the name Protium heptaphyllum resin, or PROTIUM RESIN, or WHITE BREU RESIN, and incense resins derived from the Sal tree, Shorea robusta.

Advantageously, the resin(s) are in mixture with one or more fatty substances as defined below according to the invention, preferably selected from volatile or nonvolatile oils. Mention may be made, for example, of Shorea robusta resin with sunflower seed oil (SHOREA ROBUSTA RESIN, HELIANTHUS ANNUUS (SUNFLOWER) SEED OIL, TOCOPHEROL: 50-75% by weight shorea robusta resin, 25-50% by weight sunflower seed oil) marketed under the name KAHLRESIN 6720, and the Shorea robusta resin with octyldodecanol (SHOREA ROBUSTA RESIN and OCTYLDODECANOL 50-70% by weight shorea robusta resin, 30-50% by weight octyldodecanol) marketed by KAHLRESIN 6720. t) Rosins Preferably, the natural resin(s) are selected from Rosins. Rosins are new resins, from renewable resources, and can be modified (e.g. esterified, hydrogenated, substituted).

Rosin gums are preferably purified, distilled, from the balm of various pine oils (up to 80 different species).

Their composition is determined by climate, soil composition, and other botanical and meteorological factors. For example, mention may be made of rosins from Pinus austriaca (black pine) Austria, Central America, Caribea (slash pine), United States, Caribbean, densiflora Japan, elliottii United States, halepensis (Aleppo pine) Greece, Portugal, Spain, langifolia India, maritima (seashore pine) France, Spain, Portugal, masoniana (Chinese red pine) China, mercusii Indonesia, Burma, Philippines, nigra (black pine) Austria, oocarpa Central America, Honduras, palustris (sampe pine), United States (longleaf pine), pseudostrobus Central America, Mexico, sylvestris (Scots pine) Germany, Poland, tonkinensis China, yunnanensis China.

The average composition is approx. 70 to 75% rosin and 20 to 25% turpentine.

Wood rosin [8050-09-7]

Rosin comes from US strains that have remained in the soil for at least 10 years to make resin-rich duramen available.

Pine strains contain between 10 and 30% by weight (approx. 19% rosin), between 1 and 10% by weight (preferably 4%) in turpentine oil, between 1 and 10% by weight (preferably 4%) of resins insoluble in petroleum ether, between 20 and 30% by weight (preferably 23%) of water and between 40 and 60% by weight (preferably 50%) of cellulose and lignin type.

According to a particular embodiment of the invention, the resin(s) are selected from the rosins.

Tall oil rosins (Rosin and rosinate) [8052-10-6]

Tall oil rosins often contain small amounts of higher fatty acids, especially with a carbon atom number of 6 or more carbon atoms. According to one embodiment, tall oil rosins are free of oxocarboxylic acid. They are particularly soluble in organic solvents.

The rosin resins of the invention in particular comprise rosin acids belonging to terpenes. The numbering of carbon atoms in rosin acid molecules is indicated using abietic acid as an example.

Rosin acids have a molecular chemical formula of C20 H30 02 and therefore belong to the family of diterpenes (four units of isoprene). A large number of isomers exist of tricyclic rosin acids which differ in the position of the two double bonds. Advantageously, said resin according to the invention is selected from: gum rosin obtained by incision on living trees, wood rosin that is extracted from tree stumps or pine wood, and tall oil rosin that is obtained from a by-product from paper production. Advantageously, said resin(s) include rosin acids; preferably mostly selected from abietic and pimaric type acids; and especially selected from: levopimaric acid, neoabietic acid, abietic acid, dehydroabietic acid, tetrahydroabietic acid, dihydroabietic acid, dextropimaric acid, isodextropimaric acid; or palustric acid; and mixtures thereof.

Rosin derivatives may in particular be derived from polymerisation, hydrogenation and/or esterification (e.g. with polyhydric alcohols such as ethylene glycol, glycerol, pentaerythritol) of rosin acids. Mention may be made, for example, of the rosin esters marketed under the reference FORAL 85, PENTALYN H and STAYBELITE ESTER 10 by the company HERCULES; SYLVATAC 95 and ZONESTER 85 by the company ARIZONA CHEMICAL or UNIREZ 3013 by the company UNION CAMP.

According to one embodiment of the invention, the resin(s) are selected from rosinates (alkaline agent salts of rosin acids, especially the salts of alkali metals such as sodium or potassium, alkaline-earth metals such as calcium, or metals such as zinc, or magnesium).

According to another preferred embodiment of the invention, the resin(s) are selected from rosin acid esters, especially rosin acid esters as defined previously and of (C1 -C6) alkanol, polyhydroxy(C1 -C6) alkane polyols such as glycerol, pentaerythritol, and mixtures thereof, more preferably selected from glyceryl rosinate marketed under the name RESIESTER GUM A 35, glyceryl rosinate in mixture with a hydrogenated vegetable oil and/or castor seed oil (GLYCERYL ROSINATE, RICINUS COMMUNIS SEED OIL, HYDROGENATED VEGETABLE OIL marketed under the name EFP BIOTEK) pentaerythrityl rosinate marketed under the name RESIESTER N 35 S and RESIESTER 80.

According to another embodiment of the invention, the resin(s) are selected from poly(carboxy)(C2-C6) alkane or poly(carboxy)(C2-C6) alkene adducts, especially from maleic acids with the rosin acids.

According to another embodiment of the invention, the resin(s) are selected from phenol-modified rosins. In particular those modified by (C1 -C4) alkylene phenols or diphenols, possibly substituted with one or more (C1 -C4) alkyl groups such as methyl or t-butyl, more particularly rosins modified by 4-tert-butylphenol and 4.4'- isopropylidenediphenol (bisphenol A).

According to another embodiment of the invention, the resin(s) are selected from dimerised rosins; especially those whose abietic acid is polymerised. Preferably, the rosins contain more than 50% dimeric acids and are thus called dimerised rosins. According to one embodiment, the rosins are polymerised and contain from 30% to 90% by weight of dimer acid (especially at least 40%, 60 or 80% of dimer acids).

According to a preferred embodiment of the invention, the resin(s) are selected from hydrogenated rosins. The double bonds, especially of acids such as abietic acid, are subject to oxidation, which can be removed by hydrogenation. It is understood that the resin(s) of the invention may be esterified, saltified, adduced, modified by phenols, and/or dimerised and further hydrogenated.

According to a preferred embodiment, the resin comprises at least one rosin acid ester selected from the group consisting of glyceryl rosinate, pentaerythrityl rosinate, silicone rosinate, diethylene glycol rosinate, dilinoleyl dimer hydrogenated rosinate, dipentaerythrityl hexahydroxystearate/hexastearate/hexarosinate, glyceryl dibehenate/hydrogenated rosinate, glyceryl diisostearate/hydrogenated rosinate, triglyceryl hydrogenated rosinate, glycol rosinate, hydrogenated methyl rosinate, methyl rosinate, hydrogenated pentaerythrityl rosinate, hydrogenated triethylene glycol rosinate; and mixtures thereof.

According to a particular embodiment, the resin(s) of the invention are selected from hydrogenated pentaerythrityl rosinate (PENTAERYTHRITYL HYDROGENATED ROSINATE), hydrogenated methyl rosinate (METHYL HYDROGENATED ROSINATE) marketed under the name SYMRISE BIO4326.

Furthermore, the resin(s) of the invention may be mixed with fatty substances, especially waxes or butters. Mention may be made of mixtures of glyceryl rosinate with one or more fatty substances especially selected from waxes or butters such as the mixture with shea butter or olive oil such as (GLYCERYL ROSINATE, RICINUS COMMUNIS SEED OIL, HYDROGENATED VEGETABLE OIL), BUTYROSPERMUM PARKII (SHEA BUTTER) GLYCERYL ROSINATE, OLEA EUROPAEA (OLIVE) OIL UNSAPONIFIABLES GLYCERYL ROSINATE, OLEA EUROPAEA(OLIVE) OIL UNSAPONIFIABLES marketed by SHEA BUTTER & GLYCERYL ROSINATE & OILS. v) resins extracted from vegetable waxes

Natural vegetable waxes as such are not considered as resins. Although they are one of the substances secreted/excreted by plants and naturally contain very low resins, they contain less than 30% by weight of terpenes over the total weight of wax. For example, Carnauba wax is naturally secreted by the leaves of a Copernica Cerifera palm to prevent the leaves from drying out. Candelilla wax is obtained from a shrub called Euphorbia Antisyphilitica originating in northern Mexico. The wax protects the plant from its medium and prevents excessive evaporation. For example, candelilla wax consists mainly of hydrocarbons (about 50%, chains of 29 to 33 carbon atoms), esters of higher molecular weight (20 to 29%), free acids (7 to 9%), and resins (12-14%, mainly triterpene esters).

Nonetheless, the definition of 'natural resins' within the meaning of the present invention also includes resins derived from vegetable waxes, when they have been previously concentrated, isolated or extracted from these waxes, provided that the resinous or terpenic ingredient in question contains the minimum content of terpenes (30% by weight over the total weight of the ingredient) required by the present invention. Mention may be made especially of the Candelilla resin (100% pure resin extracted from the corresponding wax), named INCI: EUPHORBIA CERIFERA (CANDELLILA) WAX EXTRACT, marketed under the name CANDELILLA RESIN E-1 by JAPAN NATURAL PRODUCTS. WO2013/147113 A1 also refers to Carnauba resin, a terpenic resin extracted from Carnauba wax, and having physical properties similar to those of conventionally described natural resins, such as a softening temperature and not a melting temperature which differentiates the resin from the wax.

Table 1 of the examples shows certain characteristic differences between waxes and resins according to the invention, with regard to their thermal properties.

Resins have a softening point and glass transition temperature, but no melting temperature.

The opposite is true for waxes which have a melting temperature.

Preferably, the resin(s) are selected from the resin(s) j), k), and t) as defined previously, and the resins v) extracted from waxes, especially candelilla, or carnauba; and mixtures thereof.

According to a preferred embodiment of the invention, the resin(s) are selected from the following references, indicated by their INCI name, used alone or in a mixture:

- resins extracted from vegetable waxes (type v resins), preferably EUPHORBIA CERIFERA (CANDELILLA) wax extracts, such as CANDELILLA RESIN E-1 marketed by JAPAN NATURAL PRODUCTS, BOTANICAL RESIN marketed by CERA RICA NODA, TOW AX- 1 F12 marketed by TOA KASEI;

- incense resins (type k resins), preferably PROTIUM HEPTAPHYLLUM RESIN, or PROTIUM RESIN, or WHITE BREU RESIN, which may be marketed, for example, by CITROLEO or Ephyla;

- incense resins from the Sal tree, SHOREA ROBUSTA RESIN. The resin(s) may be in mixture with one or more fatty substances, preferably selected from volatile or non-volatile oils. Mention may be made, for example, of Shorea robusta resin with sunflower seed oil (SHOREA ROBUSTA RESIN, HELIANTHUS ANNUUS (SUNFLOWER) SEED OIL, TOCOPHEROL: 50-75% by weight shorea robusta resin, 25-50% by weight sunflower seed oil) marketed under the name KAHLRESIN 6720, and the Shorea robusta resin with octyldodecanol (SHOREA ROBUSTA RESIN and OCTYLDODECANOL 50-70% by weight shorea robusta resin, 30-50% by weight octyldodecanol) marketed by KAHLRESIN 6720 (k-type resin); and

- rosins (type t resins), preferably rosin acid esters (resin) such as GLYCERYL ROSINATE marketed under the name RESIESTER GUM A 35, glyceryl rosinate in mixture with a hydrogenated vegetable oil and/or castor seed oil (GLYCERYL ROSINATE, RICINUS COMMUNIS SEED OIL, HYDROGENATED VEGETABLE OIL marketed under the name EFP BIOTEK), pentaerythrityl rosinate marketed under the name RESIESTER N 35 S and RESIESTER 80 or hydrogenated rosinate such as hydrogenated pentaerythrityl rosinate (PENTAERYTHRITYL HYDROGENATED ROSINATE) or hydrogenated methyl rosinate (METHYL HYDROGENATED ROSINATE) marketed under the name SYMRISE BIO4326.

According to a preferred embodiment of the invention, the resin(s) are selected from EUPHORBIA CERIFERA (CANDELILLA) wax extracted resins, incense resins such as PROTIUM HEPTAPHYLLUM RESIN, or PROTIUM RESIN, or WHITE BREU RESIN, incense resins derived from the Sal tree such as SHOREA ROBUSTA RESIN and GLYCERYL ROSINATE. According to a preferred embodiment of the invention, the resin(s) are selected from EUPHORBIA CERIFERA (CANDELILLA) wax extracted resins, incense resins such as PROTIUM HEPTAPHYLLUM RESIN, or PROTIUM RESIN, or WHITE BREU RESIN, and incense resins derived from the Sal tree such as SHOREA ROBUSTA RESIN.

According to a preferred embodiment of the invention, the resin(s) are selected from EUPHORBIA CERIFERA (CANDELLILA) WAX EXTRACT.

Advantageously, the resin(s) are present in the composition of the invention in a content in the range of 0.1 % to 40%, preferably 0.2% to 30%, preferably 0.5% to 250%, preferably from 0.5% to 25%, preferably 0.8% to 22%, preferably 1 to 20%, and more preferably 1 .2% to 15%, preferably 1 .5% to 10%, or even more preferably 2% to 8% by weight relative to the total weight of the composition. Advantageously, the composition of the present invention comprises less than 10%, preferably less than 5%, preferably less than 1 %, preferably less than 0.5%, preferably less than 0.1%, preferably is free, of synthetic resin.

Advantageously, the composition of the present invention comprises less than 10%, preferably less than 5%, preferably less than 1%, preferably less than 0.5%, preferably less than 0.1%, preferably is free, of silicone resin, i.e. synthetic resin, wherein the base structure is a chain including siloxane groups (silicon-oxygen-silicon bonds).

According to one embodiment, the composition according to the invention comprises a weight ratio between the chitosan and the natural resin (i.e. chitosan matural resin weight ratio) between 0.00025 and 150, preferably between 0.001 and 100. Preferably, it is between 0.01 and 50, preferably between 0.05 and 10, and even more preferably between 0.1 and 2.5.

Pigment dyeing 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.

'Pigments' means 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.

'Mineral pigment' means 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 oxides of zinc, iron (black, yellow or red) or chromium, 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 in 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 range up to 10 pm, preferably from 200 nm to 5 pm, and more preferably from 300 nm to 1 pm. According to a particular form of the invention, the pigments have a size characterised by a D[50] greater than 100 nm and 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 particle size meter of the MasterSizer 3000® type from Malvern, allowing the particle size distribution of all particles to be measured over a wide range ranging from 0.01 pm to 1 ,000 pm. The data is 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 especially 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.

In the context of the present invention, the mineral pigments are more particularly iron oxide and/or titanium dioxide. By way of example, mention may 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

Nacres may also be mentioned as mineral pigments usable in the invention.

'Nacres' should be understood to be coloured particles of any shape, iridescent or not, especially, produced by certain molluscs in their shells or synthesised and that have a colour effect by optical interference.

Nacres may be selected from pearlescent pigments, such as mica titanium coated with iron oxide, mica titanium coated with bismuth oxychloride, mica titanium coated with chromium oxide, mica titanium coated with an organic dye, as well as pearlescent pigments based on bismuth oxychloride. 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, by way of example of nacres, of natural mica coated with titanium oxide, iron oxide, natural pigment or bismuth oxychloride. Among the nacres available on the market, mention may be made of TIMICA®, FLAMENCO® and DUOCHROME® (mica-based) nacres marketed by the company ENGELHARD, TIMIRON® nacres marketed by the company MERCK, PRESTIGE® mica- based nacres marketed by the company ECKART and SUNSHINE® synthetic micabased nacres marketed by the company SUN CHEMICAL.

Nacres may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or copper colour or reflection. By way of illustration of the nacres that may be implemented in the context of the present invention, mention may be made, especially, 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-shade nacres, especially, marketed by the company ENGELHARD under the name Nu-Antique Copper 340XB® (Cloisonne) and Brown CL4509® (Chromalite); copper-reflecting nacres, especially, marketed by the company ENGELHARD under the name Copper 340A® (Timica); red-reflecting nacres, especially, marketed by the company MERCK under the name Sienna Fine® (17386) (Colorona); yellow-reflecting nacres, especially, marketed by the company ENGELHARD under the name Yellow (4502) ® (Chromalite); red-shade nacres with a gold-reflecting hue, especially, marketed by the company ENGELHARD under the name Sunstone G012® (Gemtone); pink nacres, especially, marketed by the company ENGELHARD under the name T an Opale G005® (Gemtone); black nacres with a gold reflection, 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), white nacres with a silver reflection, especially, marketed by the company MERCK under the name Xirona Silver® and rose-orange nacres in green-gold, 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 colour effect, i.e. unified and stabilised as produced by the classic colouring materials, such as, for example, monochromatic pigments. Within the meaning 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 reflection particles, goniochromatic dyeing agents, diffractive pigments, thermochromic agents, optical brightening agents, as well as, especially, interferent fibres. Of course, these different materials can be combined in such a way as to provide the simultaneous manifestation of two effects, or even a new effect in accordance with the invention.

The metal reflection 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 reflective 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 blends or alloys thereof (e.g., bronzes and brasses) are preferred metals.

Metal derivatives refer to compounds derived from metals, especially, 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 designations 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 the 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 Eckart.

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

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

Examples of symmetrical interferent 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; Fe2O3/SiO2/AI/SiO2/Fe2Os, and Fe2O3/SiO2/Fe2Os/SiO2/Fe2O3, pigments having these structures being marketed under the name SICOPEARL® by the company BASF; MoS2/Si02/mica-oxide/Si02/MoS2; Fe203/Si02/mica-oxide/Si02/Fe20s; TiO2/SiO2/TiO2 and TiO2/Al2Os/TiO2; SnO/TiO2/SiO2/TiO2/SnO; Fe2Os/SiO2/Fe2O3; 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 silica/titanium oxide/tin structure oxide pigments marketed under the name XIRONA MAGIC® by the company MERCK, silica/brown iron oxide structure pigments marketed under the name XIRONA INDIAN SUMMER® by the company MERCK, and silica/titanium oxide/mica/tin oxide structure pigments 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. According to the thickness and nature of the different layers, different effects are achieved. For example, the structure Fe2O3/SiO2/AI/ SiO2/Fe2Os changes from gold-green to grey-red for SiO2 layers from 320 to 350 nm; from red to gold for SiO2 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, by way of example, of pigments with a polymeric multilayer structure, those marketed by the company 3M under the name COLOUR GLITTER®.

As goniochromatic liquid crystal particles, for example, those sold by the company CHENIX, as well as that 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 below.

This type of pigment is particularly advantageous insofar as it can be considered in significant amounts together with a significant amount of water. What’s more, insofar as they are treated with a hydrophobic compound, they exhibit a predominant affinity for the oily gel phase which can then carry them.

Of course, the compositions according to the invention may simultaneously 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 treatment of the total or partial surface 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 the person 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 embodiment, the surface treatment consists of a coating of 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 at the surface of the solid particles by simply mixing under stirring the particles and said surfactant, possibly hot, prior to the incorporation of the particles into the other ingredients of the makeup or care composition.

The coating can for example be carrried out by chemically reacting a surfactant with the surface of the solid pigment particles and creating a covalent bond between the surfactant and the particles. This method is described especially in the patent US 4,578,266.

Chemical surface treatment may consist of diluting the surfactant in a volatile solvent, dispersing the pigments in this mixture, then slowly evaporating the volatile solvent, in such a way that the surfactant deposits on 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; fluorinated surfactants; fluorosilicone surfactants; metal soaps; N- acylated amino acids or salts thereof; lecithin and derivatives thereof; isopropyl triisostearyl titanate; isostearyl sebacetate; natural vegetable or animal waxes; synthetic polar waxes; fatty esters; phospholipids; and mixtures thereof.

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

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

Organopolysiloxane compound means a compound having a structure comprising an alternation of silicone atoms and oxygen atoms and comprising organic radicals bonded to silicon atoms.

Non-elastomeric organopolysiloxane

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

The alkoxy group may be represented by the radical R-O- such as 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 pigment surface.

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

Alkylsilanes and alkoxysilanes

Silanes with alkoxy functionality 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 the 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 skeleton as described in the patents US 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 the patents US 5,219,560 and EP 0 388 582, may be used.

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

[Chem 1 1] wherein the Gi radicals, identical or different, represent hydrogen or a Ci ._c 10 alkyl radical or even a phenyl radical; the G2 radicals, identical or different, represent a Ci 10 alkylene group; G3 represents a polymeric residue resulting from the (homo)polymerisation of at least one ethylenically unsaturated anionic monomer; G4 represents a polymeric residue resulting from the (homo)polymerisation 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 ranging from 10 to 350, it is an integer ranging from 0 to 50, provided that one of the parameters a and c is different from 0.

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

- the G1 radicals refer to 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)polymerisation 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)polymerisation of at least one monomer of the (Ci-C )alkyl (meth) acrylate type, preferably of the isobutyl or methyl (meth)acrylate type.

Examples of silicone polymers meeting the formula (II) are especially polydimethylsiloxanes (PDMS) on which, via a thiopropylene-type connecting link, 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 meeting the formula (II) are especially polydimethylsiloxanes (PDMS) on which polymer units of the isobutyl poly(meth)acrylate type are grafted, via a connecting link of the thiopropylene type.

Silicone resins

The silicone surfactant may be selected from silicone resins.

Fluorinated surfactant

The pigments may be surface treated totally or partially with a compound of a fluorinated nature.

Fluorinated surfactants may be selected from perfluoroalkyl phosphates, perfluoropolyethers, polytetrafluoropolyethylenes (PTFE), perfluoroalkanes, perfluoroalkyl silazanes, hexafluoropropylene polyoxides, polyorganosiloxanes comprising perfluoroalkyl perfluoropolyether groups.

Perfluoroalkyl radical means an alkyl radical wherein all hydrogen atoms have been replaced by fluorine atoms.

The perfluoropolyethers are described especially in the 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 perfluorocarbons (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 perfluorocycloalcanes and perfluoro(alkylcycloalcanes), 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 perfluoropolycycloalcanes, 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 perfluorinated derivatives such as tetracosafluoro- tetradecahydrophenhenhrene. Among the perfluoroarenes, mention may be made of perfluoroderivatives of naphthalene such as perfluoronaphthalene and perfluoromethyl-1 -naphthalene.

By way of example of trade 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 Kasei;

- the 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 surface treated totally or partially with a compound of a fluoro-silicone nature.

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

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

By way of example of trade 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 the aluminium salt of hydrogenated tallow glutamate. As metal soaps, mention may be made especially 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 the salts of aluminium, magnesium, calcium, zirconium, zinc, sodium, potassium.

Thus, according to a particularly preferred embodiment, an N-acylated amino acid derivative may especially be a glutamic acid derivative and/or one of its salts, 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.

By way of 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 sebaceate.

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

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

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

The waxes mentioned in the compounds cited above may be those generally used in the cosmetic field, as defined hereinafter. In particular, they may be hydrocarbon-based, siliconised and/or fluorinated, possibly including ester or hydroxyl functions. They may also be of natural or synthetic origin.

Polar wax means a wax containing chemical compounds including at least one polar group. The polar groups are well known to the person skilled in the art; they may be, for example, alcohol, ester, carboxylic acid groups. Polyethylene waxes, paraffin waxes, microcrystalline waxes, ozokerite and Fisher-T ropsch waxes are not polar waxes.

In particular, the polar waxes have an average solubility parameter ba of HANSEN 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’s solubility parameters.

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

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

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

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

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

By way of illustration and not limitation of these polar waxes, mention may be made especially 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, mountain wax.

According to a particular embodiment, the pigments may be coated with at least one compound selected from siliconised surfactants; fluorinated surfactants; N- acylated amino acids or salts thereof; isopropyl trisostearyl titanate; natural vegetable 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 one of its salts, in particular by a derivative of glutamic acid and/or one of its salts, 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 one of its salts, in particular by a glutamic acid derivative and/or one of its salts, especially a stearoyl glutamate, such as for example aluminium stearoyl glutamate.

By way of examples of pigments coated 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 the 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 uncoated.

These pigments may be mineral pigments especially as defined previously.

These pigments may also be organic pigments.

Organic pigment means any pigment that meets the definition of the Ullmann encyclopaedia in the chapter on organic pigment. The organic pigment may especially be selected from compounds such as nitroso, nitro, azo, xanthene, quinolein, anthraquinone, phthalocyanine, metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, dicetopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophtalone.

The organic pigment(s) may be selected for example from carmine, carbon black, aniline black, melanin, azo yellow, quinacridon, phthalocyanine blue, sorgho red, blue pigments coded in the Colour Index under the references Cl 42090, 69800, 69825, 73000, 74100, 74160, yellow pigments coded in the Colour Index under the references Cl 11680, 11710, 15985, 19140, 20040, 21 100, 21108, 47000, 47005, green pigments coded in the Colour Index under the references Cl 61565, 61570, 74260, orange pigments coded in the Colour Index under the references Cl 1 1725, 15510, 45370, 71105, red pigments coded in the Colour Index under the 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 polymerisation of indolic derivatives, phenolics as described in the patent FR 2 679 771 . These pigments may also be in the form of composite pigments as described in the patent EP1 184426. These composite pigments may especially be composed of particles including 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 lacquer. Lacquer means insolubilised dyes adsorbed on insoluble particles, the whole thus obtained remaining insoluble during use.

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

Among the organic dyes, mention may be made of cochineal carmine. Mention may also be made of products known under the following designations: 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).

By way of examples of lacquers, mention may be made of the product known under the name 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 biological polymers, carbohydrates, polysaccharides, polyacrylates or polyethylene glycol derivatives.

By way of examples of biological polymers, mention may be made of polymers based on carbohydrate-type monomers.

More particularly, mention may be made of biosaccharide gum; chitosans and derivatives thereof, such as butoxychitosan, chitosan carboxymethyl, chitosan carboxybutyl, chitosan gluconate, adipate chitosan, glycolate chitosan, lactate chitosan, etc.; chitins and derivatives thereof, such as carboxymethyl chitin, glycolate chitin; cellulose and derivatives thereof such as cellulose acetate; microcrystalline cellulose; starch phosphate; sodium hyaluronate; soluble proteoglycans; galacto-arabinanes; glycosaminoglycans; glycogen; sclerotium gum; dextran; starch and derivatives thereof; and mixtures thereof. By way of examples of carbohydrates, mention may be made especially of polyhydroxyaldehydes or polyhydroxyketones, of general formula: Cx(H₂O)_y wherein x and y may range from 1 to 1 ,000,000.

Carbohydrates may be monosaccharides, disaccharides or polysaccharides.

In particular, mention may be made by way of examples of carbohydrates, of amylodextrins, beta-glucans, cyclodextrins, modified corn starch, glycogen, hyaluronic acid, hydroxypropylcylodextrin, lactose, maltitol, guanosine, glyceryl starch, Triticum Vulgare starch, trehalose, sucrose and derivatives thereof, raffinose, sodium chondroidine sulphate.

Can still be used as surface treatment agents, C1-C20 alkylene glycols or C1-C20 alkylene glycol ethers, alone or used in combination with tri-Ci-C2o-alkylsilanes.

Mention may be made, by way of example, 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 SW pigments.

Silicones such as dimethicones having hydrophilic groups, also known as dimethicone copolyols or alkyl dimethicone 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 the pigments coated by at least one hydrophilic compound and/or the uncoated pigments is especially conditioned by the destination of the cosmetic composition under consideration and its adjustment is of course within the competence of the formulator of the composition.

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, especially by an N-acylated amino acid and/or one of its salts, in particular by a glutamic acid derivative and/or one of its salts, especially 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.

Alpha hydroxy acid means, 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 in the final composition in the form of a free acid and/or in the form of one of its associated salts (salts with an organic base or an alkali especially), in particular according to 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-hydroxyhexadecanoic 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 mode, 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 nonionic surfactant.

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

When present, the nonionic 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 demineralised water and/or floral water such as rose water, blueberry 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 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.

The composition may comprise from 0.1 % to 25% by weight of organic solvent miscible in water, 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 between the polyol(s), if present, and the chitosan (i.e. 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 includes an oil phase, it preferably contains at least one oil, especially a cosmetic oil. It may also contain other fatty substances.

'Oil' means a non-aqueous compound, liquid at 25°C and atmospheric pressure (1 .013.10⁵ Pa), not miscible with water.

'Non-miscible' means that the mixing of 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 1 ,000 rpm); the resulting mixture being left to 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, of:

- hydrocarbon oils of animal origin, such as perhydrosqualene; - hydrocarbon oils of plant origin, such as liquid triglycerides of fatty acids including 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;

- esters and synthetic ethers, especially of fatty acids, such as the oils of formulas R1 COOR2 and R1 OR2 wherein R1 represents the remainder of a fatty acid including from 8 to 29 carbon atoms, and R2 represents a hydrocarbon chain, whether or not branched, 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, whether volatile or not, and derivatives thereof, branched-chain hydrocarbon oils including 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, the PANALANE H-300 E marketed by the company AMOCO, the VISEAL 20000 marketed by the company SYNTEAL, the REWOPAL PIB 1000 marketed by the company WITCO, or the 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 fluorinated oils as 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 mode, the oil phase contains at least one non-volatile oil, the weight content of which is less than or equal to 40%, preferably less than or equal to 30%, preferably less than or equal to 20%, preferably less than or equal to 15%, preferably less than or equal to 10% and preferably less than or equal to 8%. Advantageously, the weight ratio between the non-volatile oil and the resin is between 0.01 and 10, preferably between 0.1 and 5, preferably between 0.2 and 3, preferably between 0.5 and 1.

'Non-volatile oil' means an oil remaining on the keratin materials at room temperature and atmospheric pressure for at least several hours and having especially 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.

For the purposes of the invention, 'volatile oil' means any oil likely to evaporate on contact with the skin, at room temperature and atmospheric pressure. The volatile oils of the invention are volatile cosmetic oils, liquids 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, silicon volatile oils, fluorinated 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 Isopars® or Permethyls®.

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.

Volatile alcohol means 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 organic solvent miscible in water, relative to the total weight of the composition, preferably 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 matter 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 in a conventional manner by the person 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

Ingredients:

[Table 1]

Example 1 : Preparations of compositions according to the invention and comparisons with comparative compositions

Compositions B and D according to the invention, comparative A and C and E, were prepared.

Compositions B and D according to the invention contain chitosan, candelilla resin, and pigments.

Comparative compositions A and C contain chitosan and pigments, but no candelilla resin.

Comparative composition E contains a resin but no chitosan.

Compositions A and B are inverse emulsions, while compositions C to E are direct emulsions.

- Protocol for spreading the compositions in a film

The products are spread on a spreading bench (Elcometer 4340 Applicator) allowing its speed and distance to be adjusted. The bench is equipped with a suction system connected to a pump so that the support on which the spreading is carried out does not move. Contrast maps with a black background and an unvarnished white background are used (1 byko-chart, uncoated N2A, code 2831 ). The spreading thickness is adjustable thanks to the square spreader placed on the support so that it is spread flush when the platform is switched on. Each slice of the spreader makes it possible to spread with a different thickness ranging from 25 pm to 200 pm. The selected thickness is 25 pm to approximate an in vivo film thickness. A 960 g weight is added above the spreader during spreading. The spreading speed is set to 1 in/sec, i.e. 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 objective

Colour measurement is carried out using 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) make it possible to characterise the coverage of a foundation by calculating the 'contrast ratio', (CR%) i.e. YFN/YFB x 100, where YFN and YFB are respectively the luminance values measured on the black background and the white background, this being higher when the foundation is covering.

- Dry, water and oil resistance test protocol

The water friction resistance 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 above the spreader during abrasion. The bench speed is set to 2.54 cm/s.

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

In order to evaluate the friction resistance, the 'Contrast Ratio' is measured respectively before friction (CR Dry Deposition, %) and after abrasion (CR Dry Deposition Fric, %). The loss [(CR Dry Deposition Fric-CR Dry Deposition]/CR Dry Deposition]*! 00, as a percentage, quantifies the loss of coverage and indicates the resistance of the film to friction: 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 reverse emulsion:

Compositions A and B are prepared as follows:

Preparation of the aqueous phase:

Under defloculant rayneri, slowly add 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 defloculating rayneri resin 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 2.

[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 An and NAI-BHP-10, NAI-YHP-10 and NAI-R-800HP-10 by Miyoshi Kasei)

The results show better water and dry resistance for composition B according to the invention compared to comparative composition A. These reverse emulsion tests show that the presence of Candelilla resin significantly improves the coverage hold under dry friction or in the presence of water of a formula already containing 2% of chitosan.

Results in direct emulsion:

Compositions C to E are prepared as follows:

In the final beaker, under defloculating rayneri, mix the surfactant and water, add the chitosan in the rain then the lactic acid and leave for 5 min at 300 rpm.

Mix the resin and isododecane, then add this mixture to the aqueous phase by regularly increasing the rotational speed from 300 to 1 ,000 rpm.

Add the dry pigments and then the alcohol.

The results are in Table 3.

[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 An and NAI-BHP-10, NAI-YHP-10 and NAI-R-800HP-10 by Miyoshi Kasei)

The results show better water resistance for the composition D according to the invention compared to the comparative composition C. The comparative composition E is phase shifted.

Claims

1 . 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 native chitosan composition having a molecular weight strictly greater than 3,000 Daltons, this amount being strictly less than 15% by weight, and b) at least one natural resin.

2. 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 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. Composition according to claim 1 or 2, wherein the native chitosan has a chitosan acetylation degree 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. 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. 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. Composition according to one of the preceding claims, wherein the natural resin comprises at least 30% by weight of the total weight of resin of terpenic compounds, preferably at least 40% by weight of terpenic compounds, preferably at least 50% of terpenic compounds, and even more preferably at least 60% of terpenic compounds, or even better at least 70% by weight on the total weight of resin.

7. The composition according to one of the preceding claims, wherein the natural resin is selected from the following resins, alone or in mixture: resins extracted from vegetable waxes, preferably EUPHORBIA CERIFERA (CANDELILLA) wax extracts; incense resins, preferably PROTIUM HEPTAPHYLLUM RESIN, or PROTIUM RESIN, or WHITE BREU RESIN; incense resins derived from the Sal tree, SHOREA ROBUSTA RESIN, alone or in mixture with one or more fatty substances preferably selected from volatile or non-volatile oils, preferably Shorea robusta resin with sunflower seed oil, and Shorea robusta resin with octyldodecanol; and rosins, preferably rosin acid esters such as glyceryl rosinate, glyceryl rosinate in mixture with a hydrogenated vegetable oil and/or castor seed oil, pentaerythrityl rosinate or hydrogenated rosinates such as hydrogenated pentaerythrityl rosinate or hydrogenated methyl rosinate.

8. Composition according to one of the preceding claims, wherein the natural resin may be present in the composition according to the invention in a content ranging from 0.1% to 40%, preferably from 0.2% to 30%, preferably from 0.5% to 25%, preferably from 0.8% to 22%, preferably from 1 to 20%, and more preferably from 1 .2% to 15%, preferably from 1 .5% to 10%, or even more preferably 2% to 8% by weight relative to the total weight of the composition.

9. Composition according to one of the preceding claims, wherein the weight ratio between the chitosan and the natural resin (i.e. chitosan: natural resin weight ratio) is between 0.00025 and 150, preferably between 0.001 and 100, preferably between 0.01 and 50, preferably between 0.05 and 10, and even more preferably between 0.1 and 2.5.

10. Composition according to one of the preceding claims, further comprising at least one compound selected from pigment colouring materials.

1 1. Composition according to claim 10, 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.

12. Composition according to claim 10, wherein the pigment colouring material is an organic pigment selected from nitroso, nitro, azo, xanthene, quinolein, anthraquinone, phthalocyanine, metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, dicetopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophtalone compounds.

13. Composition according to any one of claims 10 or 11 , wherein the pigment colouring material is selected from mineral pigments, preferably from titanium dioxide, iron oxides, zirconia or cerium oxides, zinc or chromium oxides, and mixtures thereof, preferably the pigment is selected from titanium dioxide, iron oxides, and mixtures thereof.

14. Composition according to one of claims 10 to 13, wherein the pigment colouring material is present 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.

15. 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.

16. Composition according to one of the preceding claims that is substantially free of silicone different from a film-forming or tacking silicone polymer; preferably 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 0.1% by weight of silicone different from a film-forming or tacking silicone polymer, preferably the composition is completely free of silicone different from a film-forming or tacking silicone polymer, preferably the composition according to the invention is substantially free of silicone, advantageously, the composition is completely free of silicone.

17. 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 between the polyol(s), if present, and the 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.

18. Composition according to one of the preceding claims, which comprises at least one alpha hydroxy acid, preferably 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-hydroxy-nonanoic acid, 2-hydroxydecanoic acid, 2- hydroxyundecanoic acid, 2-hydroxydodecanoic acid, 2-hydroxytetradecanoic acid, 2- hydroxyhexadecanoic acid, 2-hydroxyoctadecanoic acid, 2-hydroxytetracosanoic acid, 2-hydroxyeicosanoic acid; mandelic acid; phenylactic acid; gluconic acid; galacturonic acid; aleuritic acid; ribonic acid; tartaric acid; tartaric acid; malic acid; fumaric acid; salts thereof and mixtures thereof.

19. 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.

20. Composition according to one of the preceding claims, which also comprises at least one oil phase, preferably the oil phase contains at least one oil, especially a cosmetic oil; preferably the composition is a direct or reverse emulsion.

21. Composition according to any one of the preceding claims, further comprising at least one surfactant, preferably a nonionic 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. Composition according to any one of the preceding claims, comprising at least one non-volatile oil, the weight content of which is less than or equal to 40%, preferably less than or equal to 30%, preferably less than or equal to 20%, preferably less than or equal to 15%, preferably less than or equal to 10% and preferably less than or equal to 8% and/or the weight ratio of the non-volatile oil to the resin is between 0.01 and 10, preferably between 0.1 and 5, preferably between 0.2 and 3, preferably between 0.5 and 1 .

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

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