WO2025219369A1

WO2025219369A1 - Cosmetic composition comprising a natural resin, a cellulose ether, a particular polyester, volatile compounds and a silica-type filler, and process using same

Info

Publication number: WO2025219369A1
Application number: PCT/EP2025/060332
Authority: WO
Inventors: Nathalie GUILLIER; Lyubov LUKYANOVA; Claire PRUDHON; Sandrine FERNANDES
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2024-04-19
Filing date: 2025-04-15
Publication date: 2025-10-23
Anticipated expiration: 2026-10-19

Abstract

The present invention relates to a cosmetic composition, notably for making up human keratin materials, in particular the skin and/or the lips, comprising: - at least one natural resin, - at least one alkylcellulose, the alkyl group of which is a C₂-C₃ alkyl group, - at least one polyester which is the reaction product of the following components (i), (ii) and (iii): (i) at least one polyglycerol-3, (ii) at least one dimer acid, and (iii) at least one fatty monoacid containing from 8 to 30 carbon atoms; the reacted components (i), (ii) and (iii) being in a mole ratio of 1 mol of polyglycerol-3, 0.5 to 1 mol of dimer acid and from 0.1 to less than 2.0 mol of fatty monoacid, - at least one C₂-C₆ monoalcohol, - at least one volatile oil, - optionally at least one volatile polar hydrocarbon-based solvent, preferably compatible with the abovementioned polyester, - optionally at least one nonvolatile hydrocarbon-based oil, other than the abovementioned polyester, or nonvolatile silicone oil, and also mixtures thereof, - at least one silica-type filler. The invention also relates to a process for treating, notably for making up, human keratin materials, in which this composition is applied to said keratin materials.

Description

COSMETIC COMPOSITION COMPRISING A NATURAL RESIN, A CELLULOSE ETHER, A PARTICULAR POLYESTER, VOLATILE COMPOUNDS AND A SILICA-TYPE FILLER, AND PROCESS USING SAME

The present invention relates to a cosmetic composition, preferably a makeup composition, notably for the skin and/or the lips, preferably the lips, comprising at least one natural resin, at least one alkylcellulose, at least one polyester obtained by reacting a polyglycerol-3, a dimer acid and a C8-C30 monoacid, at least one monoalcohol, at least one volatile oil, optionally at least one volatile polar hydrocarbon-based solvent, preferably compatible with said polyester and at least one silica-type filler, and also to a process using same.

Many cosmetic compositions, in particular makeup compositions, containing, inter alia, colorants such as foundations, correctors, lipsticks or lip glosses, have been developed to improve the wear property of the deposit and the transfer resistance properties. Specifically, a poor wear property over time can be reflected in particular by a poor wear property over time of the color, in particular a loss of intensity of the color of the deposit. This consequently obliges the user to reapply the makeup more often than desired, which may be considered as lost time.

Improving the wear property of compositions is obtained by means of compositions which form a film after application. Such compositions generally contain volatile solvents which evaporate on contact with the skin or the lips, leaving behind a layer comprising waxes and/or film-forming polymers, pigments and fillers. Film-forming polymers are synthetic polymers, usually silicone or acrylic polymers. Thus, mention may be made of the use of silicone resins, for instance trimethyl siloxysilicate (INCI name) or polypropylsilsesquioxane (INCI name) resins, or resins which comprise silicone polymers such as silicone acrylate dendrimer copolymers (acrylates/polytrimethyl siloxymethacrylate copolymer - INCI name). Acrylic polymers such as acrylic acid/isobutyl acrylate/isobornyl acrylate copolymers are also used. However, these compositions are often considered less comfortable, or even uncomfortable, from a sensory point of view for consumers.

Moreover, for a few years now, consumers have been becoming more demanding regarding the composition of their cosmetic products and have in particular sought to minimize the content of silicone compounds, or even to dispense with them. On the other hand, they have been seeking to use products with a higher content of natural ingredients or ingredients of natural origin, ingredients whose environmental impact is minimized and/or ingredients that are compatible with a wide range of packaging.

Thus, the formulation of environmentally-friendly cosmetic products, i.e. products whose design and development take account of environmental issues, is becoming a major preoccupation for contributing toward meeting the global challenges. It is therefore essential to propose more sustainable compositions and/or preparation processes and/or ingredients, thus enabling these environmental challenges to be met.

In this context, it is important to develop novel cosmetic compositions with a better carbon footprint, notably by promoting the use of starting materials that are renewable and/or that have a good naturalness index and/or that are of natural origin and more particularly of plant origin, while reducing the use of compounds of petrochemical origin.

The difficulty remains, however, in reconciling these latest trends with the fact that consumers do not, however, want to give up the very high performance qualities to which they have become accustomed regarding the products they already use, which notably comprise film-forming silicone polymers.

The search is thus still on for makeup compositions which perform well, are comfortable and also have a very good wear property, without it being necessary to use the film-forming polymers conventionally used, notably silicone polymers, and which are more environmentally friendly, for example by using a larger number of natural compounds or compounds of natural origin.

These and other problems are solved by the present invention, one subject of which is a cosmetic composition, preferably for making up human keratin materials, in particular the skin and/or the lips, preferably the lips, comprising, in a physiologically acceptable medium:

- at least one natural resin,

- at least one alkylcellulose, the alkyl group of which is a C₂-C₃ alkyl group, preferably ethylcellulose,

- at least one polyester which is the reaction product of the following components (i), (ii) and (iii):

(i) at least one polyglycerol-3,

(ii) at least one dimer acid, and

(iii) at least one fatty monoacid containing from 8 to 30 carbon atoms;

the reacted components (i), (ii) and (iii) being in a mole ratio of 1 mol of polyglycerol-3, 0.5 to 1 mol of dimer acid and from 0.1 to less than 2.0 mol of fatty monoacids,

- at least one C₂-C₆, more particularly C₂-C₄ monoalcohol, preferably ethanol,

- at least one volatile oil,

- optionally at least one volatile polar hydrocarbon-based solvent, preferably compatible with the abovementioned polyester,

- optionally at least one nonvolatile hydrocarbon-based oil, other than the abovementioned polyester, or nonvolatile silicone oil, and also mixtures thereof,

- at least one silica-type filler.

The present invention also relates to a process for treating human keratin materials, preferably a makeup process, in which the abovementioned cosmetic composition is applied to human keratin materials, in particular the skin and/or the lips, preferably the lips.

The composition according to the invention has the advantage of being stable over time and of being easy to apply, without dewetting on application or on blotting. Moreover, the deposit obtained is precise, uniform, not runny and sparingly or not at all tacky. The deposit does not migrate into the wrinkles and fine lines, in particular around the lips.

The resulting deposit has a very good wear property. It is also comfortable, without leaving a feeling of dryness or tautness.

The composition according to the invention is advantageously in the form of a liquid composition at room temperature (20°C) and at atmospheric pressure (1.013 x 10⁵ Pa).

The term “liquid composition” means any composition which has one or more of the following features:

i) it flows under its own weight at room temperature (20°C) and at atmospheric pressure (1.013 x 10⁵ Pa);

ii) it is not solid at room temperature and at atmospheric pressure and its viscosity or consistency characterized by its hardness may be measured;

iii) it does not have any particular shape such as that which can be obtained by hot casting in a mold or container of a given shape.

Such compositions may thus be found notably in fluid, creamy, pasty or gel form.

Protocol for measuring the viscosity

The viscosity measurement is generally performed at 25°C, using a Rheomat RM180 viscometer equipped with a No. 2, No. 3 or No. 4 spindle, the measurement being performed after 10 minutes of rotation of the spindle in the composition (after which time stabilization of the viscosity and of the spin speed of the spindle are observed), at a speed of 200 rpm.

According to one embodiment, the composition according to the invention may have, at 25°C, a viscosity of between 0.1 and 25 Pa.s, preferably between 0.2 and 20 Pa.s. Preferably, the viscosity at 25°C of a composition according to the invention may be between 0.2 and 15 Pa.s.

POLYGLYCEROL-3/DIMER ACID/FATTY MONOACID POLYESTER

The composition in accordance with the invention comprises at least one polyester which is the reaction product of the following components (i), (ii) and (iii):

(i) at least one polyglycerol-3;

(ii) at least one dimer acid; and

(iii) at least one fatty monoacid containing from 8 to 30 carbon atoms;

the reacted components (i), (ii) and (iii) being in a mole ratio of 1 mol of polyglycerol-3, 0.5 to 1 mol of dimer acid and from 0.1 to less than 2.0 mol of fatty acids.

The term “polyester” is understood to mean any polymer obtained by a condensation reaction of polycarboxylic acids with alcohols or glycols. Its macromolecular backbone contains the repetition of its ester function. The ester function denotes a characteristic group formed of an atom bonded simultaneously to an oxygen atom via a double bond and to an alkoxy group. When the bonded atom is a carbon atom, it is called a carboxylic ester, the general formula of which is R-COO-R’.

The term “polyglycerol-3” means triglycerol alone or a mixture of polyglycerols comprising at least triglycerol, and preferably triglycerol is predominant in said mixture.

The polyesters of the invention and the synthesis thereof are described in patent applications US 2021/0259945, US 2021/0259946 and US 2021/0259930 in the name of the company Nouryon.

According to a preferred embodiment, the polyester is a substantially or totally nonsequential reaction product.

The term “substantially nonsequential reaction product” means the product obtained by a substantially nonsequential reaction of the reactive components (i)-(iii).

The term “totally nonsequential reaction of the reactive components (i)-(iii)” means that the total content of each of the reagents (i)-(iii) to be made to react is added to the reaction vessel before starting the reaction.

In one embodiment of the present invention, the total content of each of the reagents (i)-(iii) to be made to react is added to the reaction vessel before starting the reaction, that is to say that the reaction is totally non-sequential, and the polymer is a product of totally non-sequential reaction of the components (i)-(iii). In other embodiments, 70-100%, or 75-100%, or 80-100%, or 85-100%, or 90-100%, or 95-100%, or 97-100% of each of the reagents (i)-(iii) are added to the reaction vessel before starting the reaction.

In one embodiment, the polyester is prepared by a one-step process which involves the introduction of all the reagents into a reaction vessel and the subsequent induction of an entirely random addition of the dimer acid and of isostearic acid to the polyglycerol-3.

POLYGLYCEROL-3

Triglycerol has the formula H-[-OGly]₃-OH in which Gly denotes a glycerol residue after removal of two hydroxyl groups.

A polyglycerol-3 according to the invention in the form of a mixture of polyglycerols containing at least triglycerol comprises polyglycerols which can be any product of oligocondensation of glycerol. Said polyglycerols preferably correspond to formula (I): H[-O-Gly]n-OH, in which each Gly is independently the residue of a glycerol molecule after removal of two hydroxyl groups; and n is a mean from 2 to 10.

Generally, the majority of the Gly groups are of the formula: -CH₂-CHOH-CH₂-, although residues comprising etherification at secondary or even tertiary hydroxyl groups are regarded as being within the scope of “Gly” and, consequently, may also be present.

Examples of polyglycerol-3 in the form of a mixture comprise diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, heptaglycerol, octaglycerol, nonaglycerol, decaglycerol and mixtures of these. In particular, preferential polyglycerols are those of formula (I) in which n in particular has a value from 2 to 7, more particularly from 2 to 5 and notably 2, 3 or 4, or mixtures of polyglycerols in these ranges.

Particularly appropriate examples of polyglycerol-3 comprise a mixture of polyglycerols having the following distribution, in which all the weight percentages are based relative to the total weight of the polyglycerol-3 in the form of a mixture:

- glycerol: 0% to 30% by weight, preferably 0% to 20% by weight, most preferably 0% to 15% by weight;

- diglycerol: 10% to 40% by weight, preferably 15% to 35% by weight, most preferably 20% to 32% by weight;

- triglycerol: 10% to 65% by weight, preferably 15% to 60% by weight, most preferably 18% to 55% by weight;

- tetraglycerol: 2% to 25% by weight, preferably 5% to 20% by weight, most preferably 8% to 20% by weight;

- pentaglycerol: 0% to 15% by weight, preferably 0% to 10% by weight, most preferably 0% to 5% by weight;

- hexaglycerol: 0% to 15% by weight, preferably 0% to 10% by weight, most preferably 0% to 5% by weight;

- heptaglycerol: 0% to 10% by weight, preferably 0% to 5% by weight, most preferably 0% to 3% by weight;

- octaglycerol: 0% to 10% by weight, preferably 0% to 5% by weight, most preferably 0% to 3% by weight;

- nonaglycerol: 0% to 5% by weight, preferably 0% to 3% by weight, most preferably 0% to 2% by weight;

- decaglycerol: 0% to 5% by weight, preferably 0% to 3% by weight, most preferably 0% to 2% by weight.

In one embodiment, a polyglycerol-3 in the form of a mixture comprises the following distribution of polyglycerols:
Glycerol: 0% to 30% by weight;
Diglycerol: 15% to 40% by weight;
Triglycerol: 10% to 55% by weight;
Tetraglycerol: 2% to 25% by weight;
Pentaglycerol and higher components: 0 to 15% by weight relative to the total weight of the polyglycerol-3 in the form of a mixture.

In one embodiment, a polyglycerol-3 in the form of a mixture is composed of at least 40% by weight, or of at least 45% by weight, or of at least 50% by weight, of a combination of diglycerol and of triglycerol, relative to the total weight of the polyglycerol-3 in the form of a mixture.

In one embodiment, a polyglycerol-3 in the form of a mixture is composed of at least 20% by weight, or of at least 25% by weight, of diglycerol; at least 15% by weight, or at least 18% by weight, of triglycerol; at least 10% by weight, or at least 12% by weight, of tetraglycerol; in which all the percentages by weight are relative to the total weight of the polyglycerol-3 in the form of a mixture.

A particularly preferred polyglycerol-3 in the form of a mixture comprises at least 25% by weight of diglycerol, at least 45% by weight of triglycerol and at least 10% by weight of tetraglycerol, relative to the total weight of the polyglycerol-3 in the form of a mixture.

The analysis of such a polyglycerol-3 composition may be performed so as to determine its median or “mean” polyglycerol number. The above examples of polyglycerols with narrow and broad distributions can also be denoted as polyglycerol-3 because it is a matter of the integer closest to the mean and/or median.

DIMER ACID

The dimer acid may be any dicarboxylic acid containing at least 4 carbon atoms. They may be linear or branched, for instance the dimers prepared from malonic acid, succinic acid, fumaric acid, dimethylglutaric acid or trimethyladipic acid, and from anhydrides thereof.

Dimer fatty acids are particularly useful. As is known, these are mixtures of acyclic and cyclic dicarboxylic acids which are obtained by a catalyzed dimerization reaction of unsaturated fatty acids containing from 12 to 22 carbon atoms.

For the preparation and use of dimer acids and their physical and chemical properties, reference will be made to the publication “The Dimer Acids: The Chemical and Physical Properties, Reactions and Applications”, Ed. E. C. Leonard; Humko Sheffield Chemical, 1975, Memphis, Tenn.

The dicarboxylic acids may also contain, to a lesser extent, tri- and polyfunctional carboxylic acids. The functionality of the mixture must not exceed a mean molar value of 2.4.

The preferred dimer acids are typically derived from triglycerides rich in C18 ester groups, which can be hydrolyzed to produce unsaturated C18 fatty monoacids. The starting materials may be derived from tallow oil and rapeseed oil, but other natural sources, such as flax seeds, soybean, pumpkin and walnut, may be used. The target monoacids used in the reaction are rich in oleic and linoleic acid forms described in the list of fatty acids contained below. Dimerization results mainly in the dimerization of unsaturated fatty acids, but trimers are also formed. After reaction, the product may be stored in the form of a mixture of reaction products or it may be further distilled or otherwise separated into molecular weight fractions. In one embodiment, the dimerization reaction produces a predominance (at least 60% by weight, more preferably at least 75% by weight) of dimer acid (C36 diacid) but also produces C54 trimer acids (less than 30% by weight, more preferably less than 25% by weight).

In one case, a standard dimer acid commercially available from Croda, Pripol 1025®, which contains 72% by weight of dimer acid and 19% by weight of trimer acid, is used.

In another case, a standard hydrogenated dimer acid from Oleon, Radiacid 0960®, which contains 87% by weight of dimer acid and 10% by weight of trimer acid, is used. In both cases, the polymer as described is characterized by a higher molecular weight, a more hydrophobic nature and a higher viscosity than those which can be provided by pure diacids of lower molecular weight. The presence of trimer acid further improves the molecular weight and the performance qualities of these polymers.

In one embodiment, the copolymer of the present invention is prepared from at least one hydrogenated dimer acid.

In another embodiment, the polymer is prepared from a hydrogenated dimer acid comprising hydrogenated dimerized C18 fatty acids, which hydrogenated dimer acid is obtained by dimerization of unsaturated C18 fatty acids and subsequent hydrogenation.

In one embodiment, the hydrogenated dimer acid has a content of trimer acid ranging from about 5% to 25% by weight, based on the total weight of hydrogenated dimer acid.

In another embodiment, the hydrogenated dimer acid contains a predominance (at least 60% by weight, more preferentially at least 75% by weight, but not more than 95% by weight, or better still not more than 90% by weight, or even better still not more than 85% by weight) of hydrogenated dimer acid (C36 diacid) and also contains hydrogenated C54 trimer acids (less than 30% by weight, more preferably less than 25% by weight, but more than 5% by weight, more preferably more than 10% by weight).

FATTY MONOACID

The C8-C30 fatty monoacids may include natural or refined fatty acids, such as hydrolyzed rapeseed oil, sunflower oils, and the like, but these contain both lower and higher MW chains. Useful fatty monoacids may be linear, branched, saturated, unsaturated and aromatic materials with an acidity provided by carboxylic acid fractions.

Acids that are suitable for use in the invention comprise caprylic acid (C8), pelargonic acid (C9), capric acid (C10), undecylic acid (C11), lauric acid (C12), tridecylic acid (C13), myristic acid (C14), pentadecylic acid (C15), palmitic acid (C16), margaric acid (C17), stearic acid (C18), isostearic acid (C18), nonadecylic acid (C19), arachidic acid (C20), behenic acid (C22) and lignoceric acid (C24).

The comparison of stearic acid and isostearic acid shows that the branching leads to an elevated melting point and results in a low viscosity at ambient temperature for isostearic acid, compared to a solid material for stearic acid. This lower viscosity can be useful in the handling of starting materials and also to make it possible for the esters manufactured with this acid to retain their liquid properties. Branched-chain fatty acids often contain a single methyl branch along the linear carbon chain and are produced in nature by microbial action. Isostearic acid is available as a reaction byproduct in the creation of the dimer acid described above.

Another way to obtain a liquid product consists in using unsaturated, linear and branched, fatty monoacids. These unsaturated acids can include palmitoleic acid (C16:1), vaccenic acid (C18:1), oleic acid (C18:1), elaidic acid (C18:1), linoleic acid (C18:2), linolelaidic acid (C18:2), α-linolenic acid (C18:3), γ-linolenic acid (C18:3), stearidonic acid (C18:4), paullinic acid (C20:1), gondoic acid (C20:1), dihomo-γ-linolenic acid (C20:3), mead acid (C20:3), arachidonic acid (C20:4), eicosapentaenoic acid (C20:5), erucic acid (C22:1), docosatetraenoic acid (C22:4), cervonic acid (C22:6) and nervonic acid (C24:1). As is well known to a person skilled in the art, the designation means that the length of the carbon chain is X carbon atoms and that there are Y double bonds in the chain.

In one embodiment, isostearic acid will be preferred.

In a particularly preferred embodiment, the polyester of the invention is a product of substantially or totally non-sequential reaction of the following components:

(i) at least one polyglycerol-3 in the form of a mixture comprising at least 25% by weight of diglycerol, at least 45% by weight of triglycerol and at least 10% by weight of tetraglycerol, relative to the total weight of polyglycerol-3 in the form of a mixture;

(ii) at least one hydrogenated dimer acid containing at least 60% by weight of hydrogenated C36 diacid and from 5% to 25% by weight of hydrogenated C54 triacid, in each case relative to the total weight of hydrogenated acid; and

iii) isostearic acid.

In one embodiment, it is preferable to have a total degree of esterification of the available polyglycerol hydroxyl fragments (total esterification) of from 24% to 74% and a degree of esterification of the available polyglycerol hydroxyl fragments by a dimer acid alone (esterification with a dimer acid) of from 20% to 40%. Even more importantly, the degree of esterification by end-cap units (esterification with a monoacid) is also defined in this description and it is important to maintain the esterification with a monoacid from 4% to 40%.

It is preferable to have a total esterification of 28% to 57% with an esterification with a dimer acid of 20% to 30% and an esterification with a monoacid of between 8% and 27%.

It is even more preferable to have a total esterification of 33% to 48% with an esterification with a dimer acid of 20% to 28% and an esterification with a monoacid of between 13% and 20%.

It is even more preferable to have a total esterification of 24% to 74% with an esterification with a hydrogenated dimer acid of 20% to 40% and an esterification with a monoacid of between 4% and 40%.

It is even more preferable to have a total esterification of 28% to 57% with an esterification with a hydrogenated dimer acid of 20% to 30% and an esterification with a monoacid of between 8% and 27%.

It is also even more preferable to have a total esterification of about 40% with an esterification with a hydrogenated dimer acid of about 20% and an esterification with a monoacid of about 20%.

It is also even more preferable to have a total esterification of about 40% with an esterification with a hydrogenated dimer acid of about 27% and an esterification with a monoacid of about 13%.

In one embodiment, the reacted components are in a mole ratio of 1 mol of polyglycerol-3, 0.5 to 1 mol of dimer acid and 0.2 to 1.7 mol of fatty acid.

In another embodiment, the reacted components are in a mole ratio of 1 mol of polyglycerol-3, 0.5 to 0.75 mol of dimer acid and 0.4 to 1.35 mol of isostearic acid.

In another embodiment, the reacted components are in a mole ratio of 1 mol of polyglycerol-3, 0.5 to 0.7 mol of dimer acid and 0.65 to 1 mol of isostearic acid.

In another embodiment, the reacted components are in a mole ratio of 1 mol of polyglycerol-3, 0.5 to 1 mol of hydrogenated dimer acid and 0.2 to 1.7 mol of isostearic acid.

In another embodiment, the reacted components are in a mole ratio of 1 mol of polyglycerol-3, 0.5 to 0.75 mol of hydrogenated dimer acid and 0.4 to 1.35 mol of isostearic acid.

In another embodiment, the reacted components are in a mole ratio of 1 mol of polyglycerol-3, 0.5 to 0.7 mol of hydrogenated dimer acid and 0.65 to 1 mol of isostearic acid.

In another embodiment, the reacted components are in a mole ratio of 1 mol of polyglycerol-3, 0.67 mol of hydrogenated C36 dimer acid and 0.67 mol of isostearic acid.

In a particularly preferred embodiment, the reacted components are in a mole ratio of 1 mol of polyglycerol-3, 0.5 mol of hydrogenated C36 dimer acid and 1 mol of isostearic acid.

By adjusting the mole ratio of the termination of the fatty acids and by balancing the amount of polyglycerol-3 and of dimer acid, it is also possible to control the degree of dimer acid-polyglycerol extension and termination so that crosslinking, for example, via the trimer acid, results in much higher viscosities.

The target viscosity of the pure polymer must be > 50 000 mPa.s and less than 5 000 000 mPa.s at 25°C.

In a preferred embodiment, the target viscosity is > 75 000 mPa.s and

< 2 500 000 mPa.s at 25°C.

In another preferred embodiment, the target viscosity is > 100 000 mPa.s and < 2 000 000 mPa.s at 25°C.

In a most preferred embodiment, the target viscosity is > 1 000 000 mPa.s and < 2 000 000 mPa.s at 25°C.

The viscosity is measured using an MCR3O2® rheometer from Anton Paar Inc. Rough or smooth twin flat plates 50 mm in diameter were used, covered with a polymer sample, adjusted to a gap of 0.5 to 1 mm, and temperature and shear rate scans were performed. The polyesters of the invention have Newtonian behavior and thus have a constant viscosity over a wide range of shear rates. In addition, the polymers of the present description demonstrated a reduced viscosity with temperature. Thus, the viscosity measurements are reported at a precisely controlled temperature and generally in the form of a shear rate of 1. The values are reported in mPa.s.

The polyesters of the invention are characterized by weight-average molecular masses > 2500 Da and < 1 000 000 Da, measured by GPC using linear polystyrene standards.

The GPC column used for these tests consisted of: Phenolgel, 300 x 4.6 mm; a continuous tetrahydrofuran (THF) phase was used and injected at 0.35 ml/min, column oven maintained at 40°C; a 50 µl injection and a Wyatt Ri refractive index detector. The calibration standards used were strictly linear polystyrene intended to be monodispersed. The narrow range polystyrene GPC calibration standards were prepared as a mobile phase and had maximum molecular weights of 1 290 000 Da, 560 000 Da, 65 500 Da, 28 500 Da, 10 100 Da, 1680 Da, 580 Da and 208 Da. Using standard methodologies, the weight- and number-average molecular mass is automatically calculated with standard GPC software.

In a preferred embodiment, the polyesters described have a weight-average molecular weight > 4000 Da and < 250 000 Da, measured by GPC using linear polystyrene standards. In a most preferred embodiment, the polymers described have a weight-average molecular weight > 5000 Da and < 150 000 Da, measured by GPC using linear polystyrene standards.

In yet another embodiment, the polyester of the invention has a combination of weight-average molecular mass > 5000 Da and < 150 000 Da, measured by GPC using linear polystyrene standards, and of viscosity at 25°C > 100 000 mPa.s and < 2 000 000 mPa.s.

In a preferred embodiment, the polyester of the invention is a product of substantially or totally non-sequential reaction of the following components:

(i) at least one polyglycerol-3 comprising at least 25% by weight of diglycerol, at least 45% by weight of triglycerol and at least 10% by weight of tetraglycerol, in each case relative to the total weight of polyglycerol-3 in the form of a mixture;

(iii) isostearic acid; in which the polymer has a combination of weight-average molecular mass > 5000 Da and < 15 000 Da, measured with GPC using linear polystyrene standards, and of viscosity of the pure polymer > 100 000 mPa.s and < 2 000 000 mPa.s at 25°C; and in which the copolymer is also characterized by a total esterification of about 40%, an esterification with a hydrogenated dimer acid of about 27% and an esterification with a monoacid of about 13%.

In practice, given that the raw ingredients contain a range of polyglycerol units and a range of dimer and trimer acid contents, the above numbers can be adjusted using the actual (and not theoretical) hydroxyl fractions and carboxylic acid fractions, as are determined by methods such as mass spectrometry, NMR and liquid chromatography. The above esterification ranges are based on the ideal structure of the polyglycerol-3 and of the C36 dimer acid. The actual ranges may thus be slightly different from the values indicated above and may be calculated on the basis of these analytical values.

It is more practical to define the extent of the polymerization by the final acid number. The initial acid numbers, in the light of the distribution of the polyglycerol, monoacid and polyacid fractions present, can be reliably calculated using the actual acid number determined by the raw ingredient used.

For example, the initial total acid number (“AV”, which is commonly defined in mg of KOH/g of total reagent), is 135 AV. This comprises 68 AV for the dimer acid and 67 AV for the isostearic acid for a preferred embodiment containing 1 mol of polyglycerol-3, 0.5 mol of hydrogenated C36 dimer acid and 1 mol of isostearic acid. All the preferred ratio embodiments described above have a corresponding initial AV which can be calculated. When, during the polymerization reaction, the AV units are reduced, this ratio gives the percentage of conversion of the reaction from the total initial reactive acid fractions to the final residual acid fractions.

Thus, the degree of completion of the reaction is defined by 1 - final AV / initial AV.

In one embodiment, the polyesters of the invention have final acid numbers of from 0.1 to < 25 mg of KOH/g of polymer.

In a preferred embodiment, the polyesters of the invention have final acid numbers of from 0.1 to < 10 mg of KOH/g of polymer.

In a most preferred embodiment, the polyesters of the invention have final acid numbers of from 0.1 to < 5 mg of KOH/g of polymer.

As the completion rate of the reaction is defined by the equation 1- final AV/initial AV, the completion rate of the reaction of such mixtures to give final polymer is > 80%.

In a preferred embodiment, the degree of completion of the reaction of such mixtures to give final polymer is > 90%.

In a most preferred embodiment, the degree of completion of the reaction of such mixtures to give final polymer is > 95%.

In a preferred embodiment, the polyester of the invention is a product of reaction of a polyglycerol-3, of a hydrogenated C36 dimer acid and of isostearic acid in a mole ratio of 1/0.5/1, as described in Example 10 (copolymer) of US 2021/0259945.

According to a preferred variant of the invention, the composition comprises at least one oily solution comprising:
a) at least one polyester which is the product of reaction of the following components (i), (ii) and (iii):
(i) at least one polyglycerol-3;
(ii) at least one dimer acid; and
(iii) at least one fatty monoacid having from 8 to 30 carbon atoms, the components (i), (ii) and (iii) reacted being in a mole ratio of 1 mol of polyglycerol, of 0.5 to 1 mol of dimer acid and of 0.1 to less than 2.0 mol of fatty acids; and
b) at least one nonvolatile oil.

Said nonvolatile oil(s) may be chosen from those which will be described below.

According to an advantageous embodiment, the oily solution comprises, as nonvolatile oil(s), at least one fatty acid triglyceride containing from 4 to 24 carbon atoms, preferably from 8 to 24 carbon atoms, and more particularly a caprylic/capric acid triglyceride (INCI name: Caprylic/Capric Triglyceride).

The oily solution of polyester can be obtained by mixing the polyester with the nonvolatile oil(s) at about 80-100°C. The combined mixture is subsequently further cooled to 50-70°C to be discharged from the reactor and stored.

Said oily solution of polyester preferably contains the polyester at a concentration of 10% to 99% by weight, more preferentially of 30% to 90% by weight, more particularly of 50% to 80% by weight, relative to the total weight of the mixture.

According to a preferred embodiment, the oily solution comprises 40% by weight of caprylic/capric acid triglyceride and 60% by weight of polyester of polyglycerol-3, of hydrogenated C36 dimer acid and of isostearic acid, relative to the total weight of the oily solution, in a mole ratio of 1/0.5/1, as described in Example 10 (copolymer) and Example 28 (oily mixture) of US 2021/0259945.

According to a particularly preferred form of the invention, the composition comprises an oily solution comprising:
a) a polyester obtained by reaction:
(i) of a polyglycerol-3; and
(ii) of a hydrogenated C36 dimer acid; and
(iii) of isostearic acid;
the reacted components (i), (ii) and (iii) being in a mole ratio of 1 mol of polyglycerol, 0.5 to 1 mol of dimer acid and from 0.1 to less than 2.0 mol of fatty acids; and
b) a triglyceride of caprylic/capric acids, said mixture having, as INCI name: Diisostearoyl Polyglyceryl-3 Dimer Dilinoleate (and) Caprylic/Capric Triglyceride.

Such an oily solution is sold under the name SolAmaze Natural® by the company Nouryon, comprising 60% by weight, as active material, of polyester and 40% by weight of a triglyceride of caprylic/capric acids, relative to the total weight of the oily solution.

According to a preferred embodiment, the amount, as active material, of polyester varies from 2.5% to 30% by weight, more preferentially from 5% to 20% 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 a number of characteristics specific to them, such as:

- the ability to permanently harden, for example for the synthetic resins under the influence of temperature and for the natural resins under the influence of oxygen;

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

Standard ISO4618:2014(fr) defines a resin as being a "macromolecular product, generally amorphous, with a consistency ranging from the solid state to the liquid state".

Natural resins are virtually exclusively of plant origin (fossil or harvested) and are secreted then exuded by plants for roles of defence, protection and communication within their ecosystem. An exception to this is shellac, which is of animal origin and is secreted by the insect Coccus lacca.

For the purposes of the invention, “natural resin” and in particular “plant resin” means any substance comprising a minimal content of terpenic compounds, i.e. at least 30% by weight of terpenic compounds relative to the total weight of the substance (or material) in question, as defined chemically below, said substance being derived directly or indirectly from the secretion and exudation, mainly by plants (and more rarely by animals), of a substance for roles of defence, protection and communication with their ecosystem.

Advantageously, the natural resin according to the invention is insoluble in water at ambient temperature (unlike latices or gums, for example).

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

Preferably, the natural resin used in the composition according to the invention has a number-average molecular weight of less than or equal to 10 000 g/mol. The resin preferably has a number-average molecular weight of less than or equal to 10 000 g/mol, particularly ranging from 250 to 10 000 g/mol, preferably less than or equal to 5000 g/mol, particularly ranging from 250 to 5000 g/mol, better still less than or equal to 2000 g/mol, particularly ranging from 250 to 2000 g/mol and even better still less than or equal to 1000 g/mol, particularly ranging from 250 to 1000 g/mol. The number-average molecular weights (Mn) are determined by gel permeation liquid chromatography (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector).

Thermal properties

Advantageously, the resins according to the invention are characterized in that they have a softening point, which denotes the temperature of transition from a pseudo-solid state to a plastic state during heating.

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

The softening point is the temperature at which a product reaches a certain degree of softening under standardized conditions. It denotes the temperature of transition from a pseudo-solid state to a plastic state during heating. It can be measured by the ring and ball method (or RBT, ring and ball temperature) for resins according to standard ASTM E284.

Depending on the class thereof, some of the resins according to the invention can also have a melting temperature, preferably of less than 360°C, preferentially less than 190°C, and even more preferentially 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 corresponds to the temperature at which the liquid and solid states of this substance can coexist in equilibrium.

Preferably, the resins of the invention have a glass transition temperature preferably within the range from 0°C to 200°C, more preferentially from 10°C to 100°C, even more preferentially from 20°C to 90°C and even more preferably still from 30°C to 70°C.

The glass transition (Tg) temperature of a material represents the temperature range through which the material passes from a rubbery state to a vitreous, solid (rigid) state.

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

- Protocol 1: Determining melting temperature Tm and crystallization temperature Tc: Starting materials alone or solubilized/dispersed in solvents, stainless steel dishes, sweeping from 5°C to 90°C, sweep rate of 5°C.min-1;

- Protocol 2: Determining glass transition temperature Tg: measurement on second heating. Aluminum dishes (40 μl) are used, containing the starting materials, a temperature sweep between -100°C and 150°C (with isotherms) is carried out in order to observe the glass transition temperature. The temperature ramp applied is 10°C/min for the glass transition temperatures (2 cycles).

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

The components which characterize resins are the terpenic compounds that they contain, preferably in a content of at least 30% by weight relative to the weight of resin.

“Terpenic compounds” means terpenes, hydrocarbons formed from isoprene having the general formula (C₅H₈)_n, and the numerous derivatives thereof (alcohols, aldehydes, ketones, acids, etc.) comprising a terpene structure (Académie de Montpellier. Les résines [Resins]: https:/tice.ac-montpellier.fr/ABCDORGA/Famille/Terpenes.html).

Among the terpenic hydrocarbons, a distinction is made between: monoterpenes of empirical formula C10H16 (n=2), sesquiterpenes of empirical 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 comprise a number of double bonds which corresponds to their empirical formula: 3 for C₁₀H₁₆; 5 for C₂₀H₃₂; 7 for C₃₀H₄₈. Others have one or more rings, so a reduced number of double bonds, for example for C₁₀H₁₆ one ring and 2 double bonds, or 2 rings 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 better still at least 70% by weight, relative to the total weight of resin or resinous substance used as starting material in the composition according to the invention.

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

According to one 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. of compounds derived from terpenes where n is greater than or equal to 4, relative to the total weight of resin, representing 100%. Thus, resins exhibiting a fraction that is solid at ambient 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 predominantly (to more than 50% by weight relative to the total weight of polyterpenes) derived from diterpenes and/or from triterpenes.

According to one preferred embodiment of the invention, the resins comprise less than 70% by weight of monoterpenic or sesquiterpenic compounds, i.e. of compounds derived from terpenes where n is less than 4, relative to the total weight of 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 derived from terpenes where n is less than 4 relative to the total weight of resin, representing 100%. Thus, for the compositions of the invention, preference is given to limiting the use of the most volatile resins, since they are less effective in terms of the wear property of a cosmetic film.

Advantageously, the natural resin(s) according to the invention are chosen from: a) acaroid resins, b) ambers, c) asphaltite and gilsonite, d) Peru balsam, e) Tolu balsam, f) benzoin resins, g) Canada balsam, h) copal resins (particularly kauri copal resins, copal resins from Manila, West African copals such as Congolese, Angolan or Cameroonian copals, East African copals such as Zanzibari or Madagascan copals, South American copals such as Brazilian or Colombian copals), i) damars, j) elemis, k) frankincenses, l) galbanums, m) labdanums, n) mastics, o) myrrh, p) sandarac, q) shellacs, r) styrax (storax), s) Venice turpentine (larch, turpentine essence), t) rosins, particularly rosin, rosinate and tall oils, v) resins extracted from plant waxes, and mixtures of these resins.

Preferably, the natural resin(s) used according to the invention are chosen from j), k), t) and v), it being understood that the resin(s) of the invention can be esterified, salified, can form adducts, can be phenol-modified, and/or dimerized and/or additionally hydrogenated.

j) Elemis

“Elemis” is a generic term to define the group of recent natural resins derived from plants of the Burseraceae family (Canarium indicum). Each type is described according to its country of origin. According to a particular embodiment of the invention, the elemi resin used originates from the Philippines, particularly Manila elemi. To extract it, the trees are cut and a flow of pathological resin appears, which solidifies over time. The elemis are yellowish to greenish in color, opaque, similar to a pomade, slimy, tacky and solidify into brownish resins scattered with crystals.

Elemis are soluble in aromatic solvents, in alcohols, esters and carbon disulfide; and less soluble in aliphatic solvents. Elemis have an acid number of between 18 and 34, a saponification number of between 25 and 60, and a softening point of approx. 80. Balsams which exude elemis contain up to 30% of essential oils.

According to a preferred embodiment of the invention, the resin(s) of the invention are chosen from elemis, particularly the elemi originating from the Canarium luzonicum family, in pure form or mixed with a latex, for example. Mention may be made of the Canarium luzonicum elemi resin sold under the name ELEMI RESIN.

k) Frankincenses

Frankincenses are present in the United Arab Emirates, Oman, Somalia, Ethiopia and Eastern India. Frankincense resins are recent and are taken from the Boswellia carterii tree frankincense. Amazonian frankincense resins also exist. The bark is intentionally injured in order to obtain a milky extract which is recovered after drying. Preferably, the resin(s) of the invention are chosen from frankincenses, particularly Amazonian frankincenses.

Frankincense resins are pale yellow and form irregular round or globular beads. They generally contain from 20% to 40% by weight (approx. 33%) of boswellic acid (C₃₂H₅₂O₄). Frankincenses have an acid number of between 30% and 50% (indirect) and are moderately soluble in ethanol in basic medium.

According to one particular embodiment of the invention, the resin(s) of the invention are chosen from frankincenses, particularly Amazonian frankincense resins sold under the name Protium Heptaphyllum resin, or Protium Resin, or White Breu Resin, and frankincense resins originating from the sal tree, Shorea robusta.

Advantageously, the resin(s) are in a mixture with one or more fatty substances, preferably chosen 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 of Shorea robusta resin, 25-50% by weight of sunflower seed oil) sold under the name Kahlresin 6720, and Shorea robusta resin with octyldodecanol (Shorea robusta resin and octyldodecanol; 50-70% by weight of Shorea robusta resin, 30-50% by weight of octyldodecanol) sold by Kahlresin 6720.

t) Rosins

Preferably, the natural resin(s) are chosen from rosins. Rosins are recent resins from renewable resources and can be modified (for example esterified, hydrogenated, substituted).

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

Their composition is determined by the climate, the soil composition and other botanical and meteorological factors. For example, mention may be made of the rosins originating from Pinus austriaca (black pine) Austria, Central America, caribaea (slash pine), United States, Caribbean, densiflora Japan, elliottii United States, halepensis (Aleppo pine) Greece, Portugal, Spain, langifolia India, maritima (seashore pine) France, Spain, Portugal, massoniana (Chinese red pine) China, mercusii Indonesia, Burma, Philippines, nigra (black pine) Austria, oocarpa Central America, Honduras, palustris (swamp 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 essence.

Wood rosin [8050-09-7]

Rosin originates from stumps in the USA which have remained in the ground for at least 10 years in order for the resin-rich duramen to be available.

The pine stumps contain between 10% and 30% by weight (approx. 19%) of rosin, between 1% and 10% by weight (preferably 4%) of turpentine oil, between 1% and 10% by weight (preferably 4%) of resins which are 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 of lignin type.

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

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

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

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

Rosin acids have the molecular chemical formula C₂₀H₃₀O₂ and therefore belong to the diterpene family (four isoprene units). A large number of isomers of tricyclic rosin acids exist, which differ in the position of the two double bonds.

Advantageously, said resin according to the invention is chosen from gum rosin, obtained by incision on live trees, wood rosin, which is extracted from pine wood or stumps, and tall oil (“tall oil rosin”), which is obtained from a by-product originating from the production of paper. Advantageously, said resin(s) comprise rosin acids, preferably predominantly chosen from acids of abietic and pimaric type, and particularly chosen from levopimaric acid, neoabietic acid, abietic acid, dehydroabietic acid, tetrahydroabietic acid, dihydroabietic acid, dextropimaric acid, isodextropimaric acid, or else palustric acid, and mixtures thereof.

The rosin derivatives may be derived in particular from the polymerization, hydrogenation and/or esterification (for example with polyhydric alcohols such as ethylene glycol, glycerol or pentaerythritol) of rosin acids. Examples that may be mentioned include the rosin esters sold under the reference Foral 85, Pentalyn H and Staybelite Ester 10 by Hercules; Sylvatac 95 and Zonester 85 by Arizona Chemical, or Unirez 3013 by Union Camp.

According to one embodiment of the invention, the resin(s) are chosen from rosinates (salts of alkaline agents of rosin acids, particularly 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 chosen from rosin acid esters, particularly esters of rosin acids as defined above and of (C₁-C₆) alkanols, polyhydroxy(C₁-C₆)alkane polyols such as glycerol, pentaerythritol, and mixtures thereof, more preferentially chosen from glyceryl rosinate sold under the name Resiester Gum A 35, glyceryl rosinate as a mixture with a hydrogenated vegetable oil and/or castor seed oil (Glyceryl Rosinate, Ricinus Communis Seed Oil, Hydrogenated Vegetable Oil sold under the name EFP Biotek), pentaerythrityl rosinate sold under the name Resiester N 35 S and Resiester 80.

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

According to another embodiment of the invention, the resin(s) are chosen from phenol-modified rosins. Particularly those modified by (C₁-C₄)alkylene phenols or diphenols, optionally substituted with one or more (C₁-C₄)alkyl groups such as methyl or tert-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 chosen from dimerized rosins, particularly those in which the abietic acid is polymerized. The rosins preferably contain more than 50% of dimeric acids and are thus referred to as dimerized rosins. According to one embodiment, the rosins are polymerized and contain from 30% to 90% by weight of dimeric acid (particularly at least 40%, 60% or 80% of dimeric acids).

According to a preferred embodiment of the invention, the resin(s) are chosen from hydrogenated rosins. The double bonds, particularly of the acids such as abietic acid, are subject to oxidation, which can be eliminated by hydrogenation. It is understood that the resin(s) of the invention can be esterified, salified, adducts, phenol-modified, and/or dimerized and additionally hydrogenated.

According to a preferred embodiment, the resin contains at least one ester of rosin acid chosen from the group constituted of glyceryl rosinate, pentaerythrityl rosinate, silicone rosinate, diethylene glycol rosinate, hydrogenated rosinate dilinoleyl dimer, dipentaerythrityl hexahydroxystearate/hexastearate/hexarosinate, glyceryl dibehenate/hydrogenated rosinate, glyceryl diisostearate/hydrogenated rosinate, trihydrogenated glyceryl 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 chosen from hydrogenated pentaerythrityl rosinate (Pentaerythrityl Hydrogenated Rosinate) and methyl hydrogenated rosinate (Methyl Hydrogenated Rosinate) sold 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 chosen especially from waxes or butters, for instance 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, sold by Shea Butter & Glyceryl Rosinate & Oils.

v) Resins extracted from plant waxes

Natural plant waxes per se are not considered resins. Although they are among the substances secreted/excreted by plants and naturally contain a very low content of resins, they contain less than 30% by weight of terpenes relative to the total weight of wax. For example, carnauba wax is secreted naturally by the leaves of a palm tree, Copernica cerifera, to prevent the leaves from dehydrating. Candelilla wax is obtained from a shrub named Euphorbia antisyphilitica which originates from northern Mexico. The wax protects the plant from its environment and prevents excessive evaporation. For example, candelilla wax is composed mainly of hydrocarbons (approximately 50%, chains from 29 to 33 carbon atoms), of higher-molecular-weight esters (20% to 29%), of free acids (7% to 9%) and of resins (12-14%, mainly triterpenic esters).

Nevertheless, the definition of “natural resins” for the purposes of the present invention also includes resins resulting from plant waxes, when they have been concentrated, isolated or extracted beforehand from these waxes, as long as the resinous or terpenic ingredient in question contains the minimal content of terpenes (30% by weight relative to the total weight of the ingredient) required by the present invention. Mention may particularly be made of candelilla resin (pure 100% resin, extracted from the corresponding wax) having the INCI name: Euphorbia Cerifera (Candellila) Wax Extract, sold under the name Candelilla Resin E-1 by Japan Natural Products. Document WO2013/147113 A1 also refers to carnauba resin, a terpenic resin extracted from carnauba wax which has similar physical properties to those of the natural resins conventionally described, such as a softening temperature and not a melting temperature, which distinguishes a resin from a wax.

The resins have a softening point and a glass transition temperature, but not a melting temperature.

The opposite applies for waxes, which have a melting temperature.

The resin(s) are preferably chosen from resin(s) j), k), and t) as defined previously, and resins v) extracted from waxes, particularly candelilla or carnauba wax and mixtures thereof.

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

- resins extracted from plant waxes (resins of type v), preferably extracts of Euphorbia cerifera (candelilla) wax (INCI name: Euphorbia Cerifera (Candelilla) Wax Extract), such as in particular Candelilla Resin E-1 sold by Japan Natural Products, Botanical Resin sold by Cera Rica Noda, Towax-1F12 sold by Toa Kasei, or else the candelilla resin sold by Multiceras;

- frankincense resins (resins of type k), preferably Protium Heptaphyllum Resin (INCI name), or Protium resin, or White Breu resin, which may be sold, for example, by Citroleo or Ephyla;

- frankincense resins originating from the sal tree, Shorea Robusta Resin (INCI name). The resin(s) may be in a mixture with one or more fatty substances, preferably chosen 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 of Shorea robusta resin, 25-50% by weight of sunflower seed oil) sold under the name Kahlresin 6720, and Shorea robusta resin with octyldodecanol (Shorea robusta resin and octyldodecanol; 50-70% by weight of Shorea robusta resin, 30-50% by weight of octyldodecanol) sold by Kahlresin 6720 (resin of type k); and

- rosins (resins of type t), preferably rosin acid esters, such as Glyceryl Rosinate (INCI name) sold under the name Resiester Gum A 35, glyceryl rosinate as a mixture with a hydrogenated vegetable oil and/or castor seed oil (glyceryl rosinate, Ricinus communis seed oil, hydrogenated vegetable oil sold under the name EFP Biotek), pentaerythrityl rosinate sold under the name Resiester N 35 S and Resiester 80 or hydrogenated rosinates such as hydrogenated pentaerythrityl rosinate (Pentaerythrityl Hydrogenated Rosinate) or hydrogenated methyl rosinate (Methyl Hydrogenated Rosinate) sold under the name Symrise BIO4326.

According to a preferred embodiment of the invention, the resin(s) are chosen from resins extracted from Euphorbia cerifera (candelilla) wax, frankincense resins, such as Protium heptaphyllum resin, or Protium resin, or White Breu resin, frankincense resins originating from the sal tree, such as Shorea robusta resin and glyceryl rosinate. According to a preferred embodiment of the invention, the resin(s) are chosen from resins extracted from Euphorbia cerifera (candelilla) wax, frankincense resins, such as Protium heptaphyllum resin, or Protium resin, or White Breu resin and frankincense resins originating from the sal tree, such as the Shorea robusta resin.

According to a preferred embodiment of the invention, the resin(s) are chosen from Euphorbia Cerifera (Candelilla) Wax Extract.

Advantageously, the resin(s) is (are) present in the composition of the invention according to a content, expressed as active material, ranging from 0.5% to 30% by weight, more particularly from 2% to 25% by weight, preferably from 3% to 20% by weight relative to the total weight of the composition.

ALKYLCELLULOSE

The composition according to the invention also comprises at least one alkylcellulose, the alkyl part of which is a C₂-C₃ alkyl part, and preferably ethylcellulose.

Ethylcellulose is a cellulose alkyl ether comprising a chain formed from β-anhydroglucose units linked together via acetal bonds. Each anhydroglucose unit contains three replaceable hydroxy groups, all or some of these hydroxy groups being able to react according to the following reaction:

RONa + R’Cl to ROR’ + NaCl, where R represents a cellulose radical and R’ represents an ethyl or propyl radical, preferably an ethyl radical.

Total substitution of the three hydroxy groups would result, for each anhydroglucose unit, in a degree of substitution of 3, in other words in a content of alkoxy groups of 54.88%.

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

The alkylcellulose, in particular ethylcellulose, used in the composition according to the invention is more particularly in pulverulent form.

It is sold, for example, under the trade names Ethocel Standard from Dow Chemicals, notably including Ethocel Standard 7 FP Premium and Ethocel Standard 100 FP Premium. Other commercially available products, such as those sold by Ashland, Inc. under the trade names Aqualon EC type-K, type-N and type-T, preferably type-N, such as N7, N100, are particularly suitable for performing the invention.

Advantageously, the content of alkylcellulose, preferably of ethylcellulose, expressed as active material, ranges from 0.5 % to 20% by weight, more particularly from 1% to 15% by weight, more advantageously from 2% to 15% by weight, and preferably from 3% to 15% by weight, relative to the total weight of the composition.

C2-C6 MONOALCOHOL

As indicated previously, the composition according to the invention comprises at least one C₂-C₆ and more particularly C₂-C₄ monoalcohol, which is preferably saturated. The monoalcohol(s) may be represented, for example, by the formula RaOH, in which Ra represents a linear or branched alkyl group comprising from 2 to 6 carbon atoms, preferably comprising from 2 to 4 carbon atoms. Monoalcohols that may be mentioned include ethanol, isopropanol, tert-butanol or butanol, or mixtures thereof. Preferably, said monoalcohol comprises at least ethanol, and even more preferentially the monoalcohol is ethanol.

According to an advantageous embodiment of the invention, preferably if the composition comprises at least one polar volatile hydrocarbon-based solvent, the monoalcohol content represents from 2% to 40% by weight, more particularly from 3% to 35% by weight, preferably from 5% to 30% by weight, relative to the total weight of the composition.

According to an advantageous embodiment of the invention, the monoalcohol content represents from 5% to 40% by weight, more particularly from 10% to 35% by weight, preferably from 15% to 30% by weight, relative to the total weight of the composition.

VOLATILE OILS

The composition also comprises at least one hydrocarbon-based or silicone volatile oil, and also mixtures thereof.

The term “oil” means any lipophilic compound that is in liquid form at ambient temperature and at atmospheric pressure.

The volatile oil(s) are chosen from nonpolar hydrocarbon-based oils and silicone oils, alone or as a mixture.

The volatile oil is different from the volatile polar hydrocarbon-based solvent.

For the purposes of the invention, the term “volatile oil” refers to any oil that is capable of evaporating on contact with the skin in less than one hour, at room temperature and atmospheric pressure. The volatile oil is a volatile cosmetic compound, which is liquid at room temperature, notably having a nonzero vapor pressure, at room temperature and atmospheric pressure, notably having a vapor pressure of at least 0.13 Pa, more particularly of at least 2.66 Pa, in particular ranging from 0.13 Pa to 13 000 Pa and preferentially ranging from 0.5 Pa to 8000 Pa (OECD 104 standard).

The term “nonpolar hydrocarbon-based oil” means an oil chosen from hydrocarbons, that is to say from compounds comprising only carbon and hydrogen atoms.

The term “silicone oil” denotes an oil comprising at least one

Si-O group, and more particularly an organopolysiloxane.

NONPOLAR VOLATILE HYDROCARBON-BASED OILS

The nonpolar hydrocarbon-based volatile oils that may be used in the context of the invention are more particularly chosen from linear or branched, preferably saturated, oils containing from 8 to 16 carbon atoms, and mixtures thereof.

The volatile hydrocarbon-based oils that may be used in the compositions according to the invention may thus be chosen from volatile linear alkanes comprising from 8 to 14 carbon atoms.

As examples of linear alkanes, in particular C8-C14 alkanes, mention may be made of n-octane (C8), n-nonane (C9), n-decane (C10), n-undecane (C11), n-dodecane (C12) and n-tridecane (C13), and mixtures thereof. Mention may notably be made of n-dodecane (C12) and n-tetradecane (C14) sold by Sasol under the respective references Parafol 12-97® and Parafol 14-97®, and also mixtures thereof. According to another embodiment, use may be made of a mixture of n-dodecane and n-tetradecane, and in particular the dodecane/tetradecane mixture sold by the company Biosynthis under the reference Vegelight 1214®. According to yet another embodiment, use may also be made of a mixture of volatile linear C9-C12 alkanes of INCI name: C9-12 Alkane, such as the product sold by the company Biosynthis under the reference Vegelight Silk®. According to yet another embodiment, use may be made of a mixture of n-undecane (C11) and of n-tridecane (C13) as obtained in Examples 1 and 2 of patent application WO 2008/155 059 from the company Cognis and such as the product sold under the trade name Cetiol Ultimate® by the company BASF.

Mention may also be made of the alkanes described in the Cognis patent applications WO 2007/068 371 or WO 2008/155 059 (mixtures of different alkanes differing by at least one carbon). These alkanes are obtained from fatty alcohols, which are themselves obtained from coconut kernel oil or palm oil.

The volatile hydrocarbon-based oils that may be used in the compositions according to the invention may be chosen from branched C8-C16 alkanes. Mention may notably be made of C8-C16 isoalkanes of petroleum origin (also known as isoparaffins), such as isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane and, for example, the oils sold under the Isopar® or Permethyl® trade names.

VOLATILE SILICONE OILS

As examples of volatile silicone oils that can be used in the invention, mention may be made of volatile silicone oils, such as linear or cyclic volatile silicone oils notably containing from 2 to 7 silicon atoms, these silicones optionally including alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oils that may be used in the invention, mention may notably be made of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.

According to a particularly preferred embodiment, the volatile oil is chosen from volatile hydrocarbon-based oils, even more particularly chosen from branched C₈-C₁₆ alkanes and from linear C₈-C₁₄ alkanes, and also mixtures thereof, and in particular isododecane, the mixture of volatile linear C₉-C₁₂ alkanes and the mixture of n-undecane (C11) and of n-tridecane (C13), and mixtures thereof.

Preferably, the content of volatile oil(s), preferably hydrocarbon-based volatile oil(s), represents from 5% to 40% by weight, preferably from 15% to 35% by weight, relative to the total weight of the composition.

Preferably, if the composition comprises at least one volatile or nonvolatile silicone oil, then their content does not exceed 5% by weight and more particularly does not exceed 3% by weight, relative to the total weight of the composition. Preferably, the composition according to the invention does not contain any.

According to a preferential form of the invention, the weight ratio of the amount of volatile oil(s) to the amount of monoalcohol(s) is less than 4, more particularly less than 3.5 and even more preferentially less than 1.5.

VOLATILE POLAR HYDROCARBON-BASED SOLVENTS

As indicated above, the composition according to the invention optionally comprises at least one volatile polar hydrocarbon-based solvent, which is preferably compatible with the abovementioned polyester.

The term “polar hydrocarbon-based solvent compatible with the abovementioned polyester” denotes a compound which is liquid at room temperature and which makes it possible to obtain a homogeneous and clear mixture from 10% by weight of the abovementioned polyester, alone or in the form of a solution with an oil if it is sold in this form, and 90% by weight of said liquid compound (solvent), at room temperature, after standing for 10 minutes following the preparation.

The term “polar hydrocarbon-based solvent” means that said solvent comprises, in addition to carbon and hydrogen atoms, at least one oxygen atom. Thus, said hydrocarbon-based solvent comprises at least one hydroxy, ester, ether and/or carboxylic function.

According to an advantageous embodiment of the invention, the volatile polar hydrocarbon-based solvent, alone or as a mixture, is chosen from linear, branched or cyclic saturated compounds, of the following formula: C_nH_2nO₃, wherein n is an integer ranging from 5 to 9, preferably from 6 to 9, said compound comprising at least one hydroxy (-OH) function and at least one function chosen from ether (-O-) and/or ester (-O-C(=O)-). It should be noted that in the formula, the limits are included.

According to a first variant, the volatile polar hydrocarbon-based solvent is chosen from hydroxycarboxylic esters in which the subscript n is an integer varying from 5 to 9, more particularly from 6 to 9, preferably from 7 to 9, such as, for example, linear or branched saturated lactates, such as ethyl lactate (C5), isopropyl lactate (C6), propyl lactate (C6), butyl lactate (C7), isobutyl lactate (C7), amyl lactate (C8), isoamyl lactate (C8) and hexyl lactate (C9), or else butyl glycolate, methyl 3-hydroxyhexanoate, tert-butyl 3-hydroxypropionate, and mixtures thereof.

Preferably, in this case, the volatile polar hydrocarbon-based solvent is chosen from lactates and even more preferentially from isopropyl lactate (C6), butyl lactate (C7) and hexyl lactate (C9) and mixtures thereof. It should be noted that the lactates are, for example, sold under the name PURASOLV by Corbion.

According to another variant, the volatile polar hydrocarbon-based solvent is chosen from those comprising a hydroxy group and two ether functions, preferably comprising at least one cyclic ether function, preferably comprising a cyclic ether containing two ether functions, such as a dioxane ring or a dioxolane ring; preferably, said polar volatile solvent comprises a hydroxy group and a 1,3-dioxolane ring, and mixtures thereof.

Preferably in this case, the subscript n is an integer varying from 6 to 8 (limits included). Preferably, said compound is chosen from 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane (or 1,2-isopropylideneglycerol), 4-(2-hydroxyethyl)-2,2-dimethyl-1,3-dioxolane, (4S)-(+)-4-(2-hydroxyethyl)-2,2-dimethyl-1,3-dioxolane, and mixtures thereof. Preferably, the compound is 1,2-isopropylideneglycerol (2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane).

It should be noted that 1,2-isopropylideneglycerol is a solvent sold under several commercial references, such as AUGEO® CRYSTAL by Solvay, or ECOETAL® by BIOINSPIR.

Advantageously, the volatile polar hydrocarbon-based solvent, preferably compatible with the abovementioned polyester, is chosen from lactates such as isopropyl lactate (C6), butyl lactate (C7) and hexyl lactate (C9) and mixtures thereof, more advantageously butyl lactate; from 1,2-isopropylidene glycerol; and mixtures thereof.

Preferably, if the composition contains any, the content of volatile polar hydrocarbon-based solvent(s), preferably compatible with the abovementioned polyester, represents from 1% to 30% by weight and preferably from 2% to 25% by weight, relative to the total weight of the composition.

According to an even more advantageous embodiment, the weight ratio of the total amount of nonpolar hydrocarbon-based oil(s) to the total amount of volatile polar hydrocarbon-based solvent(s) ranges from 70/30 to 5/95.

NONVOLATILE OILS

The composition according to the invention may optionally comprise at least one nonvolatile hydrocarbon-based oil, other than the abovementioned polyester, or nonvolatile silicone oil, and also mixtures thereof.

The term “hydrocarbon-based oil” refers to an oil mainly containing carbon and hydrogen atoms and possibly one or more functions chosen from hydroxyl, ester, ether and carboxylic functions. These oils are thus different from silicone oils.

The term “nonvolatile oil” refers to an oil whose vapor pressure at 20°C and at atmospheric pressure is nonzero and is less than 0.13 Pa. By way of example, the vapor pressure may be measured according to the static method or via the effusion method by isothermal thermogravimetry, depending on the vapor pressure of the oil (OECD 104 standard).

POLAR, NONVOLATILE HYDROCARBON-BASED OILS

The term “polar hydrocarbon-based oil” means that said oils comprise, in addition to carbon and hydrogen atoms, at least one oxygen atom. Thus, said hydrocarbon-based oil comprises at least one hydroxyl, ester, ether and/or carboxylic function.

The composition according to the invention may thus comprise at least one nonvolatile polar hydrocarbon-based oil, more particularly chosen from:

* saturated or unsaturated, linear or branched, C₁₀-C₂₆ fatty alcohols, preferably monoalcohols, which are preferably branched when they comprise at least 16 carbon atoms. More particularly, the fatty alcohol comprises from 10 to 24 carbon atoms and more preferentially from 12 to 22 carbon atoms;

* ethers of formula ROR’ or carbonates of formula RO(CO)OR', in which formulae the groups R and R’, which may be identical or different, represent a saturated or unsaturated, branched or unbranched, hydrocarbon-based group comprising not more than 16 carbon atoms, preferably a C₃-C₁₆ group;

* esters chosen from:

- hydroxylated or non-hydroxylated plant oils;

- optionally hydroxylated ester oils comprising from 1 to 4 ester functions, of which at least one of them, which is linear or branched, saturated, unsaturated or aromatic, comprises at least 8 carbon atoms;

- liquid polyesters derived from the reaction of a monounsaturated or polyunsaturated dimer acid, the fatty acid comprising from 16 to 22 carbon atoms, and of a polyol;

* and mixtures thereof.

Preferably, the polar nonvolatile hydrocarbon-based oil is chosen from:

- lauryl alcohol, isostearyl alcohol, oleyl alcohol, 2-butyloctanol, 2-undecylpentadecanol, 2-hexyldecyl alcohol, isocetyl alcohol and octyldodecanol, and mixtures thereof; preferably octyldodecanol;

- dicaprylyl ether;

- dipropyl carbonate, diethylhexyl carbonate, dicaprylyl carbonate, and C14-C15 dialkyl carbonate;

- castor oil, olive oil, jojoba oil, ximenia oil, pracaxi oil, wheat germ oil, corn oil, sunflower oil, sweet almond oil, macadamia oil, apricot kernel oil, soybean oil, rapeseed oil, groundnut oil, cottonseed oil, alfalfa oil, poppy oil, pumpkin oil, sesame oil, marrow oil, avocado oil, hazelnut oil, grape seed oil, blackcurrant oil, argan oil, evening primrose oil, millet oil, barley oil, linseed oil, quinoa oil, rye oil, safflower oil, candlenut oil, passionflower oil, musk rose oil, the liquid fraction of shea butter and the liquid fraction of cocoa butter, and mixtures thereof;

- 2-ethylhexyl palmitate, 2-octyldecyl palmitate, octyldodecyl neopentanoate, 2-octyldodecyl stearate, butyl stearate, 2-octyldodecyl erucate, C₁₂ to C₁₅ alkyl benzoates, 2-octyldodecyl benzoate, isocetyl isostearate, isostearyl isostearate, isononyl isononanoate, isopropyl palmitate, hexyl laurate, 2-hexyldecyl laurate, isopropyl myristate, 2-octyldodecyl myristate, diisostearyl malate, neopentyl glycol dicaprate, glyceryl tris(2-decyltetradecanoate), capric/caprylic acid triglycerides, C_18-36 acid triglycerides, glyceryl triheptanoate, glyceryl trioctanoate, glyceryl tris(2-decyltetradecanoate), triisostearyl citrate, tridecyl stearate, tridecyl trimellitate, pentaerythrityl tetrapelargonate, pentaerythrityl tetraisostearate, pentaerythrityl tetraisononanoate, pentaerythrityl tetrakis(2-decyltetradecanoate); isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate;

- the polyesters having the following INCI names: Dilinoleic Acid/Butanediol Copolymer, Dilinoleic Acid/Propanediol Copolymer, Dimer Dilinoleyl Dimer Dilinoleate,

- and also mixtures thereof.

NONPOLAR, NONVOLATILE HYDROCARBON-BASED OILS

The nonpolar, nonvolatile hydrocarbon-based oil may be chosen from linear or branched hydrocarbons of mineral, plant or synthetic origin, for instance:

- liquid paraffin,

- squalane, in particular of plant origin,

- isoeicosane,

- mixtures of saturated linear hydrocarbons, more particularly of C15-C28, such as the mixtures of which the INCI names are, for example, the following: C15-19 Alkane, C18-C21 Alkane, C21-C28 Alkane, for instance the products Gemseal 40, Gemseal 60 and Gemseal 120 sold by Total, and Emogreen L15 and L19 sold by SEPPIC,

- hydrogenated or non-hydrogenated polybutenes, for instance products of the Indopol range sold by the company Ineos Oligomers,

- hydrogenated or non-hydrogenated polyisobutenes, for instance the nonvolatile compounds of the Parleam® range sold by the company Nippon Oil & Fats,

- hydrogenated or non-hydrogenated polydecenes, for instance nonvolatile compounds of the Silkflo range sold by the company Ineos, and Dekanex by the company IMCD,

- and mixtures thereof.

NONVOLATILE SILICONE OILS

The composition according to the invention may comprise at least one nonvolatile phenyl silicone oil, optionally comprising at least one dimethicone fragment, or at least one nonvolatile nonphenyl silicone oil, or mixtures thereof.

The term “phenyl(ated)” specifies that said oil includes, in its structure, at least one phenyl radical.

The term “dimethicone fragment” denotes a divalent siloxane group, the silicon atom of which bears two methyl radicals, this group not being located at one or both ends of the molecule. It may be represented by the following formula: -(Si(CH₃)₂-O)-.

Preferably, the silicones do not contain a C₂-C₃ alkylene oxide group or a glycerolated group.

As nonvolatile phenylated oil comprising at least one dimethicone fragment, mention may be made of the oils having the following INCI names: Trimethylsiloxyphenyl Dimethicone, Diphenyl Dimethicone, Tetramethyl Tetraphenyl Trisiloxane and also mixtures thereof, preferably Trimethylsiloxyphenyl Dimethicone. The Diphenyl Dimethicones are notably sold by the company Shin-Etsu under the names KF-54, KF54HV, KF-50-300CS, KF-53 d and KF-50-100CS. The Trimethylsiloxy Phenyl Dimethicones are sold, for example, by the company Wacker Chemie under the names Belsil PDM 1000 and Belsil PDM 20.

Among the nonvolatile phenyl silicone oils not containing a dimethicone fragment, mention may be made of the compounds having the following INCI names: Phenyltrimethicone, Trimethyl Pentaphenyl Trisiloxane, alone or as mixtures. As nonvolatile, nonphenyl silicone oils that are suitable for performing the invention, mention may be made of those sold by the company Wacker under the Belsil DM range, by the company Dow Corning with the Xiameter PMX 200 Silicone Fluid range, and by the company Shin-Etsu with the KF-96 A range.

Representative examples of the nonvolatile nonphenyl silicone oils include polydimethylsiloxanes and alkyl dimethicones. It should be noted that the term “dimethicone” (INCI name) corresponds to a polydimethylsiloxane (chemical name). Preferably, these nonvolatile, nonphenyl silicone oils are chosen from polydimethylsiloxanes and alkyl dimethicones comprising at least one C₂-C₂₄ alkyl group, and also mixtures thereof. Thus, these oils may be chosen from dimethicone, cetyl dimethicone and stearyl dimethicone, alone or as mixtures. As nonvolatile, nonphenyl silicone oils that are suitable for use, mention may be made of those sold by the company Wacker under the Belsil DM range, by the company Dow Corning with the Xiameter PMX 200 Silicone Fluid range, and by the company Shin-Etsu with the KF-96 A range. The alkyldimethicones may be sold, for example, under the trade names Abil Wax 9800 and Abil Wax 9801 from Evonik Goldschmidt, or Dowsil 2502 Cosmetic Fluid, Dowsil 2503 Cosmetic Wax, from Dow Corning; and mixtures thereof.

Preferably, if the composition comprises any, the nonvolatile oil is chosen from polar hydrocarbon-based oils, alone or as mixtures, other than the abovementioned polyester, in particular chosen from alcohol oils and esters.

In accordance with an even more preferred embodiment, if the composition comprises any, the nonvolatile oil(s) is/are chosen from octyldodecanol, plant oils, ester oils, which are optionally hydroxylated, comprising 1 to 4 ester functions, at least one of which is linear or branched, saturated, unsaturated or aromatic, comprising at least 8 carbon atoms, and also mixtures thereof.

According to a preferred embodiment, the nonvolatile oil is chosen from octyldodecanol, triglycerides of fatty acids containing from 8 to 24 carbon atoms, and more particularly a caprylic/capric acid triglyceride (INCI name: Caprylic/Capric Triglyceride), plant oils, and also mixtures thereof.

Preferably, the composition comprises at least one nonvolatile oil chosen from polar hydrocarbon-based oils other than the abovementioned polyester, in particular from fatty alcohols, esters and mixtures thereof.

In accordance with an even more preferred embodiment, the composition comprises at least one nonvolatile oil chosen from fatty alcohols, plant oils, ester oils, which are optionally hydroxylated, comprising 1 to 4 ester functions, at least one of which is linear or branched, saturated, unsaturated or aromatic, comprising at least 8 carbon atoms, and also mixtures thereof.

According to a preferred form, the nonvolatile oil is chosen from triglycerides of fatty acids containing from 8 to 24 carbon atoms, and more particularly a caprylic/capric acid triglyceride (INCI name: Caprylic/Capric Triglyceride).

If the composition comprises any, the content of nonvolatile, preferably hydrocarbon-based oil(s) ranges from 0.5% to 20% by weight, more particularly from 1% to 10% by weight relative to the total weight of the composition.

SILICA-TYPE FILLERS

The composition according to the invention also comprises at least one silica-type filler.

The term “filler” should be understood as meaning a colorless or white solid particle of any form, which is in an insoluble form dispersed in the medium of the composition.

The silica that may be used as filler may be a precipitated or fumed silica, and preferably a precipitated silica. More particularly, the INCI name of the silica-type filler according to the invention is Silica.

Advantageously, the silica that may be used as filler has not been subjected to a hydrophobic surface treatment.

It should be noted that silicas having the INCI name Silica Silylate or Silica Dimethyl Silylate are not considered as fillers for the purposes of the invention.

It may be in any shape, preferably spherical. The term “spherical silica” means silica particles having the shape or substantially the shape of a sphere, which are insoluble in the medium of the composition according to the invention, even at the melting point of the medium (about 100°C). The spherical silica particles of the present invention may have a mean circularity of at least 0.8, and preferably of at least 0.82. The spherical porous silica particles of the present invention may have a mean circularity of less than or equal to 1, preferably less than or equal to 0.99, more preferably less than or equal to 0.98, even more preferably less than or equal to 0.97, even more preferably less than or equal to 0.96, and most preferably less than or equal to 0.95.

The “mean circularity” may be determined by an image analysis method. In particular, the “mean circularity” may be an arithmetic mean circularity obtained by image analysis of a scanning electron microscope (SEM) image of no less than 2000 silica particles, observed at a magnification of 1000 by detection of secondary electrons using a scanning electron microscope. (SEM).

The "circularity" of each silica particle is a value determined by the following formula: C = 4πS / L² in which C represents a circularity, S represents an area (projected area) of the particle in the image, and L represents a length of a periphery (perimeter) of the silica particle in the image. When the mean circularity approaches 1, the shape of each of the particles becomes more spherical.

The mean diameter of the silica particles, corresponding to the volume-mean diameter (d[50]), is advantageously between 0.5 and 30 µm, preferably between 1 and 20 μm.

The sizes of the silica particles may be measured by static light scattering using a commercial particle size analyzer such as the MasterSizer 2000® machine from Malvern. The data are processed on the basis of the Mie scattering theory. This theory, which is exact for isotropic particles, makes it possible to determine, in the case of non-spherical particles, an “effective” particle diameter. This theory is in particular described in the publication by Van de Hulst, H.C., Light Scattering by Small Particles, Chapters 9 and 10, Wiley, New York, 1957.

The silica particles used in the invention are preferably porous.

For the purposes of the present invention, the term “porous particles” means particles having a structure including pores or interstices. The structure of the particles may be matrix-like (with an outwardly open porosity) like a sponge, and/or may comprise a central cavity (hollow sphere).

More particularly, the porosity of the particles is characterized quantitatively by their specific surface area.

Preferably, the silica particles have a specific surface area of from 2 to 1000 m²/g, more particularly from 10 to 1000 m²/g, preferably from 100 to 900 m²/g.

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

According to a particular embodiment of the invention, the silica-type filler is chosen from porous spherical particles of silica, preferably chosen from porous spherical particles of amorphous silica, preferably which has not undergone any hydrophobic surface treatment; mixtures thereof.

The term “amorphous silica” means vitreous silica, i.e. non-crystalline silica in which the atoms do not respect any order at medium and long distances, unlike crystalline silica.

As examples of porous spherical amorphous silica that is not hydrophobically surface-treated, use may be made of the following commercial products: Silica 35 Beads SB-150®, SB-300® or else SB 700®, preferentially SB 300® from the company Myoshi Kasei; the Sunsphere® range from the company Asahi Glass AGC SI-TECH, notably Sunsphere H-51® or else Sunsphere 12L®, Sunsphere H-201®, H-52 and H-53; Sunsil 130 8® from the company Sunjin; Spherica P-1500® from the company Ikeda Corporation; Sylosphere® from the company Fuji Silysia; the Silica Pearl® and Satinier® ranges from the company JGC Catalysts and Chemicals, more particularly Satinier M13® and Satinier M16 silicas, MSS-500® silicas from the company Kobo, and more particularly MSS-500-20N®, Silica Shells® from the company Kobo and also the BA4 silicas from JGC Catalysts and Chemicals.

Preferably, the composition comprises from 0.2% to 10% by weight, preferably from 0.5% to 7% by weight, of silica-type filler, relative to the total weight of the composition.

WATER

The composition according to the invention may optionally comprise water.

A water that is suitable for use in the invention may be a demineralized water, a floral water such as cornflower water and/or a mineral water such as Vittel water, Lucas water or La Roche Posay water and/or a spring water.

According to a particular embodiment of the invention, if the composition according to the invention comprises water, its content is less than 20% by weight, more particularly less than 15% by weight and preferably less than 10% by weight, relative to the total weight of the composition.

COLORANTS

The composition according to the invention preferably comprises at least one colorant.

According to a particular form of the invention, the colorant may be chosen from pulverulent colorants, liposoluble dyes, water-soluble dyes and mixtures thereof.

PULVERULENT COLORANTS

The pulverulent colorants may be chosen from mineral pigments, organic pigments, nacres and mixtures thereof.

The term "pigments" means white or colored, mineral or organic particles, which are insoluble in an aqueous medium, and which are intended to color and/or opacify the resulting composition and/or deposit. These pigments may be white or colored, and mineral and/or organic.

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

The term "mineral pigment" refers to any pigment that satisfies the definition in Ullmann's Encyclopedia in the chapter on inorganic pigments. Among the mineral pigments that are useful in the present invention, mention may be made of zirconium oxide or cerium oxide, and also zinc oxide, iron oxide (black, yellow or red) or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue, titanium dioxide, and metal powders, for instance aluminum powder and copper powder. The following mineral pigments may also be used: Ta₂O₅, Ti₃O₅, Ti₂O₃, TiO, ZrO₂ as a mixture with TiO₂, ZrO₂, Nb₂O₅, CeO₂, ZnS.

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

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

The sizes are measured by static light scattering using a commercial MasterSizer 3000® particle size analyzer from Malvern, which makes it possible to determine the particle size distribution of all of the particles over a wide range which may extend from 0.01 µm to 1000 µm. The data are processed on the basis of the standard Mie scattering theory. This theory is the most suitable for size distributions ranging from submicronic to multimicronic; it makes it possible to determine an “effective” particle diameter. This theory is notably described in the publication by Van de Hulst, H.C., Light Scattering by Small Particles, Chapters 9 and 10, Wiley, New York, 1957.

d[50] represents the maximum size exhibited by 50% by volume of the particles.

According to a particular form of the invention, the mineral pigment comprises a lipophilic or hydrophobic coating, said coating preferably being present in the oily 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 chosen from metal soaps; N-acylamino acids or salts thereof; lecithin and derivatives thereof; isopropyl triisostearyl titanate; isostearyl sebacate; natural plant or animal waxes; polar synthetic waxes; fatty esters; phospholipids; and mixtures thereof.

According to a preferential embodiment, the pigments may be coated according to the invention with an N-acylamino acid or a salt thereof, which may comprise an acyl group containing from 8 to 22 carbon atoms, for instance a 2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl or cocoyl group.

The amino acid may be, for example, lysine, glutamic acid or alanine. The salts of these compounds may be the aluminum, magnesium, calcium, zirconium, zinc, sodium or potassium salts. Thus, according to a particularly preferred embodiment, the pigments may be coated with an N-acylamino acid derivative which may in particular be a glutamic acid derivative and/or a salt thereof, and more particularly a stearoyl glutamate, for instance aluminum stearoyl glutamate. As examples of pigments treated with aluminum stearoyl glutamate, mention may be made of titanium dioxide pigments and black, red and yellow iron oxide pigments sold under the trade name NAI® by the company Miyoshi Kasei.

According to a preferential embodiment, the pigments may be coated according to the invention with isopropyl triisostearyl titanate. As examples of isopropyl titanium triisostearate (ITT)-treated pigments, mention may be made of titanium dioxide pigments and the black, red and yellow iron oxide pigments sold under the trade names BWBO-I2® (iron oxide CI77499 and isopropyl titanium triisostearate), BWYO-I2® (iron oxide CI77492 and isopropyl titanium triisostearate) and BWRO-I2® (iron oxide CI77491 and isopropyl titanium triisostearate) by the company Kobo.

The pigments that may be used according to the invention may also be organic pigments.

The term “organic pigment” refers to any pigment that satisfies the definition in Ullmann’s Encyclopedia in the chapter on organic pigments. The organic pigment may notably be chosen from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal-complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane or quinophthalone compounds.

The organic pigment(s) may be chosen, for example, from carmine, carbon black, aniline black, melanin, azo yellow, quinacridone, phthalocyanine blue, sorghum red, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 73000, 74100 and 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000 and 47005, the green pigments codified in the Color Index under the references CI 61565, 61570 and 74260, the orange pigments codified in the Color Index under the references CI 11725, 15510, 45370 and 71105, the red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915 and 75470, and the pigments obtained by oxidative polymerization of indole or phenol derivatives as described in patent FR 2 679 771.

These pigments may also be in the form of composite pigments as described in patent EP 1 184 426. These composite pigments may notably be composed of particles including a mineral core at least partially covered with an organic pigment and at least one binder for fixing the organic pigments to the core.

The pigment may also be a lake. The term "lake" means insolubilized dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use.

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

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

An example of a lake that may be mentioned is the product known under the name D&C Red 7 (CI 15 850:1).

Preferably, the composition according to the invention comprises at least one pulverulent colorant of mineral pigment type, in particular chosen from metal oxides, and more particularly chosen from coated or uncoated titanium dioxides or iron oxides and mixtures thereof.

The nacres may be chosen from white nacreous pigments such as mica coated with titanium or with bismuth oxychloride, colored nacreous pigments such as titanium mica with iron oxides, titanium mica notably with ferric blue or chromium oxide, titanium mica with an organic pigment of the abovementioned type, and also nacreous pigments based on bismuth oxychloride.

Preferably, if the composition comprises any, the pulverulent colorant(s) are preferably present in a content ranging from 3% to 25% by weight, preferably from 5% to 20% by weight, more particularly from 6% to 15% by weight, relative to the total weight of the composition.

WATER-SOLUBLE OR LIPOSOLUBLE COLORANTS

A composition according to the invention may comprise at least one water-soluble or liposoluble colorant, preferably in a proportion of at least 0.01% by weight relative to the total weight of the composition.

For obvious reasons, this amount is liable to vary significantly with regard to the intensity of the desired color effect and of the color intensity afforded by the colorants under consideration, and its adjustment clearly falls within the competence of a person skilled in the art.

The additional colorants that are suitable for use in the invention may be liposoluble.

For the purposes of the invention, the term “liposoluble colorant” means any natural or synthetic, generally organic compound, which is soluble in an oily phase or in solvents that are miscible with a fatty substance, and which is capable of imparting color.

As liposoluble dyes that are suitable for use in the invention, mention may notably be made of synthetic or natural liposoluble dyes, for instance DC Red 17, DC Red 21, DC Red 27, DC Green 6, DC Yellow 11, DC Violet 2, DC Orange 5, Sudan red, carotenes (β-carotene, lycopene), xanthophylls (capsanthin, capsorubin, lutein), palm oil, Sudan brown, quinoline yellow, annatto and curcumin.

The additional colorants that are suitable for use in the invention may be water-soluble.

For the purposes of the invention, the term “water-soluble colorant” means any natural or synthetic, generally organic compound, which is soluble in an aqueous phase or water-miscible solvents and which is capable of imparting color.

As water-soluble dyes that are suitable for use in the invention, mention may be made notably of synthetic or natural water-soluble dyes, for instance FDC Red 4, DC Red 6, DC Red 22, DC Red 28, DC Red 30, DC Red 33, DC Orange 4, DC Yellow 5, DC Yellow 6, DC Yellow 8, FDC Green 3, DC Green 5, FDC Blue 1, betanine (beetroot), carmine, copper chlorophyllin, methylene blue, anthocyanins (enocianin, black carrot, hibiscus, elder), caramel and riboflavin.

The water-soluble or liposoluble dye(s), if the composition comprises any, are preferably present in contents of less than 4% by weight, or even less than 2% by weight, more preferentially ranging from 0.01% to 2% by weight and better still from 0.02% to 1.5% by weight, relative to the total weight of the composition.

COSMETIC ADDITIVES

The compositions according to the invention may include additives commonly used in care and/or makeup products, such as active ingredients like vitamins, for example vitamins A, E, C and B3, adenosine, hyaluronic acid and salts thereof; UV screening agents; additional fillers, other than the silica-type fillers in accordance with the invention; waxes; pasty compounds; hydrophilic gelling agents; film-forming agents other than the alkylcellulose (in particular ethylcellulose); lipophilic mineral thickeners, which will be described later, or organic thickeners, for instance dextrin esters of a fatty acid, in particular of a C12 to C24, preferably C14 to C18, fatty acid, or mixtures thereof, and more preferentially dextrin palmitate, dextrin myristate; fragrances; preserving agents; and mixtures thereof.

Although this does not correspond to a preferred variant of the invention, the composition may optionally comprise one or more silicone polymers, for instance silicone resins, silicone acrylate copolymers, silicone polyamides, and combinations thereof.

Among the silicone resins, examples that may be mentioned include the resins having the following INCI names: Trimethylsiloxysilicate, phenylpropyldimethylsiloxysilicate, polymethyl silsesquioxane, the MQT-propyl resins, especially described and prepared in patent application WO 2005/075542. Mention may also be made of C30-45 Alkyldimethylsilyl Polypropylsilsesquioxane (INCI name).

Among the silicone-acrylate copolymers, which may or may not be dendrimer copolymers, mention may be made, for example, of the copolymers having the INCI name Acrylates/Polytrimethylsiloxymethacrylate Copolymer; Acrylates/Dimethicone Copolymer.

As regards the acrylamide-silicone copolymers, mention may be made especially of the copolymer having the INCI name Nylon-611/Dimethicone Copolymer.

If the composition comprises any, the content of silicone polymer(s) does not exceed 5% by weight, more particularly does not exceed 3% by weight, relative to the total weight of the composition. Preferably, the composition according to the invention does not contain any.

It is a matter of routine practice for a person skilled in the art to adjust the nature and amount of the additives present in the compositions in accordance with the invention such that the desired cosmetic properties thereof are not thereby affected.

Needless to say, a person skilled in the art will take care to select the optional additional additives and/or the amount thereof such that the advantageous properties of the compositions according to the invention are not, or are not substantially, adversely affected by the envisaged addition.

ADDITIONAL FILLERS

The compositions in accordance with the invention may thus comprise at least one additional filler, other than the silica-type fillers in accordance with the invention described previously.

The additional fillers may be mineral or organic.

Preferably, they may be chosen from natural fillers or fillers of natural origin.

The term “natural filler” or “natural compound” means a compound that is obtained directly from the earth or the soil, or from plants or animals, via, where appropriate, one or more physical processes, for instance milling, refining, distillation, purification or filtration.

The term “filler of natural origin” or “compound of natural origin” means a natural compound that has undergone one or more additional chemical or industrial treatments, giving rise to modifications that do not affect the essential qualities of this compound and/or a compound predominantly comprising natural constituents that may or may not have undergone transformations. Mention may be made, as nonlimiting example of additional chemical or industrial treatment bringing about modifications which do not affect the essential qualities of a natural compound, of those permitted by the controlling bodies, such as Ecocert (Reference system for biological and ecological cosmetic products, January 2003), or defined in recognized handbooks in the field, such as “Cosmetics and Toiletries Magazine”, 2005, Vol. 120, 9: 10.

The additional fillers that may be used in the compositions according to the present invention may be in lamellar, globular or spherical form, in the form of fibers or in any other intermediate form between these defined forms.

The additional fillers may or may not be surface-coated, and in particular they may be surface-treated with amino acids or any other substance that promotes the dispersion and compatibility of the filler in the composition.

Mineral fillers

Examples of mineral fillers include, alone or as mixtures, talcs, natural or synthetic micas such as synthetic fluorphlogopites, diatomaceous earth, unmodified clays such as smectites, and preferably unmodified hectorite, kaolin, kaolin and halloysite, calcium carbonate, magnesium carbonate, hydroxyapatite, boron nitride, perlite, bismuth oxychloride, barium sulfate optionally combined with lauroyl lysine, silica combined with lauroyl lysine, glass microcapsules, borosilicates or ceramics, silica and titanium dioxide composites, such as the TSG series® sold by Nippon Sheet Glass.

Organic fillers

As examples of organic fillers, mention may be made, alone or as mixtures, of micronized natural waxes, such as micronized carnauba wax; metal soaps derived from organic carboxylic acids containing from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate or magnesium myristate; lauroyl lysine; Hordeum Vulgare Seed Flour; PHAs (polyhydroxyalkanoates), starch; quinoa extract (INCI name: Chenopodium Quinoa Seed Extract), cellulose powders, such as the product sold by Daito in the Cellulobeads® range.

Preferably, if the composition contains any, the additional filler(s) are present in the composition in a content ranging from 0.5% to 20% by weight, preferably from 1% to 15% by weight, more particularly from 2% to 10% by weight, relative to the total weight of the composition.

WAXES

The composition according to the invention may comprise at least one polar or apolar hydrocarbon-based wax.

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

For the purposes of the invention, the melting point corresponds to the temperature of the most endothermic peak observed on thermal analysis (DSC) as described in the standard ISO 11357-3; 1999. The melting point of the wax may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name DSC Q2000 by the company TA Instruments with the TA Universal Analysis software.

The measuring protocol is as follows:

A sample of 5 mg of wax is placed in a crucible and subjected to a first temperature rise ranging from -20°C to 120°C, at a heating rate of 10°C/minute, is then cooled from 120°C to -20°C at a cooling rate of 10°C/minute and is lastly subjected to a second temperature rise ranging from -20°C to 120°C at a heating rate of 5°C/minute.

During the second temperature rise, the melting point of the solid fatty substance is measured, which corresponds to the temperature of the most endothermic peak observed on the melting curve, representing the variation in the difference in power absorbed as a function of the temperature.

The enthalpy of fusion of the wax (∆Hf), corresponding to the integral of the entire melting curve obtained, may also be measured. This enthalpy of fusion of the wax is the amount of energy required to cause the compound to change from the solid state to the liquid state. It is expressed in J/g.

The waxes may be of plant, mineral, animal and/or synthetic origin.

In particular, the waxes have a melting point preferably greater than or equal to 35°C and better still greater than or equal to 40°C.

Nonpolar waxes

For the purposes of the present invention, the term “apolar hydrocarbon-based wax” means a wax constituted solely of carbon and hydrogen atoms and free of heteroatoms, for instance N, O, Si, P, etc.

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

Polar waxes

The polar waxes may notably be hydrocarbon-based or silicone waxes.

For the purposes of the present invention, the term “polar hydrocarbon-based wax” means a wax whose chemical structure is formed essentially of, or even constituted of, carbon and hydrogen atoms, and which comprises at least one heteroatom more particularly chosen from oxygen, optionally nitrogen, or mixtures thereof. It may thus contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.

The term “silicone wax” means an oil comprising at least one silicon atom and notably comprising Si-O groups.

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

A wax chosen from ester waxes and alcohol waxes is preferred as polar hydrocarbon-based wax.

According to the invention, the term “ester wax” means a wax comprising at least one ester function. The ester waxes may also be hydroxylated.

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

Use may notably be made, as ester wax, alone or as mixtures, of:

i) waxes of formula R₁COOR₂ in which R₁ and R₂ represent linear, branched or cyclic aliphatic chains, the number of atoms of which ranges from 6 to 50, notably from 10 to 50, which may contain a heteroatom, for instance O or N, and the melting point of which ranges more particularly from 30°C to 120°C. In particular, use may be made, as ester wax, of a C₂₀-C₄₀ alkyl (hydroxystearyloxy)stearate (the alkyl group comprising from 20 to 40 carbon atoms), alone or as a mixture, or a C₂₀-C₄₀ alkyl stearate. Such waxes are notably sold under the names Kester Wax K 82 P^®, Hydroxypolyester K 82 P^®, Kester Wax K 80 P^® or Kester Wax K82H by the company Koster Keunen. Use may also be made of stearyl heptanoate and stearyl caprylate and mixtures thereof;

ii) bis(1,1,1-trimethylolpropane) tetrastearate,

iii) diester waxes of a dicarboxylic acid of general formula

R³-(-OCO-R⁴-COO-R⁵), in which R³ and R⁵ are identical or different, preferably identical, and represent a C₄-C₃₀ alkyl group and R⁴ represents a linear or branched aliphatic C₄-C₃₀ group which may or may not contain one or more unsaturations. Preferably, the C₄-C₃₀ aliphatic group is linear and unsaturated;

iv) mention may also be made of the waxes obtained by catalytic hydrogenation of animal or plant oils notably containing linear or branched C₈-C₃₂ fatty chains, for instance hydrogenated jojoba oil, hydrogenated sunflower oil, hydrogenated castor oil or hydrogenated coconut kernel oil, and also the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol, such as those sold in the Phytowax Castor range, for example Phytowax Castor 22L73^®, or else the waxes obtained by hydrogenation of olive oil esterified with stearyl alcohol, such as those of the Phytowax Olive range, for example Phytowax Olive 18L57, sold by the company Sophim. Such waxes are notably described in patent application FR2792190;

v) waxes corresponding to the partial or total esters, preferably total esters, of a saturated, optionally hydroxylated, C₁₆-C₃₀ carboxylic acid with glycerol. The term “total esters” means that all the hydroxyl functions of glycerol are esterified. Examples that may be mentioned include trihydroxystearine (or glyceryl trihydroxystearate), tristearine (or glyceryl tristearate) and tribehenine (or glyceryl tribehenate), alone or as a mixture. Among the suitable compounds, mention may be made of triesters of glycerol and of 12-hydroxystearic acid, or hydrogenated castor oil, for instance Thixcin R and Thixcin E sold by Elementis Specialties;

vi) Mention may also be made of waxes of animal or plant origin, such as beeswax, synthetic beeswax, carnauba wax, candelilla wax, rice bran wax, ouricury wax, esparto grass wax, cork fiber wax, sugar cane wax, Japan wax, sumac wax, montan wax, orange wax, laurel wax, or sunflower wax, in particular in refined form;

vii) mention may also be made of natural or synthetic polyalkylenated or polyglycerolated hydrocarbon-based waxes, of animal or plant origin; the number of (C₂-C₄) oxyalkylene units may range from 2 to 100, the number of glycerol units may range from 1 to 20. Examples that may be mentioned include polyoxyethylenated beeswaxes, such as PEG-6 beeswax or PEG-8 beeswax; polyoxyethylenated carnauba waxes, such as PEG-12 carnauba; polyoxyethylenated or polyoxypropylenated and hydrogenated or non-hydrogenated lanolin waxes, such as PEG-30 lanolin or PEG-75 lanolin; PPG-5 lanolin wax glyceride; polyglycerolated beeswaxes, notably polyglyceryl-3 beeswax, the Acacia Decurrens/Jojoba/Sunflower Seed Wax/Polyglyceryl-3 Esters mixture, polyglycerolated plant waxes, such as mimosa, jojoba or sunflower waxes, and mixtures thereof (Acacia Decurrens/Jojoba/Sunflower Seed Wax Polyglyceryl-3 Esters),

According to another embodiment, the polar wax may be an alcohol wax. As alcohol waxes, mention may be made of mixtures of saturated linear C₃₀-C₅₀ alcohols, for instance the wax Performacol 550 Alcohol from New Phase Technologies, stearyl alcohol and cetyl alcohol, or mixtures thereof.

Preferably, if the composition comprises any, the wax is chosen from hydrocarbon-based waxes. More particularly, it is chosen from apolar waxes; polar hydrocarbon-based waxes such as waxes of animal or plant origin, waxes of animal or plant origin obtained by catalytic hydrogenation of animal or plant oils; alcohol waxes; and also mixtures thereof; and preferably from apolar hydrocarbon-based waxes, alone or as mixtures.

The wax content, if the composition comprises any, advantageously ranges from 1% to 20% by weight, in particular from 5% to 15% by weight, relative to the total weight of the composition.

PASTY COMPOUNDS

The composition according to the invention may also comprise at least one compound which is pasty at room temperature and atmospheric pressure.

For the purposes of the present invention, the term “pasty” refers to a lipophilic compound with a reversible solid/liquid change of state, notably having in the solid state an anisotropic crystal organization, and including at room temperature a liquid fraction and a solid fraction.

In other words, the starting melting point of the pasty compound may be lower than room temperature. The liquid fraction of the pasty compound, measured at room temperature, may represent 9% to 97% by weight of the pasty compound. This fraction that is liquid at room temperature preferably represents between 15% and 85%, more preferably between 40% and 85%, by weight.

The melting point of the pasty fatty substance is determined according to the same principle as that described in detail previously for the waxes.

In the case of a pasty compound, the measurement protocol is, however, as follows:

A sample of 5 mg of pasty fatty substance placed in a crucible is subjected to a first temperature rise ranging from -20°C to 100°C, at a heating rate of 10°C/minute, is then cooled from 100°C to -20°C at a cooling rate of 10°C/minute and is finally subjected to a second temperature rise ranging from -20°C to 100°C at a heating rate of 5°C/minute.

The melting point of the pasty fatty substance is the value of the temperature corresponding to the top of the peak on the curve representing the variation in the difference in power absorbed as a function of the temperature.

It should be noted that the liquid fraction by weight of the pasty fatty substance at room temperature is equal to the ratio of the heat of fusion consumed at room temperature to the heat of fusion of the pasty fatty substance.

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

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

The pasty compound may in particular be chosen from synthetic pasty compounds and fatty substances of plant origin.

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

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

- petroleum jelly (also known as petrolatum),

- ethers of pentaerythritol and of C₂-C₄, polyalkylene glycol, for example the compounds having the following INCI names: PEG-5 Pentaerythrityl Ether, PPG-5 Pentaerythrityl Ether, and mixtures thereof. Mention may be made, for example, of the mixture sold under the name Lanolide by the company Vevy,

- liposoluble polyethers resulting from polyetherification between one or more C₂-C₁₀₀ and preferably C₂-C₅₀ diols. Among the liposoluble polyethers, consideration is given in particular to copolymers of ethylene oxide and/or of propylene oxide with long-chain C₆-C₃₀ alkylene oxides, more preferably such that the weight ratio of the ethylene oxide and/or propylene oxide to alkylene oxides in the copolymer is from 5:95 to 70:30. In this family, mention will notably be made of the product having the INCI name PEG-45/Dodecyl Glycol Copolymer sold, for example, under the brand name Elfacos ST9 by the company Akzo Nobel,

- esters resulting from the condensation of a preferably saturated, linear or branched, C₆-C₁₀ dicarboxylic acid and of an ester of diglycerol and of optionally hydroxylated, preferably saturated, linear or branched, C₆-C₂₀ monocarboxylic acids, in particular the diester obtained by condensation of adipic acid and of a mixture of esters of diglycerol with a mixture of C₆-C₂₀ fatty acids, such as caprylic acid, capric acid, stearic acid, isostearic acid and 12-hydroxystearic acid, notably sold under the reference Softisan® 649 by the company Cremer Oleo (INCI name: Bis-Diglyceryl Polyacyladipate-2),

- triglycerides of fatty acids which are optionally hydrogenated (totally or partially), saturated or unsaturated, linear or branched, optionally mono- or polyhydroxylated, preferably C₁₂-C₁₈; for instance the glycerides of saturated C₁₂-C₁₈ fatty acids sold under the name Softisan 100® by the company Cremer Oleo (INCI name: Hydrogenated Coco-Glycerides),

- esters of dimer diol, or of polyol, and of dimer diacid, for instance:

* esters of dimer of dilinoleyl alcohol and of dilinoleic acid, the hydroxyl groups of which are esterified with a mixture of phytosterols, of behenyl alcohol and of isostearyl alcohol, for example the ester sold under the name Plandool G by the company Nippon Fine Chemical (INCI name: Bis-Behenyl / Isostearyl / Phytosteryl Dimer Dilinoleyl Dimer Dilinoleate);

* esters of dilinoleic acid and of a mixture of phytosterols, of isostearyl alcohol, of cetyl alcohol, of stearyl alcohol and of behenyl alcohol, for example the ester sold under the name Plandool H or Plandool S by the company Nippon Fine Chemical (INCI name: Phytosteryl/Isostearyl/Cetyl/Stearyl/Behenyl Dimer Dilinoleate);

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

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

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

- and mixtures thereof.

If the composition comprises at least one pasty compound, its/their content ranges from 0.5% to 20% by weight, preferably from 1% to 15% by weight, relative to the total weight of the composition.

LIPOPHILIC THICKENERS

The composition according to the invention may also comprise at least one lipophilic thickener, chosen more particularly from silicas, which may or may not have been hydrophobically treated; lipophilic clays; alone or as a mixture.

Silicas

The composition according to the invention may thus comprise, as mineral thickener, a fumed silica, preferably a hydrophobic fumed silica, or silica aerogel particles, preferably hydrophobic silica aerogel particles.

Fumed silica

Fumed silica which has been hydrophobically surface treated is suitable for use in the invention. It is in fact possible to chemically modify the surface of the silica, by chemical reaction generating a reduction in the number of silanol groups present at the surface of the silica. It is possible in particular to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained.

The hydrophobic groups may be:

- trimethylsiloxyl groups, which are notably obtained by treating fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are known as "Silica Silylate" according to the CTFA (8th edition, 2000). They are sold, for example, under the references Aerosil R812^® by Degussa, and Cab-O-Sil TS-530^® by Cabot.

- dimethylsilyloxyl or polydimethylsiloxane groups, which are notably obtained by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are known as "Silica Dimethyl Silylate" according to the CTFA (8th edition, 2000). They are sold, for example, under the references Aerosil R972^® and Aerosil R974^® by Degussa and Cab-O-Sil TS-610^® and Cab-O-Sil TS-720^® by Cabot.

Silica aerogels

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

They are generally synthesized via a sol-gel process in a liquid medium and then dried, usually by extraction with a supercritical fluid, the one most commonly used being supercritical CO₂. This type of drying makes it possible to avoid shrinkage of the pores and of the material. The sol-gel process and the various drying operations are described in detail in Brinker C.J. and Scherer G.W., Sol-Gel Science, New York, Academic Press, 1990.

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

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

The sizes of the silica aerogel particles may be measured by static light scattering using a commercial MasterSizer 2000 particle size analyzer from Malvern. The data are processed on the basis of the Mie scattering theory. This theory, which is exact for isotropic particles, makes it possible to determine, in the case of non-spherical particles, an “effective” particle diameter. This theory is in particular described in the publication by Van de Hulst, H.C., Light Scattering by Small Particles, Chapters 9 and 10, Wiley, New York, 1957.

According to an advantageous embodiment, the hydrophobic silica aerogel particles used in the present invention have a specific surface area per unit mass (S_M) ranging from 600 to 800 m²/g and a size expressed as the volume-mean diameter (D[0.5]) ranging from 5 to 20 µm and even better still from 5 to 15 µm.

The aerogels are aerogels of hydrophobic silica, preferably of silylated silica (INCI name: Silica Silylate).

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

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

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

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

Mention may also be made of the aerogels sold by the company Cabot under the references Aerogel TLD 201, Aerogel OGD 201, Aerogel TLD 203, Enova® Aerogel MT 1100 and Enova Aerogel MT 1200.

Mention may also be made of the aerogel sold under the name VM-2270 (INCI name: Silica Silylate) by the company Dow Corning, the particles of which have a mean size ranging from 5-15 microns and a specific surface area per unit mass ranging from 600 to 800 m²/g.

Lipophilic clays

The term “lipophilic clay” refers to any clay that is liposoluble or lipodispersible in the oily phase of the composition.

Clay denotes a material based on hydrated silicates and/or aluminosilicates, of lamellar structure.

The clays may be natural or synthetic, and they are made lipophilic by treatment with an alkylammonium salt such as a C10 to C22 ammonium chloride, in particular stearalkonium chloride or distearyldimethylammonium chloride. They are not considered to be fillers.

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

They are preferably chosen from hectorites and bentonites.

For example, use may be made of a lipophilic clay chosen from hydrophobically modified bentonites and hydrophobically modified hectorites, notably modified with a C10 to C22 quaternary ammonium chloride, such as:

- a bentonite modified with stearalkonium chloride, such as the commercial products sold under the name Claytone AF®, Garamite VT®, Tixogel® LG-M, Tixogel® MP 250 Tixogel® VZ and Tixogel® VZ-V XR, by the company BYK Additives Inc; or the commercial products sold under the name Viscogel® B3, Viscogel® B4, Viscogel® B7, Viscogel® B8, Viscogel® ED, Viscogel® GM, Viscogel® S4 and Viscogel® SD by the company Bentec S.P.A;

- a bentonite modified with stearalkonium chloride in the presence of at least propylene carbonate and at least one oil, such as the commercial products Dub Velvet Gum® from the company Stéarinerie Dubois Fils, Miglyol Gel T® from the company Cremer Oleo, Tixogel® CGT 6030, Tixogel® DBA 6060, Tixogel® FTN, Tixogel® FTN 1564, Tixogel® IPM, Tixogel® LAN, Tixogel® LAN 1563 from the company BYK Additives Inc.;

- a hectorite modified with distearyldimethylammonium chloride (INCI name: Disteardimonium Hectorite), for instance the product sold under the name Bentone® 38VCG Rheological Additive by the company Elementis Specialties;

- a hectorite modified with distearyldimethylammonium chloride in the presence of at least propylene carbonate or triethyl citrate and of at least one oil, such as the commercial products sold under the name Bentone® Gel DOA V, Bentone® Gel EUG V, Bentone® Gel IHD V, Bentone® Gel ISD V, Bentone® Gel MIO V, Bentone® Gel PTM V, Bentone® SS-71 V, Bentone® VS-5 PC V or Bentone® VS-5 by the company Elementis Specialities; the commercial products sold under the name Creagel Bentone CPS/Hectone CPS or Creagel Bentone ID/Hectone ID by the company Créations Couleurs; the commercial products sold under the name NS Gel DM1®, NS Gel PTIS® or NS MGel 1152® by the company Next Step Laboratories Stop.

Preferably, the lipophilic gelling agent may be present in the composition in concentrations preferably ranging from 0.1% to 5% by weight, and more preferentially from 0.2% to 3% by weight relative to the total weight of the composition.

According to a particularly advantageous variant, the present invention relates to a cosmetic composition, preferably for making up human keratin materials, in particular the skin and/or the lips, preferably the lips, which is preferably liquid at room temperature and atmospheric pressure, comprising, in a physiologically acceptable medium:

- at least one natural resin,

(i) at least one polyglycerol-3,

(ii) at least one dimer acid, and

(iii) at least one fatty monoacid containing from 8 to 30 carbon atoms;

the reacted components (i), (ii) and (iii) being in a mole ratio of 1 mol of polyglycerol-3, 0.5 to 1 mol of dimer acid and from 0.1 to less than 2.0 mol of fatty monoacid,

- at least one volatile oil,

- at least one filler of silica type, preferably spherical, preferably chosen from precipitated silicas, which has advantageously not been subjected to a hydrophobic surface treatment; the composition:

* optionally comprising at least one volatile or nonvolatile silicone oil in a content not exceeding 5% by weight and advantageously not exceeding 3% by weight, relative to the total weight of the composition; preferably, the composition is free of any;

* optionally comprising at least one silicone polymer, more particularly chosen from silicone resins, from silicone acrylate polymers, acrylamide-silicone copolymers, or mixtures thereof, in a content not exceeding 5% by weight, advantageously not exceeding 3% by weight, relative to the total weight of the composition; preferably, the composition is free of any.

COSMETIC APPLICATIONS

A subject of the invention is also a process for treating human keratin materials, notably for making up and/or caring for keratin materials, in which the composition according to the invention is applied.

Thus, the composition used according to the invention may be a composition for caring for and/or making up keratin materials such as the skin, the lips, the contour of the eyes, the eyelids, the eyelashes or the eyebrows.

In particular, the composition according to the invention is a makeup product for the skin such as foundations, face powders and eyeshadows.

In particular, the composition according to the invention is a makeup product for the lips, such as a lipstick or lip gloss.

In particular, the composition according to the invention is an eye contour makeup product such as an eyeliner, or a product for the eyelashes or the eyebrows such as a mascara.

Such compositions are notably prepared according to the general knowledge of a person skilled in the art.

The composition according to the invention may also form part of a packaging assembly, or kit, comprising:

- a packaging device comprising said cosmetic composition according to the invention as described previously,

- an applicator for said composition.

The container can delimit one or more compartment(s). The container may be, for example, in the form of a tube or a heating bag.

Such an applicator may be integral with a cap reversibly mounted on said container between a position of closure of said container and a position of application, notably of makeup.

It is also pointed out that the compositions according to the invention more particularly comprise a cosmetically (or physiologically) acceptable medium, i.e. one which has a pleasant color, odor and feel and which does not give rise to any unacceptable discomfort, i.e. stinging, tautness or redness, that is liable to discourage the user from applying such compositions.

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

The expressions “between ... and ...” and “ranging from ... to ...” should be understood as meaning limits included, unless otherwise specified.

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

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

The starting materials are referred to by their chemical or INCI name.

EXAMPLES Protocol for measuring the viscosity

The viscosity measurement is performed with a sample of the composition at 25°C, at least 24 hours after its manufacture (storage at room temperature, sealed container), using a Rheomat RM180 viscometer equipped with a No. 2, 3 or 4 spindle, the measurement being performed after 10 minutes of rotation of the spindle in the formulation, at a shear rate of 200 revolutions/minute (rpm).

Protocol for measuring the tack

The composition is deposited on several stainless steel dishes with a depth of 100 μm and levelled as quickly as possible. The dishes are left to dry at ambient temperature for one hour.

The apparatus used is a TAXT2i texture analyser. The clamp mounted on the apparatus grips an AU4G cylinder with a diameter of 6 mm, at the end of which is adhesively bonded a smooth beige synthetic skin end piece of the same diameter and with a thickness of 2 mm.

The end piece is cleaned with ethanol between each measurement.

More than one measurement is never taken at the same place in the deposit.

The parameters of the compression tests with holding over time are indicated below:

Approach speed (or pre-speed)	1 mm/s
Speed (from detection of contact)	0.1 mm/s
Force (and corresponding pressure)	0.283 N (i.e. 0.01 MPa)
Holding time	3 seconds
Withdrawal speed (or post-speed)	0.1 mm/s

The tack is characterized by the work of detachment measured during the unloading (tensile phase), corresponding to the integral of the curve under the time axis. This work is expressed positively in joules per square metre.

Protocol for measuring the wear property and the transfer

1. Preparation of the test:

Support: Beige Supplale (2.5 x 5 cm) (sold by Soudotique).

Spread the composition using a dip applicator with flocked tip (gloss applicator) over the entire surface 3 times in succession to have a sufficient and homogeneous deposit. Repeat the operation on two other strips.

Allow the deposit to dry on a plate heated to 32°C for 45 minutes.

If necessary, take a photo of each support with the deposit (made up) before stressing.

2. Stresses: Preparation of a paper tissue for each stress:

Fold each paper tissue twice along the long edge and then twice in the other direction to form a square.

Dry resistance:

Rub once with the folded tissue lengthwise against one of the three made-up supports; the force applied is that normally exerted when removing makeup from the skin or the lips.

Observe the state of the rubbed support and the used surface of the tissue, in particular the remaining color and the transferred color.

If necessary, take a photo.

It should be noted that the transfer resistance is evaluated with this stress.

If several passes are made, they would be performed with the same force and always in the same direction (i.e. after each pass, the tissue is lifted to be repositioned at the “start” of the strip so as to be reapplied on the deposit in the same way as the previous pass). If necessary, take a photo between each step or only at the end of the evaluation. This type of process can be used to evaluate the overall resistance of the deposit.

Water resistance :

Insert the second made-up support, without folding it, into a centrifuge tube.

Add 10 grams of demineralized water.

Centrifuge for 10 minutes at 450g.

If necessary, take a photo of the support after mixing, immediately after the operation.

Rub once with a tissue along the length of the support, without waiting, with the same force as that applied for the dry resistance.

If necessary, take a photo.

The protocol for multiple passes is the same as that detailed previously for the dry resistance.

Oil resistance:

Perform the same protocol as for the water resistance, on the third made-up support, replacing the water with the same amount of olive oil (Refined Olive Oil - Aarhuskarlshamn).

Grading:

For each stress, record the result according to the table below:

Deposit grade	State of the deposit	Tissue grade	Surface of the tissue in contact with the deposit
5	Total or partial removal of the deposit from the rubbed area; the surface of the support appears in places	5	Very intense coloring - very substantial to total color transfer
4	Partial removal resulting in significantly and visibly less intense coloring of the deposit.	4	Intense coloring - substantial color transfer
3	Decrease in color intensity of the deposit which is noticeable but does not reveal the support	3	Medium coloring - moderate color transfer
2	No substantial change in the deposit color	2	Slight coloring - little color transfer
1	No variation in the deposit color	1	No coloring or barely visible coloring - very little or no color transfer

Example 1 1. Compositions

The following compositions, the list of ingredients and mass percentages of the contents of which are collated in the table below, were prepared.

In these examples, the wear properties of a lipstick according to the invention containing a silica-type filler (composition 1) are compared with a lipstick not containing any filler (composition A).

Phase	Ingredients (INCI name or chemical name)	1 Invention	2 Invention	3 Invention	A Comp.
A	Tribehenin (Syncrowax HRC-PA-(MH) from Croda)	2	2	2	2
B	Diisostearoyl Polyglyceryl-3 Dimer Dilinoleate (60%) (and) Caprylic/Capric Triglyceride (40%) (SolAmaze Natural® - Nouryon)	15	15	15	15
C	Isododecane	qs 100	qs 100	qs 100	qs 100
D	Isopropylidene glycerol (Augeocrystal from Solvay)	8	8	8	8
D	Denatured alcohol	20	20	20	20
E	Ethylcellulose (Aqualon EC N7 Pharm from Ashland)	5	5	5	5
F	Euphorbia Cerifera (Candelilla) Wax Extract (Candellila Resin E-1 from Japan Natural Products)	2.5	2.5	2.5	2.5
F	Protium Heptaphyllum Resin (Citrobreu from Citroleo)	2.5	2.5	2.5	2.5
G	Silica (SUNSPHERE H 51 from AGC-SI Tech)	5	-	-	-
G	Silica (SILICA SHELLS from Kobo)	-	5	-	-
G	Silica (and) sodium chloride (Resifa FB-82 from AGC-SI tech)	-	-	5	-
H	Mica (Mearlmica SV, Sun Chemicals)	2.5	2.5	2.5	2.5
H	Red 7 (Unipure Red LC 3079, Sensient)	7.5	7.5	7.5	7.5
I	Oleic acid (Wilfarin OA-7075 from Wilmar)	3.0	3.0	3.0	3.0
	Total	100	100	100	100

2. Preparation of the compositions

1. In a beaker, mix the polyester (B) and the tribehenin at 60°C with stirring. Once the mixture has been homogenized, allow it to return to room temperature and add the isododecane with stirring (Rayneri deflocculator at 500 rpm) until a homogeneous mixture is obtained.

2. Add the isopropylidene glycerol with stirring at 500 rpm, then the denatured alcohol (Rayneri deflocculator at 500 rpm) to obtain a homogeneous mixture, then add the ethanol under the same conditions.

3. Once the mixture has been homogenized, introduce the ethylcellulose (E) as a fine mist into the vortex created by the deflocculator at 500 rpm and then leave stirring (approximately 10 minutes).

4. Once the mixture has been homogenized, introduce the previously ground resins (F) as a fine mist, with the deflocculator at 500 rpm, and then leave stirring to obtain a homogenous mixture (approximately 10 minutes).

5. Introduce, as appropriate, the silica (G), while maintaining the stirring until a homogeneous mixture is obtained.

6. Preparation of phase H: place the ingredients of phase H in the bowl of an IKA MV20 mill and blend at maximum speed four times for 15 seconds, taking care after each 15 seconds to loosen any powder that may have adhered to the walls.

7. Add phase H to the mixture from step 5.

8. Finally, introduce oleic acid, with stirring at 500 rpm, until the mixture is homogenized.

9. Package the resulting composition in a pot fitted with a dip applicator with a flocked tip (gloss applicator).

3. Evaluation of the compositions

Each composition is stable and is easily applied to the lips as a uniform and comfortable deposit.

The table below collates the results of the evaluations of dry resistance, water resistance and oil resistance as described above:

	Deposit grade			Tissue grade
Type of stress	Dry	Water	Oil	Dry	Water	Oil
Composition 1 Invention	2	1	2	2	1	3
Composition 2 Invention	1	2	2	2	1	3
Composition 3 Invention	1	1	2	2	1	3
Composition A Comparative	3	5	5	3	3	5

It is found that the presence of a silica-type filler makes it possible to improve the wear property performance and also to reduce the color transfer, compared to the composition which is free thereof.

Example 2 1. Compositions

In these examples, the holding properties of a lipstick according to the invention containing a silica-type filler (composition 4) are compared with a lipstick not containing any filler (composition C).

Phase	Ingredients (INCI name or chemical name)	4 Invention	B Comparative	C Comparative
A	Diisostearoyl Polyglyceryl-3 Dimer Dilinoleate (60%) (and) Caprylic/Capric Triglyceride (40%) (SolAmaze Natural® - Nouryon)	15	15	15
B	Isododecane	qs 100	qs 100	qs 100
B	C9-12 alkane (Vegelight Silk 100 - Biosynthis)	5	5	5
C	Disteardimonium hectorite (and) propylene carbonate (Bentone Gel ISD V - Elementis)	10	10	10
D	Denatured alcohol	20	20	20
E	Ethylcellulose (Aqualon EC N7 Pharm from Ashland)	5	5	5
F	Euphorbia Cerifera (Candelilla) Wax Extract (Candellila Resin E-1 - Japan Natural Products)	5	5	5
G	Silica (Silica Shells - Kobo)	5	-	-
G	Calcium carbonate (Omyacare Extra 35-OG, Omya)	-	-	5
H	Mica (Mearlmica SV, Sun Chemicals)	2.5	2.5	2.5
H	Red 7 (Unipure Red LC 3079, Sensient)	7.5	7.5	7.5
I	Oleic acid (Wilfarin OA-7075 - Wilmar)	3	3	3
	Total	100	100	100

2. Preparation of the compositions

1. In a beaker, mix the polyester, isododecane and C9-12 alkane with stirring (Rayneri deflocculator at 500 rpm) until a homogeneous mixture is obtained.

2. Add the mixture with disteardimonium hectorite (C) while stirring at 500 rpm to obtain a homogeneous mixture, then add the ethanol under the same conditions.

4. Once the mixture has been homogenized, introduce the previously ground candelilla resin (F) as a fine mist, with the deflocculator at 500 rpm, and then leave stirring to obtain a homogeneous mixture (around 10 minutes).

5. Introduce the filler (G) while maintaining stirring until a homogeneous mixture is obtained.

7. Add phase H to the mixture from step 5.

9. Package the resulting composition in a hot water bottle equipped with a dip applicator with flocked tip (gloss applicator).

3. Evaluation of the compositions

	Deposit grade			Tissue grade
Type of solicitation	Dry	Water	Oil	Dry	Water	Oil
Composition 4 Invention	2	2	2	2	1	3
Composition B Comparative	3	3	5	3	2	5
Composition C Comparative	2	2	4	2	2	5

It is found that the presence of a silica-type filler makes it possible to improve the wear property performance and also to reduce the color transfer.

Example 3 1. Composition

The following composition, the list of ingredients and the mass percentage contents of which are collated in the table below, was prepared:

Phase	Ingredients (INCI name or chemical name)	5 Invention
A	Tribehenin (SYNCROWAX HRC-PA-(MH) - Croda)	2
B	Diisostearoyl polyglyceryl-3 dimer dilinoleate (SolAmaze Natural® - Nouryon)	15
C	Isododecane	20
C	C9-12 alkane (Vegelight Silk 100 - Biosynthis)	4.55
D	Disteardimonium hectorite (and) propylene carbonate (BENTONE GEL ISD V - Elementis)	10
E	Denatured alcohol	20.46
F	Ethylcellulose (AQUALON EC N7 PHARM from Ashland)	5
G	Euphoria cerifera (candellilla) wax extract / euphorbia cerifera cera extract (CANDELILLA RESIN E-1 from Japan Natural Products)	5
H	Silica (Sunsphere H 51 from AGC Si-Tech)	2.5
H	Silica (Silica SHELLS from Kobo)	2.5
I	Mica (Mearlmica SV, Sun Chemicals)	1.45
I	Red 7 (Unipure Red LC 3079, Sensient)	2.1
I	Black iron Oxide (SunPURO Black Iron Oxide C33-7001 from Sun Chemical)	0.14
I	Red 28 (SunCROMA D&C Red 28 AL Lake C14-6623 from Sun Chemical)	6.3
J	Oleic acid (Wilfarin OA-7075 from Wilmar)	3
	Total	100

2. Preparation of the compositions:

1. In a beaker, melt the polyester and the tribehenin at 60°C; then allow the mixture to return to room temperature.

2. Add the isododecane and C9-12 alkane with stirring (Rayneri deflocculator at 500 rpm) until a homogeneous mixture is obtained.

3. Add the mixture with disteardimonium hectorite (D) while maintaining the stirring at 500 rpm to obtain a homogeneous mixture, then add the ethanol under the same conditions.

4. Once the mixture has been homogenized, introduce the ethylcellulose (F) as a fine mist into the vortex created by the deflocculator at 500 rpm, and then leave stirring (around 10 minutes).

5. Once the mixture has been homogenized, introduce the previously ground candelilla resin (G) as a fine mist, with the deflocculator at 500 rpm, and then leave stirring to obtain a homogeneous mixture (around 10 minutes).

7. Add phase H to the mixture from step 5.

3. Evaluation of the composition

A stable composition is obtained, which is easily applied to the lips as a uniform and comfortable deposit.

	Deposit grade			Tissue grade
Type of solicitation	Dry	Water	Oil	Dry	Water	Oil
Composition 5 Invention	1	1	2	2	1	3

It is found that the presence of a silica-type filler makes it possible to improve the holding performance and to reduce the color transfer.

Claims

A cosmetic composition, preferably for making up human keratin materials, in particular the skin and/or the lips, preferably the lips, which is preferably liquid at room temperature and atmospheric pressure, comprising, in a physiologically acceptable medium:
- at least one natural resin,
- at least one alkylcellulose, the alkyl group of which is a C₂-C₃ alkyl group, preferably ethylcellulose,
- at least one polyester which is the reaction product of the following components (i), (ii) and (iii):
(i) at least one polyglycerol-3,
(ii) at least one dimer acid, and
(iii) at least one fatty monoacid containing from 8 to 30 carbon atoms;
the reacted components (i), (ii) and (iii) being in a mole ratio of 1 mol of polyglycerol-3, 0.5 to 1 mol of dimer acid and from 0.1 to less than 2.0 mol of fatty monoacid,
- at least one C₂-C₆, more particularly C₂-C₄ monoalcohol, preferably ethanol,
- at least one volatile oil,
- optionally at least one volatile polar hydrocarbon-based solvent, preferably compatible with the abovementioned polyester,
- optionally at least one nonvolatile hydrocarbon-based oil, other than the abovementioned polyester, or nonvolatile silicone oil, and also mixtures thereof,
- at least one silica-type filler, which is preferably spherical.
The composition as claimed in the preceding claim, characterized in that the natural resin is chosen from the following resins, alone or as a mixture:
- resins extracted from plant waxes, preferably extracts of Euphorbia cerifera (candelilla) wax;
- frankincense resins, preferably Protium heptaphyllum resin, or Protium resin, or White Breu resin;
- frankincense resins originating from the sal tree, Shorea robusta resin; and
- rosins, preferably rosin acid esters such as glyceryl rosinate, pentaerythrityl rosinate or hydrogenated rosinates such as hydrogenated pentaerythrityl rosinate or hydrogenated methyl rosinate;
and preferably from resins extracted from Euphorbia cerifera (candelilla) wax, frankincense resins, such as Protium heptaphyllum resin, or Protium resin, or White Breu resin and frankincense resins originating from the sal tree, such as the Shorea robusta resin.
The composition as claimed in either of the preceding claims, characterized in that the natural resin, expressed as active material, represents from 0.5% to 30% by weight, more particularly from 2% to 25% by weight and preferably from 3% to 20% by weight relative to the total weight of the composition.
The composition as claimed in any one of the preceding claims, characterized in that the content of alkylcellulose represents from 0.5% to 20% by weight, advantageously from 1% to 15% by weight, preferably from 2% to 15% by weight, relative to the total weight of the composition.
The composition as claimed in any one of the preceding claims, characterized in that the polyester is a substantially or totally nonsequential reaction product, preferably prepared by a one-step process which involves the introduction of all the reagents into a reaction vessel and the subsequent induction of an entirely random addition of the dimer acid and of the isostearic acid to the polyglycerol-3.
The composition as claimed in any one of the preceding claims, characterized in that the polyester is a substantially or totally nonsequential product of reaction of the following components:
(i) at least one polyglycerol-3 in the form of a mixture comprising at least 25% by weight of diglycerol, at least 45% by weight of triglycerol and at least 10% by weight of tetraglycerol, in each case relative to the total weight of the polyglycerol-3 in the form of a mixture;
(ii) at least one hydrogenated dimer acid containing at least 60% by weight of hydrogenated C36 diacid and from 5% to 25% by weight of hydrogenated C54 triacid, in each case relative to the total weight of hydrogenated acid; and
(iii) isostearic acid.
The composition as claimed in any one of the preceding claims, characterized in that the polyester is a reaction product of polyglycerol-3, of hydrogenated C₃₆ dimer acid and of isostearic acid in a mole ratio of 1/0.5/1.
The composition as claimed in any one of the preceding claims, characterized in that the content of polyester, expressed as active material, represents from 2.5% to 30% by weight and preferably from 5% to 20% by weight, relative to the total weight of the composition.
The composition as claimed in any one of the preceding claims, characterized in that the content of monoalcohol represents from 2% to 40% by weight, more particularly from 3% to 35% by weight, preferably from 5% to 30% by weight, relative to the total weight of the composition.
The composition as claimed in any one of the preceding claims, characterized in that the volatile oil(s) are chosen from volatile nonpolar hydrocarbon-based oils, volatile silicone oils, and mixtures thereof; and preferably from branched C₈-C₁₆ alkanes, linear C₈-C₁₄ alkanes, and also mixtures thereof, and preferably from isododecane, undecane and tridecane, alone or as mixtures.
The composition as claimed in any one of the preceding claims, characterized in that the content of volatile, preferably hydrocarbon-based, oil(s) represents from 5% to 40% by weight and preferably from 15% to 35% by weight, relative to the total weight of the composition.
The composition as claimed in any one of the preceding claims, characterized in that the volatile polar hydrocarbon-based solvent, preferably compatible with the abovementioned polyester, is chosen, alone or as a mixture, from linear, branched or cyclic saturated compounds, of the following formula: C_nH_2nO₃, wherein n is an integer ranging from 5 to 9, preferably from 6 to 9, said compound comprising at least one hydroxy (-OH) function and at least one function chosen from ether (-O-) and/or ester (-O-C(=O)-), preferably chosen from linear or branched saturated lactates containing from 6 to 9 carbon atoms, 1,2-isopropylideneglycerol, and mixtures thereof, and preferably butyl lactate, 1,2-isopropylideneglycerol, and mixtures thereof.
The composition as claimed in any one of the preceding claims, characterized in that the content of volatile polar hydrocarbon-based solvent(s), preferably compatible with the abovementioned polyester, represents from 1% to 30% by weight and preferably from 2% to 25% by weight, relative to the total weight of the composition.
The composition as claimed in any one of the preceding claims, characterized in that the silica has a mean particle size (d[50] by volume) of between 0.5 and 30 µm, preferably between 1 and 20 µm.
The composition as claimed in any one of the preceding claims, characterized in that the silica is precipitated, preferably not having been subjected to a hydrophobic surface treatment.
The composition as claimed in any one of the preceding claims, characterized in that the composition has a silica content of between 0.2% and 10% by weight, preferably from 0.5% to 7% by weight, relative to the total weight of the composition.
The composition as claimed in any one of the preceding claims, characterized in that the water content represents less than 20% by weight and preferably less than 10% by weight, relative to the total weight of the composition.
The composition as claimed in any one of the preceding claims, characterized in that it comprises at least one nonvolatile hydrocarbon-based oil, other than the abovementioned polyester, chosen from polar nonvolatile hydrocarbon-based oils, nonpolar nonvolatile hydrocarbon-based oils, and also mixtures thereof, preferably from polar nonvolatile hydrocarbon-based oils, and in particular chosen from fatty alcohols, esters and mixtures thereof.
The composition as claimed in any one of the preceding claims, characterized in that the nonvolatile hydrocarbon-based oil is chosen from octyldodecanol, plant oils, ester oils, which are optionally hydroxylated, comprising 1 to 4 ester functions, at least one of which is linear or branched, saturated, unsaturated or aromatic, comprising at least 8 carbon atoms, and also mixtures thereof; and preferably from octyldodecanol, fatty acid triglycerides containing from 8 to 24 carbon atoms, notably such as Caprylic/Capric Triglyceride (INCI name), plant oils, and also mixtures thereof.
The composition as claimed in the preceding claim, characterized in that the content of nonvolatile, preferably hydrocarbon-based oil(s) ranges from 0.5% to 20% by weight and preferably from 1% to 10% by weight, relative to the total weight of the composition.
A process for treating, preferably for making up, human keratin materials, in particular the skin and/or the lips, preferably the lips, in which the composition as claimed in any one of the preceding claims is applied.