WO2012069319A2 - Composition for making up keratin fibres - Google Patents

Abstract

The present invention relates to a cosmetic makeup composition comprising a continuous oily phase, and containing: - at least one lipophilic film-forming polymer, - at least one apolar wax, - at least one polar wax, and - at least one surfactant having, at 25°C, an HLB balance, within the Griffin meaning, of less than or equal to 6. The present invention also relates to a process for coating keratin fibres with said cosmetic composition.

Description

COMPOSITION FOR MAKING UP KERATIN FIBRES

The present invention relates to cosmetic compositions for making up keratin fibres which are capable of resisting water and of being easily removed.

More particularly, the compositions according to the invention may constitute a makeup product for the eyelashes, eyebrows and hair, and more particularly an eyelash makeup product.

It may in particular be a makeup composition, a transparent or coloured composition to be applied over or under a makeup, also known, respectively, as "top coat" or "base coat", or alternatively a composition for treating the eyelashes.

The composition according to the invention may be in the form of a product for the eyelashes or mascara, of a product for the eyebrows or of a makeup product for the hair. More especially, the invention relates to a mascara.

There are in practice essentially two types of mascara formulation, namely, firstly, mascaras with an aqueous continuous phase, known as "emulsion mascaras", which are in the form of an emulsion of waxes in water, and, secondly, mascaras with a solvent or oil continuous phase, which are anhydrous or have a low content of water and/or water- soluble solvents, known as "waterproof mascaras", which are formulated in the form of a dispersion, in nonaqueous solvents, of at least one oily structuring agent which may be a wax, a polymer, in particular a semi-crystalline polymer, or a lipophilic gelling agent.

The present invention relates to the compositions or mascaras of "waterproof type as defined above.

These "waterproof mascaras are known to give rise to difficult, or even impossible, makeup removal with certain makeup removers, in particular makeup removers that are mainly water-based or water-soluble, especially aqueous solutions. The makeup removal is therefore as a general rule performed using specific makeup removers based on oils or on organic solvents. However, these makeup removers may be irritant to the eyes, may especially cause stinging or may leave a veil on the eyes, or alternatively may leave an uncomfortable greasy residual film on the skin around the eyes (eyelids).

There is therefore a need for cosmetic makeup compositions that are capable of showing both good water resistance and a good ability to be removed, including with the usual makeup removers. Documents FR 2 785 801, EP 1 152 022, FR 2 774 996, WO 95/35089 and WO 99/26445 describe thickening compositions, known as "thickening latices", "thickeners" or "inverse latices".

Documents FR 2 785 801 and FR 2 774 996 especially disclose compositions comprising an aqueous phase, an oily phase, an emulsifier of O/W (oil-in-water) type and an emulsifier of W/O (water-in-oil) type, and also a branched or crosslinked anionic polyelectrolyte based on a monomer containing a strong acid function.

Document WO 99/52499 describes mainly lipsticks comprising a sodium polyacrylate, for the purpose of producing a volumizing effect.

It has now been discovered that it is possible to obtain cosmetic compositions for making up keratin fibres, which are capable of combining improved makeup removal irrespective of the type of makeup remover and excellent water resistance and sebum resistance.

According to a first aspect, the present invention relates to a cosmetic makeup composition comprising a continuous oily phase, and containing:

- at least one lipophilic film-forming polymer,

- at least one apolar wax,

- at least one polar wax, and

- at least one surfactant having, at 25°C, an HLB balance, within the Griffin meaning, of less than or equal to 6.

As emerges from the examples below, the compositions according to the invention show such technical advantages.

According to a second aspect, the present invention also relates to a process for coating eyelashes with a makeup composition as defined previously, in which said process comprises a step of applying said composition to keratin fibres, and in particular eyelashes.

Continuous oily phase

The expression "cosmetic composition with an oily continuous phase" is understood to mean a system capable of becoming diluted or dispersed on contact with said solvent medium or oil. The composition according to the invention thus comprises an oily medium, constituting an oily phase, which forms the continuous phase of the composition. The oily phase of the composition according to the invention is thus a continuous oily phase. The expression "composition with a continuous oily phase" is understood to mean that the composition has a conductivity, measured at 25°C, of less than 23 μ8/αη (microSiemens/cm), the conductivity being measured, for example, using an MPC227 conductimeter from Mettler Toledo and an Inlab730 conductivity measuring cell. The measuring cell is immersed in the composition so as to remove the air bubbles that might be formed between the two electrodes of the cell. The conductivity reading is taken once the conductimeter value has stabilized. A mean is determined on at least three successive measurements.

Preferably, the oily phase of the composition according to the invention is present in an amount at least equal to 30% by weight relative to the total weight of the composition, preferably in an amount at least equal to 40% by weight.

Oil or organic solvent

The compositions according to the present application thus contain one or more oil(s) or organic solvent(s). The term "oil" means a fatty substance that is liquid at room temperature and at atmospheric pressure. The composition according to the invention may comprise at least one volatile oil and/or at least one non-volatile oil, and mixtures thereof. Volatile oil

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

The term "volatile oil" means an oil (or non-aqueous medium) that can evaporate on contact with the skin in less than one hour, at room temperature and atmospheric pressure. The volatile oil is a cosmetic volatile oil, which is liquid at room temperature. More specifically, a volatile oil has an evaporation rate of between 0.01 and 200 mg/cm²/min, limits included. To measure this evaporation rate, 15 g of oil or of oil mixture to be tested are placed in a crystallizing dish 7 cm in diameter, which is placed on a balance in a large chamber of about 0.3 m³ that is temperature-regulated, at a temperature of 25°C, and hygrometry-regulated, at a relative humidity of 50%. The liquid is allowed to evaporate freely, without stirring it, while providing ventilation by means of a fan (Papst-Motoren, reference 8550 N, rotating at 2700 rpm) placed in a vertical position above the crystallizing dish containing said oil or said mixture, the blades being directed towards the crystallizing dish, 20 cm away from the bottom of the crystallizing dish. The mass of oil remaining in the crystallizing dish is measured at regular intervals. The evaporation rates are expressed in mg of oil evaporated per unit area (cm²) and per unit of time (minutes).

This volatile oil may be hydrocarbon-based.

The volatile hydrocarbon-based oil may be chosen from hydrocarbon-based oils containing from 7 to 16 carbon atoms.

The composition according to the invention may contain one or more volatile branched alkane(s). The expression "one or more volatile branched alkane(s)" means, without preference, "one or more volatile branched alkane oil(s)".

As volatile hydrocarbon-based oils containing from 7 to 16 carbon atoms, mention may be made especially of C₈-Ci₆ branched alkanes, for instance C₈-Ci₆ isoalkanes (also known as isoparaffins), isododecane, isodecane, isohexadecane and for example the oils sold under the trade names Isopar or Permethyl, C₈-Ci₆ branched esters such as isohexyl neopentanoate, and mixtures thereof. Preferably, the volatile hydrocarbon-based oil containing from 8 to 16 carbon atoms is chosen from isododecane, isodecane and isohexadecane, and mixtures thereof, and is especially isododecane.

The composition according to the invention may contain one or more volatile linear alkane(s). The term "one or more volatile linear alkane(s)" means, without preference, "one or more volatile linear alkane oil(s)".

A volatile linear alkane that is suitable for the invention is liquid at room temperature (about 25°C) and at atmospheric pressure (760 mmHg).

A "volatile linear alkane" that is suitable for the invention means a cosmetic linear alkane, which is capable of evaporating on contact with the skin in less than one hour, at room temperature (25°C) and atmospheric pressure (760 mmHg, i.e. 101 325 Pa), which is liquid at room temperature, especially having an evaporation rate ranging from 0.01 to 15 mg/cm²/min, at room temperature (25°C) and atmospheric pressure (760 mmHg).

The linear alkanes, preferably of plant origin, comprise from 7 to 15 carbon atoms, in particular from 9 to 14 carbon atoms and more particularly from 11 to 13 carbon atoms.

As examples of linear alkanes that are suitable for the invention, mention may be made of the alkanes described in patent applications WO 2007/068 371 or WO 2008/155 059 by the company Cognis (mixtures of distinct alkanes that differ by at least one carbon). These alkanes are obtained from fatty alcohols, which are themselves obtained from coconut oil or palm oil.

As examples of linear alkanes that are suitable for the invention, mention may be made of n-heptane (C7), n-octane (C8), n-nonane (C9), n-decane (CIO), n-undecane (CI 1), n-dodecane (C12), n-tridecane (C13), n-tetradecane (C14) and n-pentadecane (C15), and mixtures thereof, and in particular the mixture of n-undecane (Cl l) and n-tridecane (C13) described in Example 1 of patent application WO 2008/155 059 by the company Cognis. Mention may also be made of n-dodecane (C12) and n-tetradecane (C14) sold by Sasol under the references, respectively, Parafol 12-97 and Parafol 14-97, and also mixtures thereof.

The linear alkane may be used alone or as a mixture of at least two distinct alkanes that differ from each other by a carbon number of at least 1, and especially a mixture of at least two linear alkanes comprising from 10 to 14 distinct carbon atoms that differ from each other by a carbon number of at least 2, and in particular a mixture of CI 1/C13 volatile linear alkanes or a mixture of C12/C14 linear alkanes, in particular an n- undecane/n-tridecane mixture (such a mixture may be obtained according to Example 1 or Example 2 of WO 2008/155 059).

As a variant or additionally, the composition prepared may comprise at least one volatile silicone oil or solvent that is compatible with cosmetic use.

The term "silicone oil" means an oil containing at least one silicon atom, and especially containing Si-0 groups. According to one embodiment, said composition comprises less than 10% by weight of non- volatile silicone oil(s), relative to the total weight of the composition, better still less than 5% by weight, or even is free of silicone oil.

Volatile silicone oils that may be mentioned include cyclic polysiloxanes and linear polysiloxanes, and mixtures thereof. Volatile linear polysiloxanes that may be mentioned include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, tetradecamethylhexasiloxane and hexadecamethylheptasiloxane. Volatile cyclic polysiloxanes that may be mentioned include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecam ethyl cyclohexasiloxane.

As a variant or additionally, the composition prepared may comprise at least one volatile fluoro oil.

The term "fluoro oil" means an oil containing at least one fluorine atom.

Volatile fluoro oils that may be mentioned include nonafluoromethoxybutane and perfluoromethylcyclopentane, and mixtures thereof.

The volatile oil may be present in a content ranging from 0.05% to 90% by weight, preferably ranging from 0.1% to 70% by weight and preferentially ranging from 0.1%) to 50% by weight, relative to the total weight of the composition. In particular, the volatile oil may be present in the composition in a content ranging from 0.05% to 30%, preferably 0.1% to 15% by weight relative to the total weight of the composition. As a variant, the composition may be free of volatile oil. Non-volatile oil

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

The term "non-volatile oil" means an oil that remains on the skin or the keratin fibre at room temperature and pressure. More precisely, a non-volatile oil has an evaporation rate strictly less than 0.01 mg/cm²/min. Said at least one non-volatile oil that is suitable for the present invention may be chosen from hydrocarbon-based oils and silicone oils.

The non-volatile hydrocarbon-based oils that are suitable for the present invention may be chosen in particular from:

- hydrocarbon-based oils of plant origin, such as triglycerides formed from fatty acid esters of glycerol, the fatty acids of which may have varied chain lengths from C4 to C28, these chains possibly being linear or branched, and saturated or unsaturated; these oils are especially wheatgerm oil, sunflower oil, grapeseed oil, sesame seed oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, sesame seed oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil and musk rose oil; or alternatively caprylic/capric acid triglycerides such as those sold by the company Stearineries Dubois or those sold under the names Miglyol 810^®, 812^® and 818^® by the company Sasol,

- synthetic ethers containing from 10 to 40 carbon atoms;

- linear or branched hydrocarbons of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam, and squalane, and mixtures thereof;

- synthetic esters such as oils of formula R1COOR2 in which Rl represents a linear or branched fatty acid residue containing from 1 to 40 carbon atoms and R2 represents an in particular branched hydrocarbon-based chain containing from 1 to 40 carbon atoms, on condition that Rl + R2 > 10, for instance purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12-C15 alkyl benzoate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, alkyl or polyalkyl octanoates, decanoates or ricinoleates such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate and diisostearyl malate; and pentaerythritol esters;

- fatty alcohols that are liquid at room temperature, with a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and 2- undecylpentadecanol; and

- higher fatty acids such as oleic acid, linoleic acid or linolenic acid, and mixtures thereof. The non-volatile silicone oils that are suitable for the present invention may be chosen in particular from:

- the non-volatile silicone oils that may be used in the composition in accordance with the invention may be non-volatile polydimethylsiloxanes (PDMSs), polydimethylsiloxanes comprising alkyl or alkoxy groups, that are pendent and/or at the end of a silicone chain, the groups each containing from 2 to 24 carbon atoms, phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes and 2-phenylethyl trimethylsiloxysilicates.

The content of non-volatile oil or organic solvent in the composition in accordance with the invention may range from 0.01% to 30% by weight, in particular from 0.1% to 25% by weight and better still from 0.1% to 20% by weight relative to the total weight of the composition.

Besides this continuous oily phase, the composition according to the invention comprises at least one apolar wax, at least one polar wax, and at least one lipophilic film- forming polymer. Waxes

The composition according to the invention comprises at least one apolar wax and at least one polar wax.

The term "wax" is understood, within the meaning of the present invention, to mean a lipophilic compound, which is solid at room temperature (25°C), with a reversible solid/liquid change of state, which has a melting point of greater than or equal to 30°C, which may be up to 120°C.

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

Preferably, the measuring protocol is as follows: A sample of 5 mg of wax placed in a cmcible 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 increase ranging from -20°C to 100°C at a heating rate of 5°C/minute. During the second temperature increase, the variation of the difference in power absorbed by the empty crucible and by the crucible containing the sample of wax is measured as a function of the temperature. The melting point of the compound is the temperature value corresponding to the top of the peak of the curve representing the variation in the difference in power absorbed as a function of the temperature.

The wax may especially have a hardness ranging from 0.05 MPa to 15 MPa and preferably ranging from 6 MPa to 15 MPa. The hardness is determined by measuring the compressive force, measured at 20°C using the texture analyser sold under the name ΤΑ-ΤΧ2Ϊ by the company Rheo, equipped with a stainless-steel cylinder with a diameter of 2 mm, travelling at a measuring speed of 0.1 mm/second, and penetrating the wax to a penetration depth of 0.3 mm.

The waxes may be hydrocarbon-based waxes or fluoro waxes, and may be of plant, mineral, animal and/or synthetic origin. In particular, the waxes have a melting point of greater than 25°C and better still greater than 45°C.

Preferably, the composition according to the invention comprises a wax content between 1% and 40% by weight, relative to the total weight of the composition, preferably between 3% and 30% by weight, better still from 5% to 20% and even better still from 7% to 15% by weight relative to the total weight of the composition.

Apolar waxes:

The composition according to the invention comprises at least one apolar wax. For the purposes of the present invention, the term "apolar wax" means a wax whose solubility parameter at 25°C as defined below, 5_a, is equal to 0 (J/cm³)^½.

Apolar waxes are in particular hydrocarbon-based waxes constituted solely of carbon and hydrogen atoms, and free of heteroatoms such as N, O, Si and P. In particular, the expression "apolar wax" is understood to mean a wax that is constituted solely of apolar wax, rather than a mixture also comprising other types of waxes that are not apolar waxes.

As illustrations of apolar waxes that are suitable for the invention, mention may be made especially of hydrocarbon-based waxes, for instance microcrystalline waxes, paraffin waxes, ozokerite, polyethylene waxes, and a mixture thereof.

Polyethylene waxes that may be mentioned include Performalene 500-L Polyethylene and Performalene 400 Polyethylene sold by New Phase Technologies.

An ozokerite that may be mentioned is Ozokerite Wax SP 1020 P.

As microcrystalline waxes that may be used, mention may be made of Multiwax W 445^® sold by the company Sonneborn, and Microwax HW^® and Base Wax 30540^® sold by the company Paramelt.

As microwaxes that may be used in the compositions according to the invention as apolar wax, mention may be made especially of polyethylene microwaxes such as those sold under the names Micropoly 200^®, 220^®, 220L^® and 250S^® by the company Micro Powders.

Preferably, the composition according to the invention comprises a content of apolar wax, and in particular of apolar hydrocarbon-based wax, ranging from 3% to 15% by weight of wax relative to the total weight of the composition and better still from 3% to 12% by weight, in particular from 3% to 10% by weight relative to the total weight of the composition, more preferably from 5% to 8% by weight relative to the total weight of the composition.

Polar wax

According to one embodiment, the composition according to the invention may comprise at least one polar wax.

For the purposes of the present invention, the term "polar wax" means a wax whose solubility parameter at 25°C, 5_a, is other than 0 (J/cm³)^½ In particular, the term "polar wax" means a wax whose chemical structure is formed essentially from, or even constituted of, carbon and hydrogen atoms, and comprising at least one highly electronegative heteroatom such as an oxygen, nitrogen, silicon or phosphorus atom.

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

According to this Hansen space:

- δο characterizes the London dispersion forces derived from the formation of dipoles induced during molecular impacts;

- δρ characterizes the Debye interaction forces between permanent dipoles and also the Keesom interaction forces between induced dipoles and permanent dipoles;

- 5_h characterizes the specific interaction forces (such as hydrogen bonding, acid/base, donor/acceptor, etc.); and

- 5_a is determined by the equation: δ₃ = (δρ² + 5_h ²)^½.

The parameters δρ, δ_¾ ¾> and δ₃ are expressed in (J/cm³)^½

The polar waxes may especially be hydrocarbon-based, fluoro or silicone waxes.

The term "silicone wax" means a wax comprising at least one silicon atom, especially comprising Si-0 groups.

The term "hydrocarbon-based wax" means a wax formed essentially from, or even constituted of, carbon and hydrogen atoms, and optionally oxygen and nitrogen atoms, and that does not contain any silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.

According to a first preferred embodiment, the polar wax is a hydrocarbon- based wax. As a hydrocarbon-based polar wax, a wax chosen from ester waxes and alcohol waxes is in particular preferred. The expression "ester wax" is understood according to the invention to mean a wax comprising at least one ester function. The expression "alcohol wax" is understood according to the invention to mean a wax comprising at least one alcohol function, i.e. comprising at least one free hydroxyl (OH) group.

In particular, use may be made, preferably, as an ester wax, of those chosen from: i) Waxes of formula R₁COOR₂ in which Ri and R₂ represent linear, branched or cyclic aliphatic chains, the number of atoms of which varies from 10 to 50, which may contain a heteroatom such as O, N or P and the melting point of which varies from 25°C to 120°C. In particular, use may be made, as an 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 especially sold under the names Kester Wax K 82 P^®, Hydroxypolyester K 82 P^®, Kester Wax K 80 P^® and Kester Wax K82H by the company Koster Keunen.

Use may also be made of a glycol and butylene glycol montanate (octacosanoate) such as the wax Licowax KPS Flakes (INCI name: glycol montanate) sold by the company Clariant. ii) Bis(l, l,l-trimethylolpropane) tetrastearate, sold under the name Hest 2T-4S^® by the company Heterene, 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 (alkyl group comprising from 4 to 30 carbon atoms) and R⁴ represents a linear or branched C4-C30 aliphatic group (alkyl group comprising from 4 to 30 carbon atoms) which may or may not contain one or more unsaturated groups, and preferably that is linear and unsaturated, iv) Mention may also be made of the waxes obtained by catalytic hydrogenation of animal or plant oils having linear or branched C8-C32 fatty chains, for example such as hydrogenated jojoba oil, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil, and also the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol, such as those sold under the names Phytowax ricin 16L64^® and 22L73^® by the company SOPHIM. Such waxes are described in patent application FR-A-2792190 and the waxes obtained by hydrogenation of olive oil esterified with stearyl alcohol such as that sold under the name Phytowax Olive 18 L 57, or else; v) Beeswax, synthetic beeswax, polyglycerolated beeswax, carnauba wax, candelilla wax, oxypropylenated lanolin wax, rice bran wax, ouricury wax, esparto grass wax, cork fibre wax, sugar cane wax, Japan wax, sumach wax; montan wax, orange wax, laurel wax and hydrogenated jojoba wax.

According to another embodiment, the polar wax may be an alcohol wax. The expression "alcohol wax" is understood according to the invention to mean a wax comprising at least one alcohol function, i.e. comprising at least one free hydroxyl (OH) group.

Alcohol waxes that may be mentioned include for example the wax Performacol 550-L Alcohol from New Phase Technologies, stearyl alcohol and cetyl alcohol.

According to a second embodiment, the polar wax may be a silicone wax such as siliconized beeswax, or an alkyl dimethicone such as the C30-C45 alkyl dimethicone sold under the reference SF1642 by Momentive Performance Materials.

Preferably, the composition according to the invention comprises a content of polar wax, and in particular of polar hydrocarbon-based wax, ranging from 0.5% to 20% by weight of wax relative to the total weight of the composition, and better still from 2% to 18%) by weight, in particular from 5%> to 15%> by weight relative to the total weight of the composition, more specifically from 8%> to 14%> by weight relative to the total weight of the composition. Preferably, the weight ratio of apolar wax(es) to polar wax(es) is greater than or equal to 0.01, better still greater than or equal to 0.1 and preferably is between 0.05 and 10. The total wax content is preferably, limits included, between 5% and 40% by weight, better still between 8% and 25% by weight relative to the total weight of the composition.

Lipophilic film-forming polymer

The composition according to the invention comprises at least one lipophilic film-forming polymer.

The lipophilic film-forming polymer may be present in the composition according to the invention in a solids content ranging from 0.1% to 20% by weight, preferably from 2% to 15% by weight and better still from 4% to 10% by weight, relative to the total weight of the composition.

In the present invention, the term "film-forming polymer" means a polymer that is capable, by itself or in the presence of an auxiliary film-forming agent, of forming a macroscopically continuous film that adheres to keratin fibres, and preferably a cohesive film, and better still a film whose cohesion and mechanical properties are such that said film can be isolated and manipulated separately, for example when said film is made by casting onto a non-stick surface, for instance a Teflon-coated or silicone-coated surface.

Among the film-forming polymers that can be used in the composition of the present invention, mention may be made of synthetic polymers, of free-radical type or of polycondensate type, and polymers of natural origin, and mixtures thereof.

Free-radical film-forming polymers

The expression "free-radical film-forming polymer" means a polymer obtained by polymerization of unsaturated and especially ethylenically unsaturated monomers, each monomer being capable of homopolymerizing (unlike poly condensates).

The film-forming polymers of free-radical type may especially be vinyl polymers or copolymers, especially acrylic polymers. The vinyl film-forming polymers may result from the polymerization of ethylenically unsaturated monomers containing at least one acid group and/or esters of these acid monomers and/or amides of these acid monomers.

Monomers bearing an acid group which may be used are α,β-ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid or itaconic acid. (Meth)acrylic acid and crotonic acid are preferably used, and more preferably (meth)acrylic acid.

The esters of acid monomers are advantageously chosen from (meth)acrylic acid esters (also known as (meth)acrylates), especially alkyl (meth)acrylates, in particular C1-C30 and preferably C1-C20 alkyl (meth)acrylates, aryl (meth)acrylates, in particular C₆-Cio aryl (meth)acrylates, and hydroxyalkyl (meth)acrylates, in particular C2-C6 hydroxyalkyl (meth)acrylates.

Alkyl (meth)acrylates that may be mentioned include methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate and cyclohexyl methacrylate.

Hydroxyalkyl (meth)acrylates that may be mentioned include hydroxyethyl acrylate, 2- hydroxypropyl acrylate, hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.

Aryl (meth)acrylates that may be mentioned include benzyl acrylate and phenyl acrylate.

The (meth)acrylic acid esters that are particularly preferred are the alkyl (meth)acrylates. According to the present invention, the alkyl group of the esters may be either fluorinated or perfluorinated, i.e. some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.

Examples of amides of the acid monomers that may be mentioned are (meth)acrylamides, and especially N-alkyl(meth)acrylamides, in particular of a C2-C12 alkyl. The N- alkyl(meth)acrylamides that may be mentioned include N-ethylacrylamide, N-t- butyl aery 1 amide, N-t-octylacrylamide and N-undecylacryl amide.

The vinyl film-forming polymers may also result from the homopolymerization or copolymerization of monomers chosen from vinyl esters and styrene monomers. In particular, these monomers may be polymerized with acid monomers and/or esters thereof and/or amides thereof, such as those mentioned previously.

Examples of vinyl esters that may be mentioned are vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butylbenzoate. Styrene monomers that may be mentioned include styrene and a-methylstyrene. Film-forming polycondensates

Among the film-forming polycondensates that may be mentioned are polyurethanes, polyesters, polyester-amides, polyamides, epoxyester resins and polyureas. The polyurethanes may be chosen from anionic, cationic, nonionic and amphoteric polyurethanes, polyurethane-acrylics, polyurethane-polyvinylpyrrolidones, polyester- polyurethanes, polyether-polyurethanes, polyureas and polyurea-polyurethanes, and mixtures thereof.

The polyesters may be obtained, in a known manner, by polycondensation of dicarboxylic acids with polyols, in particular diols.

The dicarboxylic acid may be aliphatic, alicyclic or aromatic. Examples of such acids that may be mentioned include: oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2,2-dimethylglutaric acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2,5-norbornanedicarboxylic acid, diglycolic acid, thiodipropionic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid. These dicarboxylic acid monomers may be used alone or as a combination of at least two dicarboxylic acid monomers. Among these monomers, the ones preferentially chosen are phthalic acid, isophthalic acid and terephthalic acid.

The diol may be chosen from aliphatic, alicyclic and aromatic diols. The diol used is preferably chosen from: ethylene glycol, diethylene glycol, triethylene glycol, 1,3- propanediol, cyclohexanedimethanol and 4-butanediol. Other polyols that may be used are glycerol, pentaerythritol, sorbitol and trimethylolpropane.

The polyesteramides may be obtained in a manner analogous to that of the polyesters, by polycondensation of diacids with diamines or amino alcohols. Diamines that may be used are ethylenediamine, hexamethylenediamine and meta- or para- phenylenediamine. An amino alcohol that may be used is monoethanolamine. According to one embodiment variant of the composition according to the invention, the lipophilic film-forming polymer may be a polymer dissolved in a liquid fatty phase comprising oils such as those described previously (the film-forming polymer is then said to be a liposoluble polymer). Preferably, the liquid fatty phase comprises a volatile oil, optionally mixed with a non-volatile oil, the oils possibly being chosen from the oils mentioned above.

Examples of liposoluble polymers that may be mentioned are copolymers of a vinyl ester (the vinyl group being directly linked to the oxygen atom of the ester group and the vinyl ester containing a saturated, linear or branched hydrocarbon-based radical having 1 to 19 carbon atoms, linked to the carbonyl of the ester group) and of at least one other monomer which may be a vinyl ester (other than the vinyl ester already present), an oc- olefin (containing from 8 to 28 carbon atoms), an alkyl vinyl ether (in which the alkyl group comprises from 2 to 18 carbon atoms) or an allyl or methallyl ester (containing a saturated, linear or branched hydrocarbon-based radical having 1 to 19 carbon atoms, linked to the carbonyl of the ester group).

These copolymers may be crosslinked with the aid of crosslinking agents, which may be either of the vinyl type or of the allyl or methallyl type, such as tetraallyloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate and divinyl octadecanedioate.

Examples of these copolymers that may be mentioned include the following copolymers: vinyl acetate/allyl stearate, vinyl acetate/vinyl laurate, vinyl acetate/vinyl stearate, vinyl acetate/octadecyl vinyl ether, vinyl propionate/allyl laurate, vinyl propionate/vinyl laurate, vinyl stearate/ethyl vinyl ether, vinyl propionate/cetyl vinyl ether, vinyl stearate/allyl acetate, vinyl 2,2-dimethyloctanoate/vinyl laurate, allyl 2,2- dimethylpentanoate/vinyl laurate, vinyl dimethylpropionate/vinyl stearate, allyl dimethylpropionate/vinyl stearate, vinyl propionate/vinyl stearate, crosslinked with 0.2% divinylbenzene, vinyl dimethylpropionate/vinyl laurate, crosslinked with 0.2% divinylbenzene, vinyl acetate/octadecyl vinyl ether, crosslinked with 0.2% tetraallyloxyethane, vinyl acetate/allyl stearate, crosslinked with 0.2% divinylbenzene, vinyl acetate/ 1-octadecene, crosslinked with 0.2% divinylbenzene, and allyl propionate/allyl stearate, crosslinked with 0.2% divinylbenzene. According to one particular embodiment, the composition of the invention comprises at least one liposoluble polymer.

In particular, said liposoluble polymer is chosen from copolymers of a vinyl ester (the vinyl group being directly linked to the oxygen atom of the ester group and the vinyl ester bearing a saturated, linear or branched hydrocarbon-based radical having 1 to 19 carbon atoms, linked to the carbonyl of the ester group) and of an allyl or methallyl ester (bearing a saturated, linear or branched hydrocarbon-based radical having 1 to 19 carbon atoms, linked to the carbonyl of the ester group).

Preferably, said liposoluble polymer is chosen from vinyl acetate/allyl stearate copolymers.

Examples of liposoluble film-forming polymers that may also be mentioned are liposoluble copolymers, and in particular those resulting from the copolymerization of vinyl esters containing from 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, and alkyl radicals containing from 10 to 20 carbon atoms.

Such liposoluble copolymers may be chosen from copolymers of polyvinyl stearate, polyvinyl stearate crosslinked with the aid of divinylbenzene, of diallyl ether or of diallyl phthalate, copolymers of polystearyl (meth)acrylate, polyvinyl laurate and polylauryl (meth)acrylate, it being possible for these poly(meth)acrylates to be crosslinked with the aid of ethylene glycol dimethacrylate or tetraethylene glycol dimethacrylate.

The liposoluble copolymers defined above are known and are described in particular in patent application FR-A-2 232 303; they may have a weight-average molecular weight ranging from 2000 to 500 000 and preferably from 4000 to 200 000.

According to another embodiment, at least one copolymer resulting from the copolymerization of vinyl esters containing from 9 to 22 carbon atoms, and in particular polyvinyl laurate copolymers, may be used as liposoluble polymer.

According to one particular embodiment, the composition according to the invention comprises at least one liposoluble polymer chosen from vinyl acetate/allyl stearate copolymers and polyvinyl laurate copolymers, and mixtures thereof. As liposoluble film-forming polymers that may be used in the invention, mention may also be made of polyalkylenes and in particular copolymers of C2-C20 alkenes, such as polybutene, alkyl celluloses with a linear or branched, saturated or unsaturated Ci to C₈ alkyl radical, for instance ethyl cellulose and propyl cellulose, copolymers of vinylpyrrolidone (VP) and in particular copolymers of vinylpyrrolidone and of a C₂ to C40 and better still C3 to C20 alkene. As examples of VP copolymers which may be used in the invention, mention may be made of the VP/vinyl acetate, VP/ethyl methacrylate, butylated polyvinylpyrrolidone (PVP), VP/ethyl methacrylate/methacrylic acid, VP/eicosene, VP/hexadecene, VP/triacontene, VP/styrene or VP/acrylic acid/lauryl methacrylate copolymers.

Mention may also be made of silicone resins, which are generally soluble or swellable in silicone oils, which are crosslinked polyorganosiloxane polymers. The nomenclature of silicone resins is known under the name "MDTQ", the resin being described as a function of the various siloxane monomer units it comprises, each of the letters M, D, T and Q characterizing a type of unit.

As examples of commercially available polymethylsilsesquioxane resins, mention may be made of those sold:

- by the company Wacker under the reference Resin MK, such as Belsil PMS

MK;

- by the company Shin-Etsu under the reference KR-220L.

Siloxysilicate resins that may be mentioned include trimethyl siloxysilicate (TMS) resins such as those sold under the reference SR 1000 by the company General Electric or under the reference TMS 803 by the company Wacker. Mention may also be made of trimethyl siloxysilicate resins sold in a solvent such as cyclomethicone, sold under the name KF-7312J by the company Shin-Etsu or DC 749 and DC 593 by the company Dow Corning.

Mention may also be made of copolymers of silicone resins such as those mentioned above with polydimethylsiloxanes, for instance the pressure-sensitive adhesive copolymers sold by the company Dow Corning under the reference Bio-PSA and described in document US 5 162 410, or the silicone copolymers derived from the reaction of a silicone resin, such as those described above, and of a diorganosiloxane, as described in document WO 2004/073 626. According to one embodiment of the invention, the film-forming polymer is a film-forming linear block ethylenic polymer, which preferably comprises at least one first block and at least one second block that have different glass transition temperatures (T_g), said first and second blocks being linked together via an intermediate block comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block.

Advantageously, the first and second blocks of the block polymer are mutually incompatible.

Such polymers are described, for example, in documents EP 1 411 069 or WO 04/028 488.

The lipophilic film-forming polymer may also be present in the composition in the form of particles dispersed in a non-aqueous phase. Examples of non-aqueous dispersions of film-forming polymers that may be mentioned include acrylic dispersions in isododecane, for instance Mexomer PAP® from the company Chimex, dispersions of particles of a grafted ethylenic polymer, which is preferably acrylic, in a liquid fatty phase, the ethylenic polymer advantageously being dispersed in the absence of additional surface stabilizer of particles, as described especially in document WO 04/055 081. Lipophilic gelling agents

The composition according to the invention may also comprise at least one lipophilic gelling agent. This gelling agent may be organic or mineral, polymeric or molecular.

Mineral lipophilic gelling agents that may be mentioned include optionally modified clays, for instance hectorites modified with a C₁₀ to C₂₂ fatty acid ammonium chloride, for instance hectorite modified with distearyldimethylammonium chloride, for instance the product sold under the name Bentone 38V by the company Elementis.

Mention may also be made of fumed silica optionally subjected to a hydrophobic surface treatment, the particle size of which is less than 1 μπι. Specifically, it is possible to chemically modify the surface of silica, via a chemical reaction that generates a reduction in the number of silanol groups present at the surface of the silica. It is especially possible to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained. The hydrophobic groups may be:

- trimethylsiloxyl groups, which are obtained especially by treating fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are known as "Silica silylate" according to the CTFA (6th edition, 1995). They are sold, for example, under the references Aerosil R812® by the company Degussa, and Cab-O-Sil TS-530® by the company Cabot;

- dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained especially by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are known as "Silica dimethyl silylate" according to the CTFA (6th edition, 1995). They are sold, for example, under the references Aerosil R972® and Aerosil R974® by the company Degussa, and Cab-O-Sil TS-610® and Cab-O-Sil TS-720® by the company Cabot.

The hydrophobic fumed silica preferably has a particle size that may be nanometric to micrometric, for example ranging from about 5 to 200 nm.

The polymeric organic lipophilic gelling agents are, for example, partially or completely crosslinked elastomeric organopolysiloxanes of three-dimensional structure, for instance those sold under the names KSG6®, KSG16® and KSG18® by Shin-Etsu, TREFIL E-505C® and Trefil E-506C® by Dow Corning, Gransil SR-CYC®, SR DMF10®, SR-DC556®, SR 5 CYC gel®, SR DMF 10 gel® and SR DC 556 gel® by Grant Industries and SF 1204® and JK 113® by General Electric; ethyl cellulose, for instance the product sold under the name Ethocel® by Dow Chemical; polycondensates of polyamide type resulting from the condensation between (a) at least one acid chosen from dicarboxylic acids containing at least 32 carbon atoms, such as fatty acid dimers, and (β) an alkylenediamine and in particular ethylenediamine, in which the polyamide polymer comprises at least one carboxylic acid end group esterified or amidated with at least one saturated and linear monoalcohol or monoamine containing from 12 to 30 carbon atoms, and in particular ethylenediamine/stearyl dilinoleate copolymers such as the product sold under the name Uni clear 100 VG® by Arizona Chemical; galactomannans comprising from one to six and in particular from two to four hydroxyl groups per saccharide, substituted with a saturated or unsaturated alkyl chain, for instance guar gum alkylated with Ci to C₆, and in particular Ci to C₃, alkyl chains, and mixtures thereof. Block copolymers of "diblock", "triblock" or "radial" type, of the polystyrene/polyisoprene or polystyrene/polybutadiene type, such as the products sold under the name Luvitol HSB^® by the company BASF, of the polystyrene/copoly(ethylene-propylene) type, such as the products sold under the name Kraton^® by the company Shell Chemical Co., or of the polystyrene/copoly(ethylene-butylene) type, and mixtures of triblock and radial (star) copolymers in isododecane, such as those sold by the company Penreco under the name Versagel^®, for instance the mixture of butylene/ethylene/styrene triblock copolymer and of ethyl ene/propylene/styrene star copolymer in isododecane (Versagel M 5960).

Among the lipophilic gelling agents that may be used in the compositions according to the invention, mention may also be made of fatty acid esters of dextrin, such as dextrin palmitates, especially the products sold under the name Rheopearl TL® or Rheopearl KL® by the company Chiba Flour.

Surfactants

The composition according to the invention comprises at least one surfactant having, at 25°C, an HLB balance (hydrophilic-lipophilic balance), within the Griffin meaning, of less than or equal to 6.

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

Reference may be made to the Kirk-Othmer Encyclopedia of Chemical Technology, volume 22, p. 333-432, 3rd edition, 1979, Wiley, for the definition of the properties and functions of surfactants, in particular p. 347-377 of this reference.

Preferably, said at least one surfactant is chosen from:

- glucose fatty acid esters, such as methylglucose dioleate;

- glycerol fatty acid esters, such as glyceryl isostearate, glyceryl oleate, and glyceryl ricinoleate, and preferably glycerol triesters such as glyceryl tristearate (tristearine), such as the mixture of acetylated glycol stearate and of glyceryl tristearate, sold under the name Unitwix by the company United Guardian;

- sorbitol fatty acid esters, such as sorbitan tristearate and sorbitan dioleate or trioleate; - silicone emulsifiers such as polyalkyl polyether siloxanes bearing polyoxyalkylene groups grafted to the main silicone chain, among which use will preferably be made of polyalkyl polyether siloxanes bearing polyoxyalkylene groups grafted to the main silicone chain;

and mixtures thereof.

Among the silicone emulsifiers, use will more particularly be made of those chosen from the group formed by polydiorganosiloxanes of formulae (I) and (II) below, it being possible for these compounds themselves to be dispersed in a volatile dimethicone,

CH₃ - CH, (I)

in which:

Ri denotes a linear or branched C₁₂-C₂₀ and preferably a C₁₂-C₁₈ alkyl group, R₂ denotes the group: ~C„H2n~(-OC2H4-)x~(-OC₃H₆-)_y--0— R₃,

R₃ denotes a hydrogen atom or a linear or branched alkyl radical comprising from 1 to about 12 carbon atoms,

a denotes an integer ranging from 0 to about 500,

b is an integer ranging from 0 to about 500,

c denotes an integer ranging from 1 to about 500,

n is an integer ranging from 2 to 12;

x and y respectively denote an integer ranging from 0 to about 50,

the sum x + y being greater than or equal to the value 1. Among the preferred polyorganosiloxane emulsifiers, mention may be made of those of formula (I), in which a is an integer ranging from 2 to 450, b is equal to 0, c is an integer ranging from 2 to 40, n is an integer ranging from 2 to 5, x is an integer ranging from 1 to 30, y is an integer ranging from 0 to 30, with x > y. Among these silicone emulsifiers, use may more particularly be made of the mixture of cyclomethicone and dimethicone copolyol (CTFA name) such as the product sold by the company Dow Corning under the trade name Silicone DC 3225 C or the product sold by the company Goldschmidt under the name Abil EM 97.

Among the preferred polyorganosiloxane emulsifiers, mention may be made of those of formula (I), in which a is equal to 0 and b is other than 0, such as, more particularly, the lauryl methicone copolyol (CTFA nomenclature - 7th edition - 1997) sold by the company Dow Corning under the trade name Q2-5200 Formulation Aid or else the cetyl dimethicone copolyol that is for example sold under the names Abil WE09® and Abil EM90® by the company Goldschmidt.

The surfactant is present in the composition according to the invention in a content ranging from 0.5% to 7% by weight, preferably from 1% to 6% by weight and more preferably still from 2% to 5% by weight relative to the total weight of the composition.

Preferably, a composition according to the invention comprises less than 1% by weight, relative to the total weight of the composition, of surfactant(s) other than one or more surfactants possessing at 25°C an HLB balance (hydrophilic-lipophilic balance), within the Griffin meaning, of less than or equal to 6, more preferably still less than 1% by weight, relative to the total weight of the composition, of surfactant(s) possessing at 25°C an HLB balance (hydrophilic-lipophilic balance), within the Griffin meaning, of greater than or equal to 6. Preferably, a composition according to the invention is furthermore free of such surfactant(s). Aqueous phase

The composition in accordance with the invention may comprise an aqueous phase comprising water and/or at least one water-soluble solvent. This aqueous phase is continuous.

In the present invention, the term "water-soluble solvent" denotes a compound that is liquid at room temperature and water-miscible (miscibility in water of greater than 50% by weight at 25°C and atmospheric pressure).

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

Among the water-soluble solvents that may be used in the compositions in accordance with the invention, mention may be made especially of lower monoalcohols containing from 1 to 5 carbon atoms, such as ethanol and isopropanol, glycols containing from 2 to 8 carbon atoms, such as ethylene glycol, propylene glycol, 1,3-butylene glycol and dipropylene glycol, C₃ and C₄ ketones and C₂-C4 aldehydes.

The aqueous phase (water and optionally the water-miscible solvent) may be present in a content of less than or equal to 15% by weight relative to the total weight of the composition. In particular, this aqueous phase may be present in the composition in a content ranging from 1% to 12% by weight, preferably ranging from 2% to 10% by weight and preferentially ranging from 3% to 8% by weight, relative to the total weight of the composition.

This aqueous phase may optionally comprise at least one hydrophilic film- forming polymer and/or at least one hydrophilic thickener.

Dyestuffs

The compositions in accordance with the invention may also comprise at least one dyestuff, for instance pulverulent dyestuffs, liposoluble dyes and water-soluble dyes.

The pulverulent dyestuffs may be chosen from pigments and nacres. The pigments may be white or coloured, mineral and/or organic, and coated or uncoated. Among the mineral pigments, mention may be made of titanium dioxide, optionally surface-treated, zirconium, zinc or cerium oxide, and also iron or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue. Among the organic pigments that may be mentioned are carbon black, pigments of D & C type and lakes based on cochineal carmine or on barium, strontium, calcium or aluminium.

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

The liposoluble dyes are, for example, Sudan Red, D&C Red 17, D&C Green 6, β-carotene, soybean oil, Sudan Brown, D&C Yellow 11, D&C Violet 2, D&C Orange 5, quinoline yellow and annatto.

These dyestuffs may be present in a content ranging from 0.01% to 15% by weight, relative to the total weight of the composition.

Fillers

The compositions in accordance with the invention may also comprise at least one filler.

The fillers may be selected from those that are well known to those skilled in the art and commonly used in cosmetic compositions. The fillers may be mineral or organic, and lamellar or spherical. Mention may be made of talc, mica, silica, kaolin, polyamide powders, for instance the Nylon^® powders sold under the name Orgasol^® by the company Atochem, poly- -alanine powders and polyethylene powders, powders of tetra-fluoroethylene polymers, for instance Teflon^®, lauroyllysine, starch, boron nitride, expanded polymeric hollow microspheres such as those of polyvinylidene chloride/acrylonitrile, for instance the products sold under the name Expancel^® by the company Nobel Industrie, acrylic powders such as those sold under the name Polytrap^® by the company Dow Corning, polymethyl methacrylate particles and silicone resin microbeads (for example Tospearls^® from Toshiba), precipitated calcium carbonate, magnesium carbonate and magnesium hydrogen carbonate, hydroxyapatite, hollow silica microspheres (Silica Beads^® from Maprecos), glass or ceramic microcapsules, metal soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms and in particular from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate and magnesium myristate. It is also possible to use a compound that is capable of swelling on heating, and especially heat-expandable particles such as non-expanded microspheres of vinylidene chloride/acrylonitrile/methyl methacrylate copolymer or of acrylonitrile homopolymer or copolymer, for instance those sold, respectively, under the references Expancel^® 820 DU 40 and Expancel^® 007WU by the company Akzo Nobel.

The fillers may represent from 0.1% to 15% by weight and in particular from 0.2% to 10%) by weight relative to the total weight of the composition.

Fibres

The compositions in accordance with the invention may also comprise at least one fibre that can improve the lengthening effect.

The term "fibre" should be understood as meaning an object of length L and of diameter D such that L is very much greater than D, D being the diameter of the circle in which the cross section of the fibre is inscribed. In particular, the ratio L/D (or aspect ratio) is chosen in the range from 3.5 to 2500, in particular from 5 to 500 and more particularly from 5 to 150.

The fibres that may be used in the composition of the invention may be mineral or organic fibres, of synthetic or natural origin. They may be short or long, individual or organized, for example braided, and hollow or solid. They may have any shape and may especially have a circular or polygonal (square, hexagonal or octagonal) cross section depending on the specific application envisaged. In particular, their ends are blunted and/or polished to prevent injury.

In particular, the fibres have a length ranging from 1 μπι to 10 mm, in particular from 0.1 mm to 5 mm and more particularly from 0.3 mm to 3.5 mm. Their cross section may be included in a circle with a diameter ranging from 2 nm to 500 μπι, in particular ranging from 100 nm to 100 μπι and more particularly from 1 μπι to 50 μπι. The weight or yarn count of fibres is often given in denier or decitex and represents the weight in grams per 9 km of yarn. In particular, the fibres according to the invention may have a yarn count chosen within the range from 0.15 to 30 denier and better still from 0.18 to 18 denier. The fibres that may be used in the composition of the invention may be chosen from rigid or non-rigid fibres, and may be mineral or organic fibres, of synthetic or natural origin.

Moreover, the fibres may or may not be surface-treated, may be coated or uncoated, and may be coloured or uncoloured.

As fibres that may be used in the composition according to the invention, mention may be made of non-rigid fibres such as polyamide (Nylon^®) fibres or rigid fibres such as polyimideamide fibres, for instance those sold under the names Kermel® and Kermel Tech® by the company Rhodia or poly(p-phenyleneterephthalamide) (or aramid) fibres sold especially under the name Kevlar^® by the company DuPont de Nemours.

The fibres may be present in the composition according to the invention in a content ranging from 0.01% to 10% by weight, in particular from 0.1% to 5% by weight and more particularly from 0.3% to 3% by weight relative to the total weight of the composition.

Cosmetic active agents

The compositions in accordance with the invention may also comprise at least one cosmetic active agent.

As cosmetic active agents that may be used in the compositions in accordance with the invention, mention may be made especially of antioxidants, preserving agents, fragrances, neutralizers, emollients, thickeners, coalescers, plasticizers, moisturizers, vitamins and screening agents, in particular sunscreens, and mixtures thereof.

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 composition according to the invention are not, or are not substantially, adversely affected by the envisaged addition.

Preferably, the composition according to the invention is a leave-in composition. Advantageously, the composition is a makeup composition and in particular a mascara.

The examples that follow are given as illustrations of the present invention, and shall not limit the scope thereof. ASSEMBLY

The assembly for coating keratin fibres according to the invention may comprise an applicator suitable for applying said composition and, where appropriate, a conditioning device suitable for receiving said composition.

Applicator

The applicator comprises means for smoothing and/or separating keratin fibres, such as the eyelashes or the eyebrows, especially in the form of teeth, bristles or other reliefs.

The applicator is arranged to apply the composition to the eyelashes or the eyebrows, and may comprise, for example, a brush or a comb.

The applicator may also be used for finishing of the makeup, over a region of the eyelashes or eyebrows that is made up or laden with composition.

The brush may comprise a twisted core and bristles held between the turns of the core, or may be made in yet another way.

The comb is, for example, produced from a single part by moulding of a plastic.

The application member may be magnetic.

In certain embodiments, the application member is mounted at the end of a wand, which wand may be flexible, which may contribute to improving the comfort during application.

Packaging device

The packaging device comprises a container for housing the composition for coating keratin fibres. This composition may then be withdrawn from the container by immersing the applicator therein.

This applicator may be firmly attached to a member for closing the container.

This closing member may form a member for gripping the applicator. This gripping member may form a cap to be removably mounted on said container by any suitable means, such as screwing, click-fastening, coupling, etc. Such a container may thus reversibly house said applicator. This container can be optionally equipped with a wiper suitable for removing a surplus of product taken by the applicator.

A process for applying the composition according to the invention to the eyelashes or the eyebrows may also include the following steps:

- forming a deposit of the cosmetic composition on the eyelashes or the eyebrows,

- leaving the deposit on the eyelashes or the eyebrows, it being possible for the deposit to dry. It should be noted that, according to another embodiment, the applicator may form a product container. In such a case, a container may, for example, be provided for in the gripping member and an internal channel can internally connect this gripping member to the application members in relief. Finally, it should be noted that the packaging and application assembly may be in the form of a kit, it being possible for the applicator and the packaging device to be housed separately in the same packaging article.

EXAMPLES

The examples that follow are presented as nonlimiting illustrations of the invention.

1/ Compositions and preparation

Comparative Composition

Starting material Composition A Composition C Composition D example B

Rice bran wax 2.7 2.7 2.7 2.7 2.14

Carnauba wax 5.7 5.7 5.7 5.7 4.52

Paraffin 2.2 2.2 2.2 2.2 6

Beeswax 8.2 8.2 8.2 8.2 6.14 ALLYL STEARATE/VA

6.7 6.7 6.7 6.7 6.7 COPOLYMER

POLYVINYL LAURATE 0.7 0.7 0.7 0.7 0.7

Isododecane (qs) 49.57 47.57 47.57 47.57 47.57

Black iron oxide 6.4 6.4 6.4 6.4 6.4

Talc 1 1 1 1 1

Bentone 6 6 6 6 6

Propylene carbonate 1 .6 1 .6 1 .6 1 .6 1 .6

Demineralized water 6.13 6.13 6.13 6.13 6.13

Active agent(s) 3.1 3.1 3.1 3.1 3.1

POLYGLYCERYL-4

ISOSTEARATE (and)

CETYL PEG/PPG-10/1 2 2 DIMETHICONE (and)

HEXYL LAURATE

BIS-PEG/PPG-14/14

DIMETHICONE (and) 2

CYCLOPENTASILOXANE

TRISTEARIN (and)

ACETYLATED GLYCOL 2

STEARATE

The composition referred to as "comparative example" serves as a reference for the purpose of comparing compositions A, B and C in accordance with the invention.

Compositions A, B, C and D all four comprise, unlike the composition of the comparative example, a surfactant. These surfactants each have, at 25°C, an HLB balance, within the Griffin meaning, of less than or equal to 6.

These formulations were prepared as follows:

Comparative example

- In a main beaker, melt the fatty phase (waxes and lipophilic polymers) at 80- 90°C in a water bath.

- When the fatty phase has melted, add the iron oxide and the talc. Disperse using a spatula and reheat in the water bath at 80-90°C. - In a secondary beaker, bring the isododecane and bentone to room temperature. Disperse using a deflocculator. Add the propylene carbonate until a smooth and homogeneous gel is obtained.

- Add the isododecane gel to the molten fatty phase. Homogenize rapidly using a spatula and mill the assembly 3 times using a three-roll mill.

- Add the demineralized water then the active agent(s) at room temperature. Leave to disperse using a deflocculator until a smooth and homogeneous product is obtained.

EXAMPLES A. B and D

The protocol for preparing these compositions is identical to that of the comparative example, with however, addition, using a deflocculator, of the surfactant at the end of manufacture and at room temperature.

Composition C

The protocol for preparing this composition differs from that of the comparative example by the introduction of the surfactant during the first manufacturing step, into the fatty phase at 80-90°C in a water bath. The rest of the preparation protocol remains identical to that of the comparative example.

21 Tests and results

The following tests were then carried out to evaluate the ease of makeup removal, the water resistance and the sebum resistance with, for each, a prior step of making a test specimen and making up the latter.

Test specimen and makeup

Test specimens of false eyelashes were made with straight black Caucasian hair with a fringe length of 19 mm. Said fringes were mounted between two 30 mm by 30 mm plates.

The hair was made up with the composition tested by carrying out three times ten sweeps, separated by an interval of two minutes, using a mascara brush.

The composition was left to dry for one hour at room temperature (25°C). Description of the test for ease of makeup removal

2 mL of makeup remover lotion (two-phase makeup remover lotion of BIFACIL type) were applied on a makeup removal cotton pad.

The test specimen was pinched in this cotton pad for ten seconds, then said cotton pad was pulled gently to remove makeup from said test specimen.

The cotton pad was replaced, makeup remover lotion was again applied and said test specimen was subjected to the makeup removal process as many times as necessary to obtain complete removal of makeup from the test specimen. The results are expressed as the significant number of cotton pads that actually made it possible to effectively remove makeup from said test specimen. The accuracy of the test is given to plus or minus 1 cotton pad.

Description of the water resistance test

The test specimen was passed under running water at 25°C for one minute

(water fountain) then the test specimen was rubbed twice on blotting paper with a pendulum.

The test specimen was then immersed in water for one hour and rubbed ten times on blotting paper with a pendulum. The appearance of a degradation of the film (swelling, unevenness, detachment, etc.) was observed visually.

Finally, the test specimen was pinched in a cotton pad for ten seconds, then the cotton pad was pulled to remove makeup from said test specimen. The effectiveness of the makeup removal was then noted by evaluating the amount of mascara on the cotton pad. Description of the sebum resistance test

The test specimen was submerged in plant squalene for one hour and rubbed ten times on blotting paper with a pendulum. The appearance of a degradation of the film (swelling, unevenness, detachment, etc.) was observed visually.

Finally, the test specimen was pinched in a cotton pad for ten seconds, then the cotton pad was pulled to remove makeup from said test specimen. The effectiveness of the makeup removal was then noted by evaluating the amount of mascara on the cotton pad. The rating scale for the water resistance and sebum resistance tests is the following:

0 no traces

1 imperceptible traces

2 few light grey traces

3 some light grey traces

4 light grey traces

5 dark grey traces

6 very dark grey traces

7 some dark black traces

8 dark black traces

9 very dark black traces

Compositions A, B, C and D exhibit significantly improved ease of makeup removal relative to the comparative composition free of surfactant having, at 25°C, an HLB balance, within the Griffin meaning, of less than or equal to 6, while retaining, for all four, excellent water resistance and excellent sebum resistance.

It can also be seen that the increase in the content of apolar wax and the consequent decrease in the content of polar waxes in composition D relative to compositions A, B and C makes it possible to further improve the removal of a composition. In this case a ratio of apolar wax to polar waxes of around 0.47 is advantageous. It is understood that, in the context of the present invention, the weight percentages given for a compound or a family of compounds are always expressed as weight of solids of the compound in question. Throughout the application, the term "comprises one" or "includes one" should be understood as meaning "comprising at least one" or "including at least one", unless otherwise specified.

Claims

1. - Cosmetic makeup composition comprising a continuous oily phase, and containing:

- at least one lipophilic film-forming polymer,

- at least one apolar wax,

- at least one polar wax, and

- at least one surfactant having, at 25°C, an HLB balance, within the Griffin meaning, of less than or equal to 6 present in an amount ranging from 0.5% to 7% by weight relative to the total weight of the composition, and said apolar wax is present in an amount ranging from 3% to 15% by weight relative to the total weight of the composition.

2. - Composition according to Claim 1, in which said continuous oily phase has an amount of organic solvent greater than or equal to 30% by weight relative to the total weight of said composition.

3. - Composition according to Claim 1 or 2, in which said lipophilic polymer is present in an amount ranging from 0.1% to 20% by weight, preferably from 2% to 15% by weight and better still from 4% to 10% by weight relative to the total weight of the composition.

4.- Composition according to any one of the preceding claims, in which said apolar wax is chosen from hydrocarbon-based waxes.

5. - Composition according to the preceding claim, in which said apolar hydrocarbon-based waxes are chosen from microcrystalline waxes, paraffin waxes, ozokerite, polyethylene waxes, and a mixture thereof.

6. - Composition according to any one of the preceding claims, in which said polar wax is present in an amount ranging from 0.5% to 20% by weight of wax relative to the total weight of the composition and better still from 2% to 18% by weight, in particular from 5% to 15%) by weight relative to the total weight of the composition, more preferably from 8%) to 14%) by weight relative to the total weight of the composition.

7. - Composition according to any one of the preceding claims, in which said polar wax is chosen from hydrocarbon-based waxes, silicone waxes, and a mixture thereof.

8. - Composition according to the preceding claim, in which said polar hydrocarbon-based waxes are chosen from ester waxes, alcohol waxes, and a mixture thereof.

9. - Composition according to any one of the preceding claims, in which the weight ratio of apolar wax(es) to polar wax(es) is greater than or equal to 0.01.

10. - Composition according to any one of the preceding claims, in which the content of total waxes is, limits included, between 0.5% and 40% by weight relative to the total weight of the composition.

11. - Composition according to any one of the preceding claims, in which said surfactant is present in a content greater than or equal to 0.1% by weight relative to the total weight of said composition.

12. - Composition according to any one of the preceding claims, in which said at least one surfactant is chosen from:

- glucose fatty acid esters,

- glycerol fatty acid esters,

- sorbitol fatty acid esters,

- silicone emulsifiers,

and mixtures thereof.

13. - Composition according to the preceding claim, in which said silicone emulsifiers are chosen from polyalkyl polyether siloxanes bearing polyoxyalkylene groups grafted to the main silicone chain, and preferably polyalkyl polyether siloxanes bearing polyoxyalkylene groups grafted to the main silicone chain.

14.- Composition according to any one of the preceding claims, in which the silicone emulsifiers are chosen from the group formed by the polydiorganosiloxanes of formulae (I) and (II) below:

CH₃ - CH, (I)

in which:

Ri denotes a linear or branched C₁₂-C₂₀ and preferably a C₁₂-C₁₈ alkyl group, R₂ denotes the group: ~C„H2n~(-OC2H4-)x~(-OC₃H₆-)_y--0— R₃,

R₃ denotes a hydrogen atom or a linear or branched alkyl radical comprising from 1 to about 12 carbon atoms,

a denotes an integer ranging from 0 to about 500,

b is an integer ranging from 0 to about 500,

c denotes an integer ranging from 1 to about 500,

n is an integer ranging from 2 to 12,

x and y respectively denote an integer ranging from 0 to about 50,

the sum x + y being greater than or equal to the value 1.

15. - Process for coating eyelashes with a makeup composition according to any one of the preceding claims, in which said process comprises a step of applying said composition to keratin fibres, and in particular eyelashes.