EP2416753A2 - Eyelash make-up process - Google Patents

Abstract

The subject matter of the invention is a method for making up eyelashes which consists in: a) coating the eyelashes with a deposit of at least one composition comprising, in a physiologically acceptable medium, at least one compound which enables the composition to attain, in the at least partially dry state, a modulus of rigidity Gp greater than or equal to 1 GPa, b) in the presence of a stimulus to which said compound is sensitive, placing a shaping tool in contact with the eyelashes thus coated in such a way as to modify the curvature of the eyelashes, wherein said placing in contact is maintained until the modulus of rigidity Gp of the composition is at least equal to 1 GPa, wherein the stimulus is selected in such a way that the modulus of rigidity of at least 1 GPa is obtained in a time t less than the time t0 that would be necessary to obtain said modulus by allowing the deposit to dry at ambient temperature.

Description

 Eyelash makeup process

The present invention relates to a process for making eyelashes consisting of: a) coating the eyelashes with a deposit of at least one composition comprising, in a physiologically acceptable medium, at least one compound allowing the composition to reach the at least partially dry state, a modulus of rigidity Gp greater than or equal to 1 GPa, b) in the presence of a stimulus to which said compound is sensitive, putting a shaping tool in engagement with the eyelashes thus coated so as to modify the curvature of the eyelashes, said engagement being maintained until the rigidity modulus Gp of the composition is at least equal to 1 GPa, the stimulus being chosen so that the stiffness modulus of at least 1 GPa is obtained in a time t less than the time t ₀ which would be necessary to obtain it by allowing the deposit to dry at room temperature.

The makeup process according to the invention is intended for eyelashes. The compositions may be makeup compositions, makeup bases, compositions for applying to a make-up, also called top-coat, or else compositions for cosmetic treatment of the eyelashes. More particularly, the invention relates to a mascara.

The eyelash makeup compositions, known as mascara, generally comprise, in known manner, at least one wax and at least one film-forming polymer for depositing a makeup film on the eyelashes and sheathing the eyelashes, as described, for example, in the document WO- A-95/15741. Users expect these products to have good cosmetic properties such as adhesion to the eyelashes, lengthening or bending of the eyelashes, a volumizing effect or good separation of the eyelashes, or even a good behavior of the mascara over time, in particular good resistance to friction eg fingers or tissues (handkerchiefs, towels). However, the mascara compositions do not always make it possible to obtain a permanent shaping of the eyelashes.

The object of the present invention is to provide an eyelash makeup composition which is easy to apply and which confers a permanent shaping of the eyelashes, particularly from the bending point of view.

It has been discovered that such a composition can be achieved by using a combination of specific compounds with a stimulus selected from light sources and heat sources.

The composition according to the invention is easily applied and clings well on the eyelashes. It can be seen that the shaping of the eyelashes is obtained quickly and easily after application to the eyelashes, and that this shaping is durable over time (residual effect). Makeup is comfortable for the user. By "permanent" shaping of the eyelashes, it is meant that the shaping of the eyelashes is durable over time, namely at least 6 hours, preferably at least 10 hours, preferably at least 24 hours after application. The eyelashes therefore retain the shape that was given to them during the application during this minimum period.

More specifically, the subject of the invention is a process for making eyelashes consisting of: a) coating the eyelashes with a deposit of at least one composition comprising, in a physiologically acceptable medium, at least one compound allowing the composition of attaining in the at least partially dry state, a rigidity modulus plateau Gp greater than or equal to 1 GPa, b) in the presence of a stimulus to which said compound is sensitive, putting a shaping tool in engagement with the eyelashes thus coated so as to modify the curvature of the eyelashes, said engagement being maintained until the plateau rigidity modulus Gp of the composition is at least equal to 1 GPa, the stimulus being chosen so that the module of rigidity of at least 1 GPa is obtained in a time t less than the time t ₀ which would be necessary to obtain it by allowing the deposit to dry at room temperature.

Preferably, in the process according to the invention, the time t is at least 20% and preferably at least 40% lower than the time t ₀ .

Preferably, in the method according to the invention, the platelet rigidity modulus Gp of said deposit, once reached, does not fall below 1 GPa when it is brought into contact with water or sebum.

The composition used in step a) of the process according to the invention comprises at least one compound allowing the composition to reach, in the at least partially dry state, a rigidity modulus plateau Gp greater than or equal to 1 GPa.

This modulus of rigidity can be measured according to the following method:

The composition according to the invention is characterized by its viscoelastic behavior, in particular using at least one rheological parameter.

Generally speaking, a material is said to be viscoelastic when, under the effect of shearing, it possesses at the same time the characteristics of a purely elastic material, ie capable of storing energy and the characteristics of a material. purely viscous material, ie able to dissipate energy.

More particularly, the viscoelastic behavior of the compositions in accordance with the invention can be characterized by its stiffness modulus G, its elasticity δ and its flow threshold; these parameters are defined in particular in the book "Initiation to the rheology "G. Couarraze and JL Grossiord, ^2nd edition, 1991 Edition Lavoisier-Tec 1 Doc.

These parameters are determined by measurements at 25 ° C ± 0.5 ° C using the stress rheometer "Haake RheoStress 600 ^®" of ThermoRheo equipped with a stainless steel plate / plate geometry, the plane having a diameter of 20 mm and an air gap (distance between the lower plane - called the stator plane - on which the composition is deposited and the upper plane - called the rotor plane) of 0.3 mm. The two planes are striated to limit sliding phenomena to the walls of the planes. Dynamic measurements are performed by applying a harmonic variation of the stress. In these experiments, the amplitudes of shear, shear rate and stress are small so as to remain within the linear viscoelastic domain of the material (conditions making it possible to evaluate the rheological characteristics of the composition at rest). The viscoelastic linear domain is generally defined by the fact that the response of the material (ie the deformation) is at any moment directly proportional to the value of the applied force (ie the stress). In this field, the applied stresses are weak and the material undergoes deformations without modifying its microscopic structure. Under these conditions, the material is studied "at rest" and non-destructively.

The composition is subjected to a harmonic shear according to a stress τ (t) varying sinusoidally according to a pulsation being the frequency of the shear applied). The composition thus sheared undergoes a stress τ (t) and responds according to a deformation γ (t) corresponding to micro deformations for which the stiffness modulus varies little according to the imposed constraint.

The stress τ (t) and the strain γ (t) are respectively defined by the following relations: τ ₀ being the maximum amplitude of the stress and γ ₀ being the maximum amplitude of the deformation, δ is the phase shift angle between the stress and the deformation. The measurements are made at a frequency of 1 Hz (v = 1 Hz).

The modulus of rigidity G (corresponding to the ratio of τ ₀ over γ ₀ ) and the elasticity δ (corresponding to the phase shift angle of the stress applied with respect to the measured strain) are thus measured as a function of the stress τ (t) applied. In particular, the deformation of the composition is measured for the stress zone in which the variation of modulus of rigidity G and of elasticity δ is less than 7% (area of microdeformations) and the so-called "plateau" parameters Gp are thus determined. and δ _p . The threshold stress τ _c (corresponding to the minimum force that it is necessary to apply to the composition to cause its flow) is determined from the curve δ = f (τ) and corresponds to the value of τ for which δ (τ _c ) = 1.05 δ _p .

The compound allowing the composition to reach in the at least partially dry state, a rigidity modulus plateau Gp greater than or equal to 1 GPa, may be chosen from: compounds capable of polymerizing or cross-linking under the action of UV radiation (photopolymerization), in particular in the presence of water and a reactive powder, compounds capable of polymerizing or crosslinking under the action of a chemical reaction of the hydrosilylation type, the compounds capable of polymerizing or ionically cross-linking.

Preferably, this compound is chosen from photopolymerizable ionomers, condensation or hydrosilylation-reactive silicone compounds and alginic acid-based compounds.

The invention therefore also relates to a process for making eyelashes consisting of: a) coating the eyelashes with a deposit of at least one composition comprising, in a physiologically acceptable medium, at least one compound chosen from photopolymerizable ionomers, the silicone compounds reacting by condensation or by hydrosilylation, the compounds based on alginic acid, b) in the presence of a stimulus to which said compound is sensitive, the stimulus being able to be either UV or visible light radiation, or a source of heat , putting a shaping tool in engagement with the eyelashes so coated so as to change the curvature of the eyelashes, said engagement being maintained until a curling eyelashes.

Physiologically acceptable medium means a medium compatible with keratin materials such as the skin of human beings.

The method according to the invention comprises a step of bending the eyelashes (ie placing the eyelashes in engagement with a shaping tool so as to modify the curvature of the eyelashes).

This bending step can be carried out manually using any applicator that can be used on keratinous fibers. In particular, this applicator may be provided with or without separation elements and / or smoothing keratin fibers. Such elements are in particular bristles or teeth. The applicator can thus correspond to a brush with bristles or teeth or a comb. It may also correspond to any applicator described below, and preferably to an eyelash curler.

The subject of the invention is also an eyelash makeup kit comprising the compound allowing the composition to reach, in the at least partially dry state, a plateau stiffness modulus Gp greater than or equal to 1 GPa defined above, as well as a source of stimulus and a shaping tool.

PHOTOPOLYMERISA TION

The eyelash makeup process according to the invention comprises, according to a first alternative, the following steps: a) coating the eyelashes with a first composition and a second composition, the first composition comprising at least one photopolymerizable ionomer, and the second composition comprising at least one reactive powder, the first and / or second composition comprising water, so as to form a deposit on the eyelashes, and b) simultaneously and / or after step a), put a forming tool in engagement with the eyelashes thus coated so as to modify the curvature of the eyelashes, and expose the deposit obtained to radiation of appropriate wavelength for a time sufficient to induce the crosslinking of said deposit.

According to an alternative, the first and second compositions are mixed before application on the keratinous fibers, in particular the eyelashes.

According to a second alternative, the first and second compositions are mixed in situ at the time of their application to the keratinous fibers, in particular the eyelashes.

The invention also relates to a kit for coating keratinous fibers, and in particular eyelash makeup comprising: a first composition comprising at least one photopolymerizable ionomer; a second composition comprising at least one reactive powder, and - a light source, the first and / or second composition comprising at least water, and the first and / or second composition comprising at least one additive chosen from pigments, waxes, fillers, thickeners, surfactants, film-forming polymers, and oils.

photopolymerizable lonomers These photopolymerizable ionomers are preferably chosen from the following compounds of formula (I): wherein B represents an organic backbone, X independently represents an ionic group capable of initiating a polymerization reaction in the presence of water and reactive powder,

Y is independently a photopolymerizable group, m is an integer greater than or equal to 2, n is an integer greater than or equal to 1. Preferably, B is an oligomeric or polymeric organic backbone comprising carbon-carbon bonds, optionally comprising non-substituted substituents. interfering, such as oxygen, nitrogen or sulfur heteroatoms. By "non-interfering" is meant substituents or linkers which do not unduly interfere with either the ionomer photopolymerization reaction or the dark reaction of the ionomer with the reactive powder.

Preferably, the X groups are acid groups, preferably carboxyl groups.

Among the Y groups, mention may be made of polymerizable ethylenic unsaturated groups and polymerizable epoxy groups. Ethylenic unsaturated groups are preferred, preferably those that are polymerizable by a radical reaction mechanism; examples include acrylates, methacrylates, alkenes and acrylamides, whether substituted or unsubstituted. In aqueous systems, polymerizable groups which are polymerized by a cationic mechanism, such as, for example, polymerizable ethylenic unsaturated groups such as vinyl ether groups and polymerizable epoxy groups, are less preferred because a radical mechanism is more readily usable than a cationic mechanism in such systems. Groups X and Y may be attached to backbone B directly or via a non-interfering organic group, such as substituted or unsubstituted alkyl, alkoxyalkyl, aryl, aryloxyalkyl, alkoxyaryl, aralkyl, or alkaryl groups.

The photopolymerizable ionomers of formula (I) can be prepared according to several synthetic routes. The preferred synthetic route is as follows: reaction between n groups X of a polymer of formula B (X) _{m + n} and a compound adapted to form n pendant Y groups. The adapted compound, also called a "coupler compound", comprises both a group

Y and a reactive group capable of reacting with the polymer through the X group to form a covalent bond between the coupler compound and the X group, connecting the Y group to the backbone B backbone. Preferred coupler compounds are organic compounds, optionally including non-interfering substituents and / or non-interfering linkers between the Y group and the reactive group. Preferred photopolymerizable ionomers of formula (I) are those for which each X is a carboxyl group, and each Y is an ethylenic unsaturated group which can be polymerized by radical reaction.

Such ionomers are conventionally prepared by reaction between a polyalkenoid acid (ie a polymer of formula B (X) _{m + n} where each X is a carboxyl group), and a coupler compound comprising both an ethylenic unsaturated group and a group capable of reacting with a carboxylic acid group. The molecular weight of the photopolymerizable ionomers is preferably between 250 and 500,000, preferably between 5,000 and 100,000. These ionomers are generally soluble in water, but less soluble than the polyalkenoid acids from which they are derived.

The preferred polyalkenoic acids are those prepared by homopolymerization and copolymerization of unsaturated aliphatic carboxylic acids, for example acrylic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, 2-bromoacrylic acid, 3-bromoacrylic acid, methacrylic acid, itaconic acid, maleic acid, glutamic acid, aconitic acid, citraconic acid, mesaconic acid, fumaric acid and acid tiglic. Monomers copolymerizable with unsaturated aliphatic carboxylic acids include unsaturated aliphatic compounds such as styrene, butadiene, acrylamide, acrylonitrile, methacrylonitrile, vinyl chloride, allyl chloride, vinyl acetate and the esters of acrylic and methacrylic acids such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, acrylate and the like. isobutyl, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-hydroxyethyl methacrylate. Preferably, the homopolymers and copolymers of acrylic acid are used.

The polyalkenoid acid must be cosmetically acceptable, ie free from unpolymerized monomers.

Other preferred polyalkenoid acids are homopolymers of polyacrylic acid, and copolymers of acrylic and itaconic acids, acrylic and maleic acids, methyl vinyl ether and anhydride or maleic acid, ethylene and dicarboxylic acid. anhydride or maleic acid, and styrene and anhydride or maleic acid.

The polymers of formula B (X) _{m + n} can be prepared for example by free radical polymerization, ie in solution, in emulsion or interfacially. Such polymers can react with coupler compounds in the presence of suitable catalysts.

As coupler compounds, it is especially possible to use compounds containing at least one group capable of reacting with X to form a covalent bond, as well as at least one polymerizable ethylenic unsaturated group. When X is a carboxyl group the group capable of reacting with X may be selected from Examples of coupling compounds are preferably the following corresponding methacrylates and acrylates:

with p between 1 and 20, and R is a hydrogen or an alkyl group having 1 to 6 carbon atoms, and the aIIyIe of the following formula:

Preferred coupler compounds are the following corresponding methacrylates and acrylates, with R as described above:

where q is between 1 and 18.

Preferred ionomers of formula (I) are those prepared by reaction between a polymer of formula B (X) _{m + n} where each X is a -COOH group, and a coupler compound comprising a reactive group of formula -NCO.

The photopolymerizable ionomers described above generally represent from 10 to 70% by weight, and preferably from 20 to 50% by weight of the first composition of the present invention.

Reactive powder

The reactive powder comprises at least one reactive compound selected from metal oxides, such as zinc oxide or magnesium oxide, and the glasses releasing ions.

Preferably, the reactive powder comprises releasable fluorine. Preferably, the reactive powder is chosen from the glasses releasing ions, preferably from fluoroaluminosilicate and fluoroaluminoborates.

In addition, the reactive powder may also comprise, in addition to the reactive compound, at least one polymerization initiator. Such a polymerization initiator may be chosen from photoinitiators, in particular initiators of UV-induced polymerization or visible light. Photoinitiators (or photoinitiators) usable in the cosmetic compositions of the present invention are also known in the art and are described, for example, in the following articles whose contents form an integral part of the present application: "Photoinitiators in the crosslinking of coatings ", G. Li Bassi, Double Liaison - Chemistry of Paints, No. 361, November 1985, pages 34-41; "Industrial applications of photoinduced polymerization", Henri Strub, L'Actualité Chimique, February 2000, pages 5 - 13; and "Photopolymers: Theoretical Considerations and Grip Reaction", Marc, JM Abadie, Double Liaison - Chemistry of Paints, No. 435-436, 1992, pp. 28-34.

These photoinitiators include both radical and cationic photoinitiators:

• the α-hydroxyketones, marketed for example under the designations IRGACURE ^® 184, 1173, 2959, 149, 1000, 500 and 4265 by the company Ciba,

• the α-amino ketones, for example marketed under the names I RGACU RE ^® 907 and 369 by the company Ciba,

• the chloroacétophénones marketed for example under the names P TRIGONAL ^® by Akzo and SANDORAY ^® 1000 by Sandoz,

• diones such as camphorquinone and aromatic ketones marketed for example under the names DAITOCURE ^® by DAINIPPON, UVECRYL ^® P 36 by UCB, ESACURE TZT ^® by Lamberti, and Quantacure ^® ITX by Ward BLENKINSOP. Also exemplary thioxanthones (eg UltraCure DXT ^® for SHERWIN WILLIAMS) and quinones (eg, 2-ethylanthraquinone from BASF). These diones, aromatic ketones and quinones most often require the presence of a hydrogen donor compound such as tertiary amines and more particularly alkanolamines,

• the benzoin ethers sold, for example under the name ESACURE ^® EB-3 by the company Lamberti and under the name TRIGONAL ^® 14 by AKZO,

• the α-dicarbonyl derivatives representing the most common of which is the ketal benzyldimethylamine sold under the name IRGACURE ^® 651 by Ciba. Other commercial products are marketed by the company Lamberti under the name ESACURE ^® KBO and by the company under the name WARD BENKINSOP Quantacure ^® PDO

• acylphosphine oxides such as for example bis-acylphosphine oxides (BAPO) marketed for example under the name IRGACURE ^® 819, 1700,

1800 and 1850 and DAROCUR 4265 ^® by Ciba,

• the oxime esters such as, for example IRGACURE ^® OXE01 OXE02 and marketed by Ciba, Aryl-onium salts such as diaryliodonium or triarylsulfonium or ferroce- nium salts. Preferably, the diphenyliodonium salts, such as, for example, diphenyliodonium chloride, bromide, iodide, or hexafluorophosphate, are used,

Acyl-germanium derivatives such as, for example, bis- (4-methoxybenzoyl) diethylgermanium.

In a preferred embodiment of the invention, polymeric photoinitiators or photoinitiators attached to a molecule of high molecular weight are used. The choice of such a high mass photoinitiator has the advantage of a better safety of the photocurable cosmetic compositions due to the absence of very reactive small molecules capable of diffusing towards neighboring biological substrates. As for the copolymerizable components, the weight average molecular weight of the photoinitiator is preferably at least 500.

By way of example, mention may be made of the α-hydroxyketone oligomer corresponding to the following formula:

and which is marketed under the names ESACURE KIP 150 and ESACURE KIP EM by the company LAMBERTI.

The polymer to which the photoinitiator group is attached may optionally comprise one or more ethylenic double bonds possibly allowing the integration, in the macromolecular network, of photoinitiator molecules that have not undergone photoinduced cleavage. Examples of such high molecular mass photoinitiators bearing ethylenic double bonds are those corresponding to the following formulas:

with n = 1 to 20

structures described in the following articles: S. Knaus, Pure Appl. Chem., A33 (7), 869 (1996); S. Knaus, J. Polym. Sci, Part A = Polym. Chem., 33, 929 (1995); and R. Liska, Rad'Tech Europe 97, Lyon, F, 1997, Proceedings Conference.

In the cosmetic compositions of the present invention, a mixture of light absorbing photoinitiators at different wavelengths is preferably used. It is thus possible to adapt the absorption spectrum of the photorefinable cosmetic compositions to the emission spectrum of the light sources used.

The concentration of the photoinitiator (s) used depends on a large number of factors such as, for example, the reactivity of the various components of the mixture, the the presence of pigments or dyes, the desired crosslinking density, the intensity of the light source or the exposure time.

To obtain satisfactory mechanical properties, a total amount of photoinitiator (s) of at least 0.01% by weight and at most equal to 5% by weight, and preferably between 0.1% and 5%, will generally be used. by weight, based on the total weight of compound having ethylenic double bonds.

Preferably, a photoinitiator is used which is a diphenyliodonium salt, preferably diphenyliodonium chloride. Such a photoinitiator is present especially in commercial compositions also comprising a reactive compound such as fluoroaluminosilicate glass, sold by 3M under the references Vitrebond 7512P and Vitrebond 7510.

Preferably, the ratio by weight powder (ie reactive powder or reactive powder + ionomer): liquid is between 1: 1 and 5: 1.

Light source

The light source according to the invention corresponds to a radiation source. Such radiation sources are chosen from sources of ultraviolet radiation or visible light.

The radiation suitable for crosslinking the cosmetic compositions of the present invention has a wavelength of between 10 and 500 μm, preferably between 400 and 700 nm, and preferably between 400 and 520 nm. We can also consider the use of lasers.

In a preferred embodiment of the invention, a UV lamp is used and in particular a mercury vapor lamp, possibly doped with other elements, such as gallium, making it possible to modify the emission spectrum of the source. light. The radiation suitable for crosslinking the cosmetic compositions of the present invention has a power of between 500 and 2400 mW / cm ² , preferably between 700 and 850 mW / cm ² .

The exposure time of the radiation deposited film depends on various factors such as the chemical nature and the concentration of the reactive components or the desired crosslinking density. For the compositions according to the invention, it will generally be sought to obtain satisfactory results for an exposure time of between 10 seconds and 10 minutes, preferably between 10 seconds and 1 minute, preferably between 15 and 40 seconds.

Hydrophilic solvent

The first and / or second composition comprises water.

When it comprises water, the first and / or second composition may also comprise at least one cosolvent. By "cosolvent" is meant a compound assisting in the dissolution of the photoreactive ionomer in water to form a homogeneous aqueous solution of cosolvent and ionomer. Said cosolvent is chosen from water-miscible solvents (solvent / water mixture capable of forming a homogeneous and transparent mixture at 25 ° C. with the eye), such as lower monoalcohols having from 1 to 5 carbon atoms such as ethanol or isopropanol, diols such as glycols having 2 to 8 carbon atoms such as propylene glycol, ethylene glycol, 1,3-butylene glycol, dipropylene glycol, or 1, 3-propanediol or 1,4-butanediol, C3-C5 ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone, C2-C4 aldehydes, and mixtures thereof, but also among the hydrophilic copolymerizable alkenyl solvents low molecular weight, such as 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate. By "copolymerizable" is meant that the cosolvent is able to react in a manner compatible with the ionomer.

The water, and optionally the water-miscible organic solvent, may be present in a content ranging from 1% to 95%, preferably from 5% to 80%, and more preferably from 10% to 60%, by weight. relative to the total weight of the first and / or second composition.

The compositions according to the invention may also comprise, in addition to the compounds mentioned above, pigments, oils, waxes, surfactants, film-forming polymers, fillers, thickeners, powdery compounds, or any other cosmetic additive.

COMPOUNDS CAPABLE OF POLYMERIZING UNDER THE ACTION OF A CHEMICAL CROSSLINK

Silicone compounds reacting by hydrosilylation or by condensation

The eyelash makeup process according to the invention comprises, according to a second alternative, the following steps: a) coating the eyelashes with a first composition and a second composition, the first composition comprising at least one silicone compound X, and the second composition comprising at least one silicone compound Y, in order to form a deposit on the eyelashes, and b) simultaneously and / or after step a), putting a shaping tool in engagement with the eyelashes thus coated so as to modify the curvature of the eyelashes, and for a time sufficient to induce the cross-linking of said eyelashes deposit.

According to an alternative, the first and second compositions are mixed before application on the keratinous fibers.

According to a second alternative, the first and second compositions are mixed in situ at the time of their application to the keratinous fibers. 1- Silicone compounds X and Y likely to react by hydrosilylation

According to one embodiment, the compounds X and Y are capable of reacting by hydrosilylation, this reaction being simplified in the following way: with W representing a carbon chain and / or silicone comprising one or more unsaturated aliphatic groups.

In this case, the compound X may be chosen from silicone compounds comprising at least two unsaturated aliphatic groups. By way of example, the compound X may comprise a main silicone chain whose unsaturated aliphatic groups are pendant to the main chain (lateral group) or located at the ends of the main chain of the compound (terminal group). In the remainder of the description, these particular compounds will be called polyorganosiloxanes with unsaturated aliphatic groups.

According to one embodiment, the compound X and / or the compound Y carries at least one polar group, as described above, capable of forming at least one hydrogen bond with the eyelashes. This polar group is advantageously carried by the compound X which comprises at least two unsaturated aliphatic groups.

According to one embodiment, the compound X is chosen from polyorganosiloxanes comprising at least two unsaturated aliphatic groups, for example two or three vinyl or allylic groups, each bonded to a silicon atom.

According to an advantageous embodiment, the compound X is chosen from polyorganosiloxanes comprising siloxane units of formula:

in which :

R represents a linear or cyclic monovalent hydrocarbon group comprising from 1 to 30 carbon atoms, preferably from 1 to 20, and more preferably from 1 to 10 carbon atoms, for example a short-chain alkyl radical, for example comprising from 1 to 10 carbon atoms, in particular a methyl radical or a phenyl group, preferably a methyl radical, m is equal to 1 or 2 and R 'represents: an unsaturated aliphatic hydrocarbon group comprising from 2 to 10, preferably from 2 to 5 carbon atoms, for example a vinyl group or a group - R "-CH = CHR '" in which R "is a divalent aliphatic hydrocarbon chain comprising from 1 to 8 carbon atoms, bound to the silicon atom and R '"is a hydrogen atom or an alkyl radical comprising 1 to 4 carbon atoms, preferably a hydrogen atom; mention may be made, as group R ', of vinyl groups, alkyl groups and mixtures thereof; or o an unsaturated cyclic hydrocarbon group comprising from 5 to 8 carbon atoms, for example a cyclohexenyl group.

Preferably R 'is an unsaturated aliphatic hydrocarbon group, preferably a vinyl group.

According to one particular embodiment, the polyorganosiloxane also comprises units of formula

wherein R is a group as defined above, and n is 1, 2 or 3.

According to one variant, the compound X may be a silicone resin comprising at least two ethylenic unsaturations, said resin being capable of reacting with the compound Y by hydrosilylation. Mention may be made, for example, of resins of the MQ or MT type bearing itself unsaturated reactive ends -CH = CH2. These resins are crosslinked organosiloxane polymers.

The nomenclature of the silicone resins is known under the name of "MDTQ", the resin being described according to the different siloxane monomeric units that it comprises, each of the letters "MDTQ" characterizing a type of unit.

The letter M represents the monofunctional unit of formula (CH ₃ ) ₃ SiOi / ₂ , the silicon atom being connected to a single oxygen atom in the polymer comprising this unit. The letter D is a difunctional unit (CH _{3) 2} Si0 _2/2 in which the silicon atom is bonded to two oxygen atoms

The letter T represents a trifunctional unit of formula In the units M, D and T defined above, at least one of the methyl groups may be substituted by a group R other than the methyl group such as a hydrocarbon radical (in particular alkyl) having from 2 to 10 carbon atoms or a phenyl group or else a hydroxyl group.

Finally, the letter Q means a tetrafunctional unit SiO4 / 2 in which the silicon atom is bonded to four hydrogen atoms themselves linked to the rest of the polymer. Examples of such resins that may be mentioned are MT silicone resins such as poly (phenyl-vinylsilsesquioxane), such as those sold under the reference SST-3PV1 by Gelest.

Preferably, compounds X comprise from 0.01 to 1% by weight of unsaturated aliphatic groups.

Advantageously, the compound X is chosen from polyorganopolysiloxanes, especially those comprising the siloxane units (I) and optionally (II) previously described.

Compound Y preferably comprises at least two free Si-H groups (hydrogenionic groups).

The compound Y may advantageously be chosen from organosiloxanes comprising at least one alkylhydrogenosiloxane unit of the following formula:

in which :

R represents a linear or cyclic monovalent hydrocarbon group comprising from 1 to 30 carbon atoms, for example an alkyl radical having from 1 to 30 carbon atoms, preferably from 1 to 20 and better still from 1 to 10 carbon atoms; in particular a methyl radical, or a phenyl group and p is 1 or 2. Preferably R is a hydrocarbon group, preferably methyl.

These organosiloxane compounds Y with alkylhydrogensiloxane units may also comprise units of formula:

as defined above.

The compound Y may be a silicone resin comprising at least one unit selected from the units M, D, T, Q as defined above and comprising at least one Si-H group such as the marketed poly (methyl-hydridosilsesquioxane) under the reference SST-3MH1.1 by the company Gelest Preferably, these organosiloxane compounds Y comprise from 0.5 to 2.5% by weight of Si-H groups.

Advantageously, the radicals R represent a methyl group in formulas (I), (II), (III) above. Preferably, these organosiloxanes Y comprise terminal groups of formula (CHa) ₃ SiOiZ ₂ .

Advantageously, the organosiloxanes Y comprise at least two alkylhydrogensiloxane units of formula (H ₃ C) (H) SiO and optionally comprise (H ₃ C) ₂ SiO units.

Such organosiloxane compounds Y having hydrogenosilane groups are described, for example, in document EP 0465744.

1a Additional reactive compounds

According to one embodiment, the compositions comprising compound X and / or Y may further comprise an additional reactive compound, such as organic or inorganic particles comprising at their surface at least 2 unsaturated aliphatic groups, for example treated silicas. on the surface by for example, silicone compounds with vinyl groups such as, for example, cyclotetramethyltetravinylsiloxane treated silica, silazane compounds such as hexamethyldisilazane.

1b Catalyst

The hydrosilylation reaction is advantageously carried out in the presence of a catalyst which may be present in one or other of the compositions comprising compound X and / or compound Y or in a separate composition, the catalyst preferably being platinum or tin base.

There may be mentioned, for example, platinum catalysts deposited on a silica gel or charcoal powder (charcoal) support, platinum chloride, platinum and chloroplatinic acid salts. The chloroplatinic acids are preferably used in hexahydrate or anhydride form, which is easily dispersible in organosilicone media.

It is also possible to mention platinum complexes such as those based on chloroplatinic acid hexahydrate and divinyl tetramethyldisiloxane.

The catalyst may be present in one or other of the compositions useful in the present invention in a content ranging from 0.0001% to 20% by weight relative to the total weight of the composition comprising it.

It is also possible to introduce polymerization inhibitors or retarders, and more particularly catalyst inhibitors, into the compositions of the invention, in order to increase the stability of the composition over time or to retard the polymerization. In a nonlimiting manner, mention may be made of cyclic polymethylvinylsiloxanes, and in particular tetravinyl tetramethylcyclotetrasiloxane, acetylenic alcohols, which are preferably volatile, such as methylisobutynol.

The presence of ionic salts, such as sodium acetate, in one and / or the other of the first and second compositions may influence the rate of polymerization of the compounds.

As an example of a combination of compounds X and Y reacting by hydrosilylation, mention may be made of the following references proposed by Dow Corning: DC 7-9800 Soft Skin Adhesive Parts A & B, as well as mixtures A and B following products prepared by Dow Corning: MIXING TO:

MIXING B:

Advantageously, the compounds X and Y are chosen from silicone compounds capable of reacting by hydrosilylation; in particular, compound X is chosen from polyorganosiloxanes comprising units of formula (I) described above and compound Y is chosen from organosiloxanes comprising alkylhydrogensiloxane units of formula (III) described above. According to one particular embodiment, the compound X is a polydimethylsiloxane with terminal vinyl groups, and the compound Y is methylhydrogensiloxane.

X and Y compounds likely to react by condensation

According to this embodiment, compounds X and Y are capable of reacting by condensation, either in the presence of water (hydrolysis) by reaction of 2 compounds bearing alkoxysilane groups, or by so-called "direct" condensation by reaction of a compound carrier of group (s) alkoxysilane (s) and a group-bearing compound) silanol (s) or by reaction of 2 compounds bearing group (s) silanol (s). When the condensation is done in the presence of water, it can be in particular the ambient humidity, the residual water of the eyelashes, or the water brought by an external source, for example by prior moistening of the eyelashes (for example by a fogger, natural or artificial tears).

In this condensation reaction mode, the compounds X and Y, which are identical or different, may therefore be chosen from silicone compounds whose main chain comprises at least two alkoxysilane groups and / or at least two silanol groups (Si-OH), side and / or at the end of the chain.

According to one embodiment, the compound X and / or the compound Y carries at least one polar group, as described above, capable of forming at least one hydrogen bond with the eyelashes.

According to an advantageous embodiment, the compounds X and / or Y are chosen from polyorganosiloxanes comprising at least two alkoxysilane groups. By "alkoxysilane" group is meant a group comprising at least a portion -Si-OR, R being an alkyl group comprising from 1 to 6 carbon atoms. The compounds X and Y are in particular chosen from polyorganosiloxanes comprising alkoxysilane end groups, more specifically those which comprise at least 2 terminal alkoxysilane groups, preferably terminal trialkoxysilanes. These compounds X and / or Y preferably comprise mainly units of formula wherein R ⁹ independently represents a radical selected from alkyl groups comprising 1 to 6 carbon atoms, phenyl, fluorinated alkyl groups, and S is 0, 1, 2 or 3. Preferably, R ⁹ independently represents an alkyl group having 1 to 6 carbon atoms. Alkyl groups include methyl, propyl, butyl, hexyl and mixtures thereof, preferably methyl or ethyl. As the fluoroalkyl group, 3,3,3-trifluoropropyl may be mentioned.

According to a particular embodiment, the compounds X and Y, which are identical or different, are polyorganosiloxanes comprising units of formula in which R ⁹ is as described above, preferably R ⁹ is a methyl radical, and f is in particular such that the polymer has a viscosity at 25 ° C ranging from 0.5 to 3000 Pa · s, preferably ranging from from 5 to 150 Pa s, for example f can range from 2 to 5000, preferably from 3 to 3000, more preferably from 5 to 1000.

These polyorganosiloxane compounds X and Y comprise at least 2 terminal trialkoxysilane groups per polymer molecule, said groups having the following formula: in which the R radicals independently represent a methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or isobutyl group, preferably a methyl or ethyl group, R ¹ is a methyl or ethyl group, x is equal to 0 or 1, preferably x is equal to 0, and

Z is chosen from: the divalent hydrocarbon groups not containing ethylenic unsaturation and comprising from 1 to 18 carbon atoms, preferably from 2 to 18 carbon atoms (alkylene groups), the combinations of divalent hydrocarbon radicals and of siloxane segments of formula (IX) below:

R ⁹ being as described above, G is a divalent hydrocarbon radical having no ethylenic unsaturation and comprising 1 to 18 carbon atoms, preferably 2 to 18 carbon atoms and c is an integer ranging from 1 to 6. Z and G may especially be chosen from alkylene groups such as methylene, ethylene, propylene, butylene, pentylene, hexylene, arylene groups such as phenylene. Preferably Z is an alkylene group. , and better ethylene.

These polymers may have on average at least 1, 2 terminal groups or terminal chains trialkoxysilanes per molecule, and preferably on average at least 1, 5 trialkoxysilane end groups per molecule. Since these polymers may have at least 1.2 trialkoxysilane terminal groups per molecule, some may comprise other types of terminal groups such as terminal groups of formula or formula wherein R ⁹ is as defined above and each R ⁶ group is independently selected from R ⁹ or vinyl. Examples of such end groups include trimethoxysilane, triethoxysilane, vinyldimethoxysilane and vinylmethyloxyphenylsilane.

Such polymers are described in particular in US Pat. No. 3,175,993, US Pat. No. 4,772,675, US Pat. No. 4,871,827, US Pat. No. 4,888,380, US Pat. No. 4,898,910, US Pat. No. 4,906,719 and US Pat. No. 4,962,174, the contents of which are incorporated by reference. to the present application.

As compound X and / or Y, in particular, the polymer of formula

wherein R, R ¹ , R ⁹ , Z, x and f are as described above.

Compounds X and / or Y may also comprise a polymer mixture of formula (VII) above with polymers of formula (VIII) below:

wherein R, R ¹ , R ⁹ , Z, x and f are as described above.

When the compound X and / or Y polyorganosiloxanes with alkoxysilane group (s) comprises such a mixture, the various polyorganosiloxanes are present in contents such that the terminal organosilyl chains represent less than 40%, preferably less than 25% by weight. number of terminal strings

Particularly preferred compounds X and / or Y polyorganosiloxanes are those of formula (VII) described above. Such compounds X and / or Y are described, for example, in WO 01/96450. According to a preferred embodiment, the compounds X and Y represent a mixture of polydimethylsiloxanes containing methoxysilane groups.

As indicated above, the compounds X and Y may be the same or different.

According to one variant, one of the two reactive compounds X or Y is of a silicone nature and the other is of organic nature. For example, the compound X is chosen from organic oligomers or polymers or oligomers or hybrid organic / silicone polymers, said polymers or oligomers comprising at least two alkoxysilane groups, and Y is chosen from silicone compounds such as the polyorganosiloxanes described herein. - above. In particular, the oligomers or organic polymers are chosen from vinyl, (meth) acrylic, polyester, polyamide, polyurethane and / or polyurea oligomers or polyethers, polyethers, polyolefins, perfluoropolyethers, dendrimers and organic hyperbranched polymers, and their mixtures.

According to one embodiment, the compound X of organic nature or organic hybrid nature / silicone carries at least one polar group, as described above, capable of forming at least one hydrogen bond with the eyelashes.

The organic polymers of vinyl nature or (meth) acrylic, bearing alkoxysilane side groups, may in particular be obtained by copolymerization of at least one vinyl organic monomer or (meth) acrylic with a (meth) acryloxypropyltrimethoxysilane, a vinyl trimethoxysilane, a vinyltriethoxysilane, an allyltrimethoxysilane etc.

For example, mention may be made of the (meth) acrylic polymers described in the KUSABE document. M, Pitture e Verniei - European Coating; 12-B, pages 43-49, 2005, and in particular the alkoxysilane polyacrylates referenced Kaneka MAX or those described in the publication PROBSTER, M, Adhesion-Kleben & Dichten, 2004, 481 (1-2), pages 12 -14.

The organic polymers resulting from a polycondensation or a polyaddition, such as polyesters, polyamides, polyurethanes and / or polyureas, polyethers, and bearing side and / or terminal alkylsilane groups, may result for example from the reaction of a oligomeric prepolymer as described above with one of the following silane co-reactants bearing at least one alkoxysilane group: aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, mercaptopropyltrimethoxysilane.

Examples of polyethers and polyisobutylenes with alkoxysilane groups are described in the KUSABE publication. M., Pitture e Verniei - European Coating; 12-B, pp. 43-49, 2005. Examples of polyurethanes with terminal alkoxysilane groups include those described in PROBSTER, M., Adhesion-Kleben & Dichten, 2004, 481 (1-2), p.12 -14 or those described in the document LANDON, S., Pitture e Verniei vol. 73, No. 11, pages 18-24, 1997 or in the document HUANG, Moowo, Pitture e Verniei Vol. 5, 2000, pages 61-67, there may be mentioned polyurethanes alkoxysilane groups of OSI-WITCO-GE.

As compounds X and / or Y polyorganosiloxane, there may be mentioned resins of MQ or MT type itself bearing alkoxysilane ends and / or silanols such as poly (isobutylsilsesquioxane) resins functionalized with silanol groups proposed under the reference SST-S7C41 (3 Si-OH groups) by Gelest.

2a Additional reactive compound

One of the compositions useful in the present invention may further comprise an additional reactive compound comprising at least two alkoxysilane or silanol groups. Mention may be made, for example, of organic or inorganic particles comprising, on their surface, alkoxysilane and / or silanol groups, for example fillers surface-treated with such groups.

2b Catalyst

The condensation reaction may be carried out in the presence of a metal catalyst which may be present in one or other of the compositions comprising X and / or Y or in a separate composition. The catalyst useful in this type of reaction is preferably a titanium catalyst.

There may be mentioned catalysts based on tetraalkoxytitanium of formula wherein R ² is selected from tertiary alkyl radicals such as tert-butyl, tert-amyl and 2,4-dimethyl-3-pentyl; R ³ represents an alkyl radical comprising from 1 to 6 carbon atoms, preferably an ethyl, n-propyl or isopropyl methyl group, n-butyl, sec-butyl, hexyl and y is a number ranging from 3 to 4, more preferably from 3.4 to 4.

The catalyst may be present in one or other of the compositions useful in the present invention in a content ranging from 0.0001% to 20% by weight relative to the total weight of the composition or compositions containing it.

2c Thinner

Useful compositions comprising X and / or Y may further comprise a volatile silicone oil (or diluent) for decreasing the viscosity of the composition. This oil may be chosen from linear short chain silicones such as hexamethyldisiloxane, octamethyltrisiloxane, cyclic silicones such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and mixtures thereof. This silicone oil may represent from 5% to 95%, preferably from 10% to 80% by weight relative to the weight of each composition.

By way of example of a combination of compounds X and Y bearing alkoxy-silane and condensation-reactive groups, mention may be made of the combination of the following mixtures A 'and B' prepared by Dow Corning:

Mixture A ':

Mix B ':

It should also be noted that the identical compounds X and Y are combined in the mixture A '. COMPOUNDS CAPABLE OF POLYMERIZING BY ACTION OF IONIC CROSSLINK

The eyelash makeup process according to the invention comprises, according to a third alternative, the following steps: a) coating the eyelashes with a first composition and a second composition, the first composition comprising at least one compound based on alginic acid, and the second composition comprising at least one complexing agent, so as to form a deposit on the eyelashes, and b) simultaneously and / or after step a), put a shaping tool into engagement with the eyelashes thus coated so as to modify the curvature of the eyelashes, and for a time sufficient to induce the cross-linking of said deposit.

According to an alternative, the first and second compositions are mixed before application on the keratinous fibers.

According to a second alternative, the first and second compositions are mixed in situ at the time of their application to the keratinous fibers.

Compounds based on alginic acid

By "alginic acid-based compound" is meant in particular alginic acid, alginic acid derivatives and alginic acid salts (alginates) or derivatives thereof. Preferably, the alginic acid-based compound is water soluble.

Alginic acid, a natural substance derived from brown algae or certain bacteria, is a polyuronic acid composed of 2 uronic acids linked by glycosidic linkages: β-D-Manuronic acid (M) and α-acid. L-glucuronic (G).

The alginic acid is capable of forming water-soluble salts (alginates) with alkali metals such as sodium, potassium, lithium, lower amine and substituted ammonium cations such as methylamine, ethanolamine, diethaniolamine, triethanolamine. These alginates are water-soluble in aqueous medium at pH 4 but dissociate into alginic acid at a pH of less than 4.

These alginates are capable of crosslinking with each other in the presence of complexing agents, by formation of ionic bonds between said complexing agents and the charged group. The formation of multiple crosslinks between several alginate molecules leads to the formation of a matrix forming a water-insoluble gel.

Alginic acid-based compounds having a weight average molecular weight of from 10,000 to 1,000,000, preferably from 15,000 to 500,000 and most preferably from 20,000 to 250,000, are preferably used.

According to a preferred embodiment, the alginic acid-based compound is a sodium or potassium alginate.

The compound based on alginic acid may be present in a content ranging from 0.1 to 30% by weight relative to the total weight of the composition comprising it, preferably from 0.5 to 20% by weight and preferably from 1 to at 10% by weight.

Complexation agent

The complexing agent is capable of complexing with the alginic acid-based compound by ionic bond formation. This complexation is reversible. The complexing agent may be chosen in particular from cationic polyelectrolytes, multivalent ions and their salts, in particular salts of multivalent cations or polycations. It is preferably in water-soluble form in the second composition.

The multivalent ions may in particular be cations such as polycations or multivalent cations, preferably having a valency of from 2 to 4 and more preferably divalent cations, in particular calcium, magnesium, aluminum, barium cations. zinc, nickel, copper (+ II), manganese and mixtures thereof. Mention may in particular be made of the chlorides or sulphates of the cations mentioned above and in particular the chorides such as calcium chloride.

Examples of polyelectrolytes that may be mentioned include polyamines such as poly (ethyleneimine), also known as poly (ethyleneamine), poly (L-lysine), poly (L-glutamine), polyvinylamine or chitosan and quaternized polyamines such as hydroxy-2-propyl-1-N-methylammonium polychloride, hydroxy-2-propyl-1,1-N-dimethylammonium polychloride, vinyl-2-imidazolinium polyhydrogen sulphate or diallyl polychloride -dimethyl-ammonium. The complexing agent (s) may be present in a content ranging from 0.01% to 30% by weight relative to the total weight of the composition, preferably from 0.02% to 15% by weight and better still from 0.05% to 5% by weight. % in weight.

The reaction rate between the polysaccharide and the complexing agent can be modulated by modifying the pH and / or temperature conditions of the composition, or else by adding a compound making it possible to accelerate or delay the reaction. between the polysaccharide and the complexing agent, such as, for example, sodium phosphate, which makes it possible to retard the crosslinking of the alginic acid derivative.

OILS

The composition may comprise at least one oil. Such a component, when it is volatile, evaporates during the drying of the composition according to the invention.

For the purposes of the invention, the term "volatile oil" means volatile cosmetic oils which are liquid at ambient temperature and have a non-zero vapor pressure at ambient temperature and atmospheric pressure, in particular ranging from 10 ^-2 to 300 mm. Hg (1.33 Pa to 40,000 Pa) and preferably greater than 0.3 mmHg (30 Pa).

By "non-volatile oil" is meant an oil having in particular a vapor pressure of less than 10 ^-2 mmHg (1.33 Pa).

These oils may be hydrocarbon oils, silicone oils, fluorinated oils, or mixtures thereof.

The term "hydrocarbon-based oil" means an oil containing mainly hydrogen and carbon atoms and optionally oxygen, nitrogen, sulfur and phosphorus atoms. Volatile hydrocarbon oils may be chosen from hydrocarbon oils having 8 to 16 carbon atoms, and especially branched alkanes, C ₈ -C ₆ isoalkanes C8-C- | g of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and for example the oils sold under the trade names of Isopars or permetyls, branched C8-C- | isohexyl neopentanoate, and mixtures thereof. Other volatile hydrocarbon oils such as petroleum distillates, especially those sold under the name Shell SoIt by Shell, can also be used. Preferably, the volatile solvent is chosen from volatile hydrocarbon oils having from 8 to 16 carbon atoms and mixtures thereof.

As volatile oils, it is also possible to use volatile silicones, for example volatile linear or cyclic silicone oils, in particular those having a viscosity site <8 centistokes (8 10 ^~ 6 m ^ / s), and having in particular 2 to 7 silicon atoms, these silicones optionally having alkyl or alkoxy groups having 1 to 10 carbon atoms. As volatile silicone oil that may be used in the invention, there may be mentioned in particular octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyl disiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane and mixtures thereof.

It is also possible to use volatile fluorinated solvents such as 1, 1, 1, 2,2,3,4,5,5,5-decafluoropentane or perfluoromethylcyclopentane.

The volatile oil may be present in the composition according to the invention in a content ranging from 1% to 95% by weight, relative to the total weight of the composition, preferably from 1% to 65% by weight.

The composition may also comprise at least one non-volatile oil, and in particular chosen from non-volatile hydrocarbon and / or silicone and / or fluorinated oils.

As non-volatile hydrocarbon oil, mention may notably be made of:

hydrocarbon oils of vegetable origin, such as triglycerides consisting of esters of fatty acids and of glycerol, the fatty acids of which may have chain lengths varying from C ₄ to C ₂₄ , the latter being linear or branched, saturated or unsaturated; these oils include wheat germ, sunflower, grape seed, sesame, maize, apricot, castor, shea, avocado, olive, soya, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, pumpkin, rapeseed, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, bancoulier, passiflora, muscat rose; or the caprylic / capric acid triglycerides, such as those sold by the company Stéarineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel,

synthetic ethers having 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, squalane; synthetic esters such as oils of formula R ₁ COOR ₂ in which R 1 represents the residue of a linear or branched fatty acid comprising from 1 to 40 carbon atoms and R ₂ represents a hydrocarbon chain, in particular a branched hydrocarbon chain, containing from 1 to 40 carbon atoms provided that R ₅ + R ₆ is> 10, such as, for example, purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C ₁₂ alcohol benzoate, Ci ₅ , hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearate isostearate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols like the diocta propylene glycol; hydroxylated esters such as isostearyl lactate, di-isostearyl malate; and pentaerythritol esters;

the branched-chain and / or unsaturated carbon-chain liquid fatty alcohols having 12 to 26 carbon atoms, such as octyl dodecanol, isostearyl alcohol, oleic alcohol, 2-hexyldecanol, 2- butyloctanol, 2-undecylpentadecanol;

higher fatty acids such as oleic acid, linoleic acid, linolenic acid

dicaprylyl carbonate sold under the name CETIOL CC by the company COGNIS; and their mixtures.

The non-volatile silicone oils that may be used in the composition according to the invention may be non-volatile polydimethylsiloxanes (PDMS), polydimethylsiloxanes comprising alkyl or alkoxy groups, during and / or at the end of the silicone chain, groups each having from 2 to 24 carbon atoms, phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenylethyl trimethylsiloxysilicates; and their mixtures.

The fluorinated oils that can be used in the invention are in particular fluorosilicone oils, fluorinated polyethers and fluorinated silicones as described in document EP-A-847752.

The non-volatile oils may be present in the composition according to the invention in a content ranging from 0.1% to 80% by weight, relative to the total weight of the composition, preferably ranging from 0.1% to 50% by weight. weight, and preferably ranging from 0.1% to 20% by weight.

CIRES

For the purposes of the present invention, the term "wax" means a lipophilic compound, solid at room temperature (25 ° C.), with a reversible solid / liquid state change, having a melting point greater than or equal to 30 ° C. and up to 120 ºC. The melting point of the wax can be measured by means of a differential scanning calorimeter (D.S.C.), for example the calorimeter sold under the name DSC 30 by the company METLER.

The waxes may be hydrocarbon-based, fluorinated and / or silicone-based and may be of vegetable, mineral, animal and / or synthetic origin. In particular, the waxes have a melting temperature above 25 ºC and better above 45 ºC. When the composition according to the invention comprises at least one wax, the latter may be present in a content at least equal to 5% by weight. Preferably, she is present in a content ranging from 10 to 50% by weight relative to the total weight of the composition, more preferably from 10 to 40% and more preferably from 15 to 30% by weight. In particular, it is possible to use hydrocarbon-based waxes such as beeswax, lanolin wax, and Chinese insect waxes; rice wax, Carnauba wax, Candelilla wax, Ouricurry wax, Alfa wax, cork fiber wax, sugar cane wax, Japanese wax and sumac wax ; montan wax, microcrystalline waxes, paraffins and ozokerite; polyethylene waxes, waxes obtained by Fisher-Tropsch synthesis and waxy copolymers and their esters. Mention may also be made of waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched C8-C32 fatty chains.

Among these, there may be mentioned hydrogenated jojoba oil, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil and hydrogenated lanolin oil, di-tetrastearate ( trimethylol-1, 1, 1 propane) sold under the name "HEST 2T-4S" by the company HETERENE, di- (trimethylol-1, 1, 1 propane) tetraprenate sold under the name HEST 2T-4B by the company HETERENE.

Mention may also be made of silicone waxes such as alkyl or alkoxy dimethicone containing from 16 to 45 carbon atoms and fluorinated waxes.

It is also possible to use the wax obtained by hydrogenation of esterified olive oil with the stearyl alcohol sold under the name "PHYTOWAX Olive 18 L 57" or even the waxes obtained by hydrogenation of castor oil esterified with alcohol. cetyl sold under the name "PHYTOWAX ricin 16L64 and 22L73", by the company SOPHIM. Such waxes are described in application FR-A-2792190.

According to one particular embodiment, the compositions in accordance with the invention may comprise at least one so-called sticky wax, that is to say having a tackiness greater than or equal to 0.7 N.s and a hardness less than or equal to 3.5 MPa. The use of a sticky wax may in particular make it possible to obtain a cosmetic composition which is easily applied to the eyelashes, having good grip on the eyelashes and which leads to the formation of a smooth, homogeneous and thickening makeup .

The tacky wax used may in particular have a tack ranging from 0.7 N to 30 N, in particular greater than or equal to 1 N, in particular ranging from 1 N to 20 N, in particular greater than or equal to 2 N. s, especially ranging from 2 N. s to 10 N. s, and in particular ranging from 2 N. s to 5 N. s. The stickiness of the wax is determined by measuring the evolution of the force (compressive force or stretching force) as a function of time, at 20 ºC using the texturometer sold under the name "TA-TX2i®" by the company RHEO, equipped with a conical acrylic polymer mobile forming an angle of 45 °. The measurement protocol is as follows:

The wax is melted at a temperature equal to the melting point of the wax + 10 ºC. The melted wax is poured into a container 25 mm in diameter and 20 mm deep. The wax is recrystallized at room temperature (25ºC) for 24 hours so that the surface of the wax is flat and smooth, then the wax is stored for at least 1 hour at 20ºC before measuring the adhesive.

The mobile of the texturometer is moved at a speed of 0.5 mm / s, then penetrates into the wax to a depth of penetration of 2 mm. When the mobile penetrated the wax to the depth of 2 mm, the mobile is held stationary for 1 second (corresponding to the relaxation time) and then removed at a speed of 0.5 mm / s. During the relaxation time, the force (compression force) decreases sharply until it becomes zero and then, when the mobile is removed, the force (stretching force) becomes negative and then increases again to the value 0. The pantyhose corresponds to the integral of the force vs. time curve for the part of the curve corresponding to the negative values of the force (stretching force). The value of the sticky is expressed in N.s.

The tacky wax that can be used generally has a hardness of less than or equal to 3.5 MPa, in particular ranging from 0.01 MPa to 3.5 MPa, in particular ranging from 0.05 MPa to 3 MPa, or even from 0 to 1 MPa at 2.5 MPa. The hardness is measured according to the protocol described above.

As sticky wax, a C20-C40 alkyl (hydroxystearyloxy) stearate (the alkyl group comprising 20 to 40 carbon atoms), alone or in a mixture, in particular a 12- (12'-hydroxystearyloxy) stearate, may be used. C20-C40 alkyl of formula (II):

wherein m is an integer from 18 to 38, or a mixture of compounds of formula

(II).

Such a wax is especially sold under the names "Kester Wax K"

82 P® "and" Kester Wax K 80 P® "by KOSTER KEUNEN. The waxes mentioned above generally have an initial melting point below 45 ° C.

It is also possible to use the microcrystalline wax sold under the reference SP18 by the company Strahl and PITSCH, which has a hardness of approximately 0.46 MPa and a tack value of approximately 1 N.sup..s.

The wax (es) may be present in the form of an aqueous microdispersion of wax. By aqueous microdispersion of wax is meant an aqueous dispersion of wax particles in which the size of said wax particles is less than or equal to about 1 μm.

Microdispersions of wax are stable dispersions of colloidal wax particles, and are especially described in "Microemulsions Theory and Practice", L. M. Prince Ed., Academy Press (1977) pages 21-32. In particular, these microdispersions of wax can be obtained by melting the wax in the presence of a surfactant, and optionally a portion of the water, and then gradually adding hot water with stirring. The intermediate formation of a water-in-oil emulsion is observed, followed by phase inversion with the final obtaining of an oil-in-water type microemulsion. On cooling, a stable microdispersion of solid colloidal particles of wax is obtained. The microdispersions of wax can also be obtained by stirring the mixture of wax, surfactant and water using stirring means such as ultrasound, the high pressure homogenizer, the turbines.

The particles of the microdispersion of wax preferably have average dimensions of less than 1 μm (in particular ranging from 0.02 μm to 0.99 μm), preferably less than 0.5 μm (in particular ranging from 0.06 μm to 0 μm). , 5 μm).

These particles consist essentially of a wax or a mixture of waxes. However, they may comprise, in a minor proportion, oily and / or pasty fatty additives, a surfactant and / or a usual fat-soluble additive / active agent.

Film-forming polymers

In the present application, the term "film-forming polymer" means a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, in particular on keratin materials. A film-forming polymer capable of forming a hydrophobic film, that is to say a polymer whose film has a solubility in water at 25 ° C. of less than 1% by weight, is preferably used.

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, polymers of natural origin, and mixtures thereof.

By radical-forming film-forming polymer is meant a polymer obtained by polymerization of unsaturated monomers, especially ethylenic monomers, each monomer being capable of homopolymerizing (unlike polycondensates). The radical-type film-forming polymers may in particular be vinyl polymers, or copolymers, in particular (metha) acrylic polymers in acid, ester or amide form.

According to the present invention, the alkyl group of the esters can be either fluorinated or perfluorinated, ie some or all of the hydrogen atoms of the alkyl group are substituted by fluorine atoms.

The vinyl film-forming polymers may also result from the homopolymerization or copolymerization of monomers selected from vinyl esters and styrene monomers. In particular, these monomers can be polymerized with acidic monomers and / or their esters and / or their amides, such as those mentioned above.

It is possible to use any monomer known to those skilled in the art falling into the categories of acrylic and vinyl monomers (including monomers modified with a silicone chain).

Among the film-forming polycondensates, mention may be made of polyurethanes, polyesters, polyester amides, polyamides, and epoxy ester resins, polyureas.

It is possible to use isophthalate / sulphoisophthalate-based copolymers, and more particularly copolymers obtained by condensation of diethylene glycol, cyclohexane dimethyl, isophthalic acid and sulphoisophthalic acid. Such polymers are sold for example under the brand name Eastman AQ® by Eastman Chemical Products.

The polymers of natural origin, which may be modified, may be chosen from shellac resin, sandarac gum, dammars, elemis, copals, cellulosic polymers, and mixtures thereof.

According to a first embodiment of the composition according to the invention, the additional film-forming polymer may be present in the form of particles in dispersion aqueous, generally known as latex or pseudolatex. The techniques for preparing these dispersions are well known to those skilled in the art.

As the aqueous dispersion of film-forming polymer, it is possible to use the acrylic dispersions sold under the names NEOCRYL XK-90®, NEOCRYL A-1070®, NEOCRYL A-1090®, NEOCRYL BT-62®, NEOCRYL A-1079®, NEOCRYL A-523® by the company AVECIA-NEORESINS, DOW LATEX 432® by the company DOW CHEMICAL, DAITOSOL 5000 AD® by the company DAITO KASEY KOGYO; or even more the aqueous polyurethane dispersions sold under the names NEOREZ R-981®, NEOREZ R-974® by the company AVECIA-NEORESINS, AVALURE UR-405®, AVALURE UR-410®, AVALURE UR-425®, AVALURE UR-450®, SANCURE 875®, SANCURE 861®, SANCURE 878®, SANCURE 2060® by GOODRICH, IMPRANIL 85® by BAYER, AQUAMERE H-151 1® by HYDROMER.

As the aqueous dispersion of film-forming polymer, it is also possible to use the polymer dispersions resulting from the radical polymerization of one or more radical monomers inside and / or partially on the surface of pre-existing particles of at least one polymer chosen from the group consisting of polyurethanes, polyureas, polyesters, polyesteramides and / or alkyds. These polymers are generally called hybrid polymers.

According to a second variant embodiment of the composition according to the invention, the additional film-forming polymer may be a water-soluble polymer and is therefore present in an aqueous phase of the composition in solubilized form. Examples of water-soluble film-forming polymers include

proteins, such as proteins of vegetable origin, such as wheat and soy proteins; proteins of animal origin such as keratins, for example keratin hydrolysates and keratin sulfonates; anionic, cationic, amphoteric or nonionic chitin or chitosan polymers;

cellulose polymers such as hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose and carboxymethylcellulose, as well as the quaternized derivatives of cellulose; acrylic polymers or copolymers, such as polyacrylates or polymethacrylates;

vinyl polymers, such as polyvinylpyrrolidones, copolymers of methylvinyl ether and of malic anhydride, the copolymer of vinyl acetate and crotonic acid, copolymers of vinylpyrrolidone and of vinyl acetate; copolymers of vinylpyrrolidone and caprolactam; polyvinyl alcohol;

polymers of natural origin, possibly modified, such as: . gum arabic, guar gum, xanthan derivatives, ka-ray gum;

. alginates and carrageenans;

. glycosaminoglycans, hyaluronic acid and its derivatives; . shellac resin, sandaraque gum, dammars, elemis, copals; . deoxyribonucleic acid;

. mucopolysaccharides such as hyaluronic acid, chondroitin sulphates, and mixtures thereof.

According to another alternative embodiment of the composition according to the invention, the film-forming polymer may be present in a liquid fatty phase comprising organic oils or solvents such as those described above. For the purposes of the invention, the term "liquid fatty phase" is intended to mean a fatty phase that is liquid at ambient temperature (25 ° C.) and atmospheric pressure (760 mmHg, ie 10 ⁵ Pa), composed of one or more liquid fatty substances at room temperature, also called oils, generally compatible with each other.

Preferably, the liquid fatty phase comprises a volatile oil, optionally mixed with a non-volatile oil, the oils being able to be chosen from the oils mentioned above.

According to a third embodiment of the composition according to the invention, the additional film-forming polymer may be present in the form of particles, surface-stabilized, dispersed in a liquid fatty phase.

The dispersion of surface-stabilized polymer particles can be manufactured as described in EP-A-749747.

The polymer particles are surface-stabilized with a stabilizer which may be a block polymer, a graft polymer, and / or a random polymer, alone or in admixture.

Dispersions of film-forming polymer in the liquid fatty phase, in the presence of stabilizing agents, are described in particular in documents EP-A-749746, EP-A-923928 and EP-A-930060, the contents of which are incorporated by reference. in this application.

The size of the polymer particles in dispersion either in the aqueous phase or in the liquid fatty phase may range from 5 nm to 600 nm, and preferably from 20 nm to 300 nm. According to a fourth embodiment of the composition according to the invention, the additional film-forming polymer may be solubilized in a liquid fatty phase, it is said that the film-forming polymer is a fat-soluble polymer.

As an example of a fat-soluble polymer, mention may be made of vinyl ester copolymers (the vinyl group being directly connected to the oxygen atom of the ester group and the vinyl ester having a saturated hydrocarbon radical, linear or branched, from 1 to 19 carbon atoms, linked to the carbonyl ester group) and from at least one other monomer which may be a vinyl ester (different from the vinyl ester already present), an α-olefin (having from 8 to 28 carbon atoms), an alkyl vinyl ether (the alkyl group of which contains 2 to 18 carbon atoms), or an allyl or methallyl ester (having a linear or branched, saturated hydrocarbon radical of 1 to 19 carbon atoms, bonded to the carbonyl ester group).

These copolymers may be cross-linked with the aid of crosslinking agents whose purpose may be either of the vinyl type, or of the allyl or methallyl type, such as tetraalyloxyethane, divinylbenzene, divinyl octanedioate, divalyl dodecanedioate and the like. - nyl, and the octadecanedioate of divinyl.

Liposoluble homopolymers, and in particular those resulting from the homopolymerization of vinyl esters having from 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, may also be mentioned as liposoluble film-forming polymers, the alkyl radicals having more or less 10 to 20 carbon atoms.

The liposoluble copolymers and homopolymers defined above are known and in particular described in application FR-A-2262303; they can have a weight average molecular weight ranging from 2,000 to 500,000 and preferably from 4,000 to 200,000.

Liposoluble film-forming polymers that can be used in the invention also include polyalkylenes, and in particular copolymers of C ₂ -C ₂ O alkenes, such as polybutene, and alkylcelluloses with a linear or branched alkyl radical, saturated or unsaturated. to C _8, for instance ethylcellulose and propylcellulose, copolymers of vinylpyroli- done (VP) and in particular copolymers of vinylpyrrolidone and an alkene, C ₂ -C ₄ 0 and preferably C ₃ to C _20.

According to a preferred embodiment of the composition according to the invention, the additional film-forming polymer may be a polymer capable of forming a deposit, in particular a film, producing at a concentration of 7% in water, a shrinkage of the isolated stratum corneum. by more than 1% at 30ºC at 40% relative humidity, preferably above 1.2%, and more preferably above 1.5%. This retraction is measured using an extensometer, according to the method described below. The composition according to the invention may comprise an auxiliary film-forming agent to allow the room-temperature filming of the multiphase particles according to the invention or of the additional film-forming polymer. The auxiliary agent may be a coalescing agent or a plasticizer known to those skilled in the art. A plasticizer is usually an organic compound which remains in the composition during film formation. A coalescing agent is usually a volatile organic compound that evaporates during film formation.

surfactants

The composition according to the invention may contain surfactants present in particular in a proportion ranging from 2 to 30% by weight relative to the total weight of the composition, and better still from 5% to 15%.

According to the invention, a surfactant suitably chosen for obtaining a wax emulsion in water or oil-in-water is generally used. In particular, it is possible to use an emulsifier having at 25 ° C. an HLB balance (hydrophilic-lipophilic balance) in the Griffin sense, greater than or equal to 8.

The HLB value according to GRIFFIN is defined in J. Soc. Cosm. Chem. 1954 (volume 5), pages 249-256. These surfactants may be chosen from nonionic, anionic, cationic, amphoteric surfactants or surfactant emulsifiers. Reference can be made to "Encyclopedia of Chemical Technology, KIRK-OTHMER", Vol. 22, p. 333-432, ^3rd edition, 1979, Wiley, for the definition of the properties and functions (emulsifying) of surfactants, in particular p. 347-377 of this reference, for anionic, amphoteric and nonionic surfactants.

The surfactants preferably used in the composition according to the invention are chosen from: a) nonionic surfactants with a HLB greater than or equal to 8 at 25 ° C., used alone or as a mixture; mention may be made in particular of: - esters and ethers of dares such as the mixture of cetylstearyl glucoside and of cetyl and stearyl alcohols, such as Montanov 68 from Seppic;

oxyethylenated and / or oxypropylenated ethers (which may contain from 1 to 150 oxyethylenated and / or oxypropylene groups) of glycerol;

oxyethylenated and / or oxypropylenated ethers (which may contain from 1 to 150 oxyethylenated and / or oxypropylenated groups) of fatty alcohols (in particular alcohol

C8-C24, and preferably C12-C18) such as oxyethylenated ether of oxyethylenated cetearyl alcohol (CTFA name "Ceteareth-30"), oxyethylenated ether of stearyl alcohol at 20 ° C. oxyethylenated groups (CTFA name "Steareth-20"), and the ether thyléné mixture of fatty alcohols C12-C15 comprising 7 oxyethylene groups (CTFA name "C12-15 Pareth-7") sold under the name Neodol ^® 25-7 by Shell Chemicals,

fatty acid esters (in particular C 8 -C 24, and preferably C 16 -C 22) and polyethylene glycol (which may comprise from 1 to 150 ethylene glycol units), such as PEG-50 stearate and monostearate, PEG-40 sold under the name Myrj 52P ^® by the company ICI Uniqema, fatty acid esters (especially of C8-C24 acid, and preferably C16-C22 acid) of oxyethylenated glyceryl ethers and / or oxypropylenated (possibly com- carry from 1 to 150 oxyethylene and / or oxypropylene) as the mono-PEG-200 glyceryl sold under the name Simulsol 220 TM ^® by Seppic; polyethoxylated glyceryl stearate with 30 ethylene oxide groups, such as the product TAGAT S ^® sold by the company GOLDSCHMIDT, polyethoxylated glyceryl oleate with 30 ethylene oxide groups, such as the product TAGAT O ^® sold by the company GOLDSCHMIDT, glycerol cocoate polyethoxylated with 30 ethylene oxide groups such as the product VARIONIC Ll 13 ^® sold by the company SHEREX, the glyceryl isostearate polyethoxylated with 30 ethylene oxide groups as the product TAGAT L ^® sold by the company GOLDSCHMIDT and polyethoxylated glyceryl laurate with 30 ethylene oxide groups, such as the product TAGAT I ^® from the company GOLDSCHMIDT,

fatty acid esters (in particular C8-C24 and preferably C16-C22 acids) and oxyethylenated and / or oxypropylenated sorbitol ethers (which can contain from 1 to 150 oxyethylene and / or oxypropylene groups), such as polysorbate 20 sold under the name Tween 20 ^® by the company Croda, polysorbate 60 sold under the name Tween 60 ^® by the company Croda, dimethicone copolyol, such as that sold under the name Q2- 5220 ^® by Dow CORNING,

- dimethicone copolyol benzoate (Finsolv SLB 101 ^® and 201 ^® of the company FINTEX), - the propylene oxide copolymers and ethylene oxide, also known as EO / PO polycondensates, and mixtures thereof.

The EO / PO polycondensates are more particularly copolymers consisting of polyethylene glycol and polypropylene glycol blocks, for example polyethylene glycol / polypropylene glycol / polyethylene glycol triblock polycondensates. These triblock polycondensates have, for example, the following chemical structure:

H- (O-CH ₂ -CH _{2) a} - (O-CH (CH ₃₎ -CH _{2) b} - (O-CH ₂ -CH _{2) a -OH!} in which a is from 2 to 120, and b ranges from 1 to 100. The EO / PO polycondensate preferably has a weight average molecular weight ranging from 1000 to 15000, and better from 2000 to 13000. Advantageously, said polycondensate OE / OP has a cloud temperature, at 10 g / l in distilled water, greater than or equal to 20 ºC, preferably greater than or equal to 60 ºC. The cloud point is measured according to ISO 1065. As EO / PO polycondensate used according to the invention, there may be mentioned polycondensates polyethylene glycol / polypropylene glycol / polyethylene glycol sold under the names Synperonic ^® as the Synperonic PE / L44 ^® and SYNPERONIC PE / F127 ^® by ICI. b) nonionic surfactants with HLB of less than 8 at 25 ºC, optionally combined with one or more nonionic surfactants of HLB greater than 8 to 25 ºC, as mentioned above such as:

- the saccharide esters and ethers such as sucrose stearate, sucrose cocoate, sorbitan stearate and mixtures thereof as Arlatone 2121 ^® sold by ICI; oxyethylenated and / or oxypropylenated ethers (which may contain from 1 to

150 oxyethylenated and / or oxypropylenated groups) of fatty alcohols (in particular of C8-C24 alcohol, and preferably of C12-C18 alcohol) such as the oxyethylenated ether of stearyl alcohol with 2 oxyethylenated groups (CTFA name "Steareth-2"); esters of fatty acids (in particular of C8-C24, and preferably of C16-C22) and of polyol, in particular glycerol or sorbitol, such as glyceryl stearate, glyceryl stearate, such as the product sold under the name Tegin M ^® by the company Goldschmidt, glyceryl laurate, such as the product sold under the name Imwitor 312 ^® by the company Hüls, polyglyceryl-2 stearate, sorbitan tristearate, glyceryl ricinoleate; lecithins, such as soy lecithins (such as Emulmetik 100 J from Cargill, or Biophilic H from Lucas Meyer); the mixture of cyclomethicone / dimethicone copolyol sold under the name Q2-3225C ^® by Dow Corning. c) anionic surfactants such as: salts of C16-C30 fatty acids, especially those derived from amines, such as triethanolamine stearate and / or amino-2-methyl-2-propane-1,3-diol stearate; salts of polyoxyethylenated fatty acids, in particular those derived from amines or alkaline salts, and mixtures thereof;

phosphoric esters and their salts, such as "DEA oleth-10 phosphate" (Crodafos N 1 ON from the company CRODA) or monocotyl monopotassium phosphate (Amphisol K from Givaudan);

sulfosuccinates such as "Disodium PEG-5 citrate lauryl sulfosuccinate" and "Disodium ricinoleamido MEA sulfosuccinate";

alkyl ether sulfates, such as sodium lauryl ether sulphate; isethionates;

- acyl glutamates such as "Disodium hydrogenated tallow glutamate" (Amisoft HS-21 R ^® sold by the company Ajinomoto) and sodium stearoyl glutamate (Amisoft HS-1 1 PF ^® sold by the company Ajinomoto), and mixtures thereof;

- soy derivatives such as potassium soyate; citrates, such as Glyceryl stearate citrate (Axol C 62 Pellets from Degussa); proline derivatives, such as Sodium palmitoyl proline (VG Seppic Sepicalm), or Sodium palmitoyl sarcosinate, Palmitoyl glutamate Magnesium, Palmitic acid and Palmitoyl proline (Sepifeel One from Seppic);

lactylates, such as Sodium stearoyl lactylate (Akolin SL from Karlhams AB); sarcosinates, such as sodi um palmitoyl sarcosinate (N ikkol sarcosi nate P N) or the mixture of Stearoyl sarcosi ne and Myristoyl sarco sine 75/25 (Crodasin S M from Croda); sulfonates, such as Sodium C14-17 alkyl seculphonate (Hostapur SAS 60 from Clariant); glycinates, such as sodium cocoyl glycinate (Amilite GCS-12 from Ajinomoto).

Particularly suitable for the invention, triethanolamine stearate.

The latter is generally obtained by simple mixing of stearic acid and triethanolamine. The compositions in accordance with the invention may also contain one or more amphoteric surfactants, such as N-acyl amino acids such as N-alkylamines. aminoacetates and disodium cocoamphodiacetate and amine oxides such as stearamine oxide or silicone surfactants such as dimethicone copolyols phosphates such as that sold under the name PECOSIL PS 100 ^® by the company Phoenix Chemical. The surfactant that can be used can also be a polymeric surfactant, in particular a thermogelling polymer.

Powdery compounds

The compositions may also comprise at least one dyestuff, for example pulverulent compounds, for example from 0.01% to 25% of the total weight of the composition. The pulverulent compounds may be chosen from pigments and / or nacres usually used in mascaras.

The pigments may be white or colored, mineral and / or organic. Among the inorganic pigments, mention may be made of titanium dioxide, optionally surface-treated, zirconium or cerium oxides, as well as iron or chromium oxides, manganese violet, ultramarine blue, hydrate of chrome and ferric blue. Among the organic pigments, mention may be made of carbon black, D & C type pigments, and lacquers based on cochineal carmine, barium, strontium, calcium, aluminum.

The pearlescent pigments may be chosen from white pearlescent pigments such as mica coated with titanium, or bismuth oxychloride, colored pearlescent pigments such as titanium mica with iron oxides, titanium mica with, in particular, ferric blue. or chromium oxide, titanium mica with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride.

The compositions according to the invention may further comprise fillers which may be chosen from those well known to those skilled in the art and commonly used in cosmetic compositions. As a load, it is possible in particular to use:

talc, which is a hydrous magnesium silicate used in the form of particles generally less than 40 microns,

micas which are aluminosilicates of various compositions in the form of flakes having dimensions of 2 to 200 microns, preferably of 5 to 70 microns and a thickness of between 0.1 to 5 microns, preferably from 0.2 to 3 microns, these micas may be of natural origin such as muscovite margarite, roscoelite, lipidolite, biotite or synthetic origin,

starch, in particular rice starch,

kaolin, which is a hydrated aluminum silicate which is in the form of particles of isotropic form with dimensions generally less than 30 microns,

zinc and titanium oxides generally used in the form of particles having dimensions not exceeding a few microns, calcium carbonate, magnesium carbonate or magnesium carbonate,

microcrystalline cellulose,

- silica,

synthetic polymer powders such as polyethylene, polyesters (isophthalate or polyethylene terephthalate), polyamides such as those sold under the trade name of "nylon" or "Teflon" and silicone powders; .

The compositions according to the invention may also comprise fibers.

By "fiber" it is necessary to understand an object of length L and of diameter D such that L is much greater than D, D being the diameter of the circle in which the section of the fiber is inscribed. In particular, the L / D ratio (or form factor) is chosen in the range from 3.5 to 2500, in particular from 5 to 500, and more particularly from 5 to 150. The fibers that can be used in the composition of the The invention may be fibers of synthetic or natural, mineral or organic origin. They can be short or long, unitary or organized, for example braided, hollow or full. Their shape can be any and in particular of circular or polygonal section (square, hexagonal or octagonal) depending on the specific application envisaged. In particular, their ends are blunt and / or polished to avoid injury.

In particular, the fibers have a length ranging from 1 μm 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 in a circle of diameter ranging from 2 nm to 500 μm, in particular ranging from 100 nm to 100 μm and more particularly from 1 μm to 50 μm. The weight or titer of the fibers is often given in denier or decitex and represents the weight in gram for 9 km of yarn. The fibers according to the invention may in particular have a title chosen in the range from 0.15 to 30 denier and in particular from 0.18 to 18 denier. The fibers that can be used in the composition of the invention may be chosen from rigid or non-rigid fibers, they may be of synthetic or natural origin, mineral or organic.

Furthermore, the fibers may or may not be treated on the surface, coated or uncoated, colored or unstained. As a usable fibers in the composition according to the invention, mention may be made of non-rigid fibers such as polyamide (Nylon®) fibers or rigid fibers such as polyimide-amide fibers such as those sold under the names KERMEL ^® , KERMEL TECH ^® by the company RH O DIA or poly- (p-phenylene terephthalamide) (or aramid) sold in particular under the name Kevlar® by the company DU PO NT DENE MO U RS.

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

The compositions according to the invention may also contain ingredients commonly used in cosmetics, such as trace elements, softeners, sequestering agents, perfumes, vitamins, proteins, ceramides, alkalinizing or acidifying agents normally used. in the cosmetic field, emollients, preservatives, sunscreens, antioxidants.

Of course, those skilled in the art will take care to choose this or these optional additional compounds, and / or their quantity, in such a way that the advantageous properties of the composition according to the invention are not, or not substantially, impaired by the proposed addition.

The compositions according to the invention may be in the form of a solution, a dispersion, a wax-in-water emulsion, water-in-wax, oil-in-water, water-in-oil. The second composition may also be in anhydrous form, ie comprising less than 10% water, preferably less than 5% water.

The compositions according to the invention may each be packaged in a container defining at least one compartment which comprises said composition, said container being closed by a closure element.

The container is preferably associated with an applicator, in particular in the form of a brush comprising an arrangement of bristles held by a twisted wire. Such a twisted brush is described in particular in US Pat. No. 4,887,622. It may also be in the form of a comb comprising a plurality of application elements, obtained in particular from molding. Such combs are described, for example, in patent FR 2 796 529. The applicator may be integral with the receptacle, as described, for example, in patent FR 2 761 959. Advantageously, the applicator is secured to a rod which, same, is integral with the closure element.

It may be a comb or a brush molded as described in WO 06/125122 or FR 2769529. The closure member may be coupled to the container by screwing. Alternatively, the coupling between the closure member and the container is other than by screwing, in particular via a bayonet mechanism, snap-fastening or clamping. By "snapping" is meant in particular any system involving the crossing of a bead or a bead of material by elastic deformation of a portion, in particular of the closure element, then by return to the position not elastically constrained of said portion after crossing the bead or the bead.

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

Alternatively, the container is made of non-thermoplastic material, in particular glass or metal (or alloy).

The container is preferably equipped with a wiper arranged in the vicinity of the opening of the container. Such a wiper makes it possible to wipe the applicator and possibly the rod which it can be secured. Such a wiper is described for example in patent FR 2 792 618. Preferably, the first composition and the second composition are packaged in separate packages.

Each composition can be packaged separately in the same packaging article. Each composition may also be packaged in a compartment within the same packaging article, the mixture of the two compositions being effected at the end or ends of the packaging article during the delivery of each composition.

Alternatively, each of the first and second compositions may be packaged in a different packaging article.

The following example is given as an illustration of the present invention, and can not limit its scope.

Example of realization

Composition 1 (Vitrebond 7512L of 3M): - Itaconic acid <42%

- 2-hydroxyethyl methacrylate 20-25%

- Water 30-40%

Composition 2 (Vitrebond 7512P from 3M): Diphenyliodonium chloride 1-5% Disodium hydrogenorthophosphate 0.5-1, 5% Fluoroaluminosilicate glass powder 95-99%

Compositions 1 and 2 are sold in kit form by 3M under the reference Vitrebond 7510.

These two compositions are mixed and then the mixture obtained is applied to a test-tube of false eyelashes. It is then exposed to a light source (power of 800mW / cm ² , wavelength 450 at 470 nm for 30s), while mechanically conferring on the test piece a curved shape.

This produces false eyelashes whose curvature is persistent over time (at least

24 hours).

These two compositions could also have been mixed directly in situ on the false eyelash specimen.

Claims

1. A process for making the eyelashes comprising: a) coating the eyelashes with a deposit of at least one composition comprising, in a physiologically acceptable medium, at least one compound allowing the composition to reach at least one partially dry, a modulus of rigidity Gp greater than or equal to 1 GPa, b) in the presence of a stimulus to which said compound is sensitive, putting a shaping tool in engagement with the eyelashes thus coated so as to modify the curvature of the eyelashes, said engagement being maintained until the rigidity modulus Gp of the composition is at least equal to 1 GPa, the stimulus being chosen so that the stiffness modulus of at least 1 GPa is obtained in a time t less than the time t ₀ which would be necessary to obtain it by allowing the deposit to dry at room temperature.

2. Makeup method according to claim 1 characterized in that the time t is less than 20% and preferably at least 40% less than the time t ₀ .

3. Makeup method according to claim 1 characterized in that, once reached, the rigidity modulus Gp said deposit does not fall below 1

GPa when in contact with water or sebum.

4. A process for making up the eyelashes, comprising the following steps: a) coating the eyelashes with a first composition and a second composition, the first composition comprising at least one photopolymerizable ionomer, and the second composition comprising at least one reactive powder, the first and / or second composition comprising water, in order to form a deposit on the eyelashes, and b) simultaneously and / or after step a), putting a shaping tool into engagement with the eyelashes thus coated so as to modify the curvature of the eyelashes, and expose the deposit obtained to radiation of appropriate wavelength for a time sufficient to induce the crosslinking of said deposit.

5. Method according to claim 4, characterized in that the first composition comprises at least one photopolymerizable ionomer of formula (I) below:

BX _n Y _m (I) wherein B is an oligomeric or polymeric organic backbone comprising carbon-carbon bonds, X represents a carboxyl group, Y independently represents an ethylenically unsaturated group selected from the acry- lates, methacrylates, alkenes and acrylamides, substituted or unsubstituted, m is an integer greater than or equal to 2, n is an integer greater than or equal to 1.

6. Method according to claim 4 or 5, characterized in that the reactive powder is chosen from fluoroaluminosilicates and fluoroaluminoborates.

7. Method according to one of claims 4 to 6, characterized in that the light source has a wavelength between 10 nm and 500 microns, preferably between 400 and 700 nm, preferably between 400 and 520 nm.

8. Method according to one of claims 4 to 7, characterized in that the light source has a power between 500 mW / cm ² and 2400 mW / cm ² , preferably between 700 and 850 mW / cm ² .

9. Method according to one of claims 4 to 8, characterized in that said first and second compositions are mixed before application to the eyelashes.

10. Method according to one of claims 4 to 8, characterized in that said first and second compositions are mixed in situ at the time of application to the eyelashes.

1. Method according to one of claims 4 to 10, characterized in that the first composition and / or the second composition comprises at least one additive chosen from pigments, waxes, fillers, thickeners, tensio- film-forming polymers and oils.

12. Kit for coating keratin fibers, comprising:

a first composition comprising at least one photopolymerizable ionomer;

a second composition comprising at least one reactive powder, and

a light source, the first and / or second composition comprising at least water, and the first and / or second composition comprising at least one additive chosen from pigments, waxes, fillers, thickeners and surfactants; , film-forming polymers, and oils.