WO2007057780A2 - Method for make-up or care of keratinous materials with electrophilic monomer - Google Patents

Abstract

The invention relates to a cosmetic method for make-up or for non-therapeutic care of keratinous materials selected from the skin, the lips and the eyelashes, the method comprising: a. depositing at least one layer of a first composition on said keratinous materials; b. depositing at least one layer of a second composition on the layer or layers of said first composition; at least one of said first and second compositions containing at least one electrophilic monomer. According to a variant, the method comprises: a. mixing, at the time of use: at least one first composition containing a cosmetically acceptable medium and at least one electrophilic monomer, and at least one second composition containing a cosmetically acceptable medium then b. applying at least one layer of said mixture on the skin, the lips, and the eyelashes.

Description

Method for make-up or care of keratinous materials with electrophilic monomer

The present invention relates to a method of make-up or of care of keratinous materials comprising the application, on said keratinous materials, of at least one first composition and at least one second composition, with at least one of said compositions containing an electrophilic monomer.

The compositions according to the invention can be compositions for the make-up or care of keratinous materials, in particular of the skin, of the lips and of keratin fibres, notably of the eyelashes, and preferably compositions for make-up.

Each composition can be a loose or compacted powder, a foundation, a blusher or eyeshadow, an anti-ring product, a blush, a lipstick, a lip balm, a lip gloss, a lip or eye pencil, a mascara, an eye-liner or a product for make-up of the body or for colouring the skin.

The care composition can be a product for care of the eyelashes and of the lips, for care of the skin of the body and of the face, notably a sun screen, or a skin colouring product (such as a self-tanning product).

The compositions for lipstick and foundation are commonly used for giving an aesthetically pleasing colour to the lips or to the skin, notably to the face. These make-up products generally contain oil phases such as waxes and oils, pigments and/or fillers and optionally additives such as cosmetic or dermatologic actives.

These compositions, when applied to the skin, exhibit the drawback of being transferred, i.e. of being deposited at least partially, leaving marks, on certain substrates with which they may come into contact and notably a glass, a cup, a cigarette, clothing or the skin. As a result, the applied film does not last well, necessitating regular reapplication of the foundation composition or lipstick. Moreover, the appearance of these unacceptable marks notably on shirt or blouse collars can put some women off using this type of make- Up.

Therefore so-called "zero-transfer" make-up compositions for the lips and the skin are sought, which offer the advantage of forming a deposit which is not deposited, at least partially, on the substrates with which they come into contact (glass, clothing, cigarette, fabrics) and are long-lasting. The use of volatile oils for limiting the transfer of cosmetic compositions is known. These volatile oils, when present in large quantity, make the make-up product, notably lipstick, uncomfortable for the user: the deposit of make-up imparts a sensation of dryness and pulling.

In the case of compositions for coating the eyelashes, or mascaras, in particular there are anhydrous mascaras or mascaras with low content of water and/or water-soluble solvents, called "waterproof mascaras", formulated as a dispersion of waxes in nonaqueous solvents, and which display good resistance to water and/or to sebum.

However, the film of make-up obtained after application of these compositions is not sufficiently resistant to water, when taking a bath or shower for example, to tears or to sweat or to sebum. Mascara tends to crumble away over time: particles are deposited and unsightly marks appear around the eyes.

The aim of the present invention is to provide a novel method of formulation of cosmetic compositions, notably for make-up, for obtaining a deposited film on keratinous materials, having good zero-transfer properties, good properties of resistance over time, in particular to water and rubbing, and a comfortable deposit on the skin, the lips or the eyelashes.

The inventors discovered that it is possible to obtain such properties using a system comprising compounds which polymerize in situ to provide better adherence to keratinous materials.

More precisely, the present invention therefore relates to a cosmetic method for make-up or non-therapeutic care of keratinous materials selected from the skin, the lips and the eyelashes, said method comprising: a. depositing at least one layer of a first composition on said keratinous materials; b. depositing at least one layer of a second composition on the layer or layers of said first composition; at least one of said first and second compositions containing at least one electrophilic monomer. The terms first and second compositions do not in any way determine the order of application of said compositions on the keratinous materials. The second composition can be applied on the first composition and vice versa.

By "cosmetically acceptable" medium, we mean a non-toxic medium that can be applied to the keratinous materials of human beings and having a pleasant appearance, odour and feel.

In particular, according to one embodiment, the first composition employed in the method according to the invention contains at least one electrophilic monomer.

According to another embodiment, the second composition employed in the method according to the invention contains at least one electrophilic monomer.

Several layers of each first and second composition can also be applied alternately to the keratinous materials.

According to another variant, the invention further relates to a cosmetic method for makeup or non-therapeutic care of keratinous materials selected from the skin, the lips and the eyelashes comprising: a. mixing, at the time of use:

- at least one first composition comprising a cosmetically acceptable medium and at least one electrophilic monomer, and

- at least one second composition comprising a cosmetically acceptable medium then b. applying at least one layer of said mixture to the skin, the lips, or the eyelashes.

According to one embodiment, at least one supplementary layer of at least one third composition containing a cosmetically acceptable medium, and preferably at least one film-forming polymer and at least one organic (or oily) or aqueous solvent medium, is applied to the layer or layers of said second composition in order for example to make the latter longer-lasting.

According to another aspect, the present invention also relates to a kit for make-up or for non-therapeutic care of keratinous materials selected from the skin, the lips and the eyelashes comprising: i) at least one first composition containing at least one electrophilic monomer and ii) at least one second composition containing a cosmetically acceptable medium.

Preferably, the make-up kit according to the invention comprises the first and second compositions packaged separately.

Each composition can be packaged separately in the same packaging article, for example in a two-compartment pen, the base composition being delivered by one end of the pen and the top composition being delivered by the other end of the pen, each end being closed notably hermetically with a cap.

Alternatively, each of the compositions can be packaged in a different packaging article.

The invention further relates to the use of a kit as described above, to obtain a deposited film on keratinous materials, exhibiting improved lasting properties.

Electrophilic monomer

At least one of the compositions according to the invention contains at least one electrophilic monomer.

By electrophilic monomer, we mean a monomer capable of polymerizing by anionic polymerization in the presence of a nucleophilic agent.

By anionic polymerization, we mean the mechanism defined in the work "Advanced Organic Chemistry", Third Edition, of Jerry March, pages 151 to 161. In an anionic polymerization, the nucleophilic agent (for example, the hydroxyl ions OH^' contained in water) initiates polymerization by the formation of a carbanion in contact with the electrophilic monomer.

By "carbanion", we mean the chemical species defined in "Advanced Organic Chemistry", Third Edition, of Jerry March, page 141. According to a particular embodiment, the electrophilic monomer corresponds to formula (A):

R1 R3

R2 R4 _(A) in which:

• R1 and R2 each denote, independently of one another, a group with low or zero electron-accepting properties (with low or zero inductively electron-accepting properties) such as:

- a hydrogen atom, - a saturated or unsaturated hydrocarbon group, linear, branched or cyclic, preferably having from 1 to 20, more preferably from 1 to 10 carbon atoms, and optionally containing one or more nitrogen, oxygen or sulphur atoms and optionally substituted with one or more groups selected from -OR, -COOR, -COR, -SH, -SR, -OH, and the halogen atoms, - a modified or unmodified polyorganosiloxane residue, a polyoxyalkylene group,

• R3 and R4 each denote, independently of one another, an electron-accepting (or inductively electron-accepting) group preferably selected from the groups -N(R)₃ ⁺, -S(R)₂ ⁺, -SH₂ ⁺, -NH₃ ⁺, -NO₂, -SO₂R, -C≡N, -COOH, -COOR, -COSR, -CONH₂, -CONHR, -F, -Cl, -Br, -I, -OR, -COR, -SH, -SR, -OH₁ the linear or branched alkenyl groups, the linear or branched alkynyl groups, the C₁-C₄ mono- or polyfluoroalkyl groups, the aryl groups such as phenyl, or the aryloxy groups such as phenoxyloxy,

R denotes a saturated or unsaturated hydrocarbon group, linear, branched or cyclic, preferably having from 1 to 20, more preferably from 1 to 10 carbon atoms, and optionally containing one or more nitrogen, oxygen or sulphur atoms and optionally substituted with one or more groups selected from -OR', -COOR', -COR', -SH, -SR',

-OH, the halogen atoms, or a polymer residue that can be obtained by radical polymerization, by polycondensation or by ring opening, with R¹ denoting a Ci-C₁₀ alkyl group.

By electron-accepting or inductively electron-accepting group (-I), we mean any group more electronegative than carbon. Reference may be made to the work PR Wells Prog. Phys. Org. Chem., VoI 6, 111 (1968). By group with low or zero electron-accepting properties, we mean any group whose electronegativity is less than or equal to that of carbon.

The alkenyl or alkynyl groups preferably have 2 to 20 carbon atoms, more preferably from 2 to 10 carbon atoms. As saturated or unsaturated hydrocarbon group, linear, branched or cyclic, preferably having from 1 to 20 carbon atoms, we may notably mention the alkyl, alkenyl or alkynyl groups, linear or branched, such as methyl, ethyl, n-butyl, tert- butyl, iso-butyl, pentyl, hexyl, octyl, butenyl or butynyl; the cycloalkyl or aromatic groups. As substituted hydrocarbon group, we may mention for example the hydroxyalkyl or polyhaloalkyl groups.

As examples of unmodified polyorganosiloxane, we may notably mention the polyalkylsiloxanes such as the polydimethylsiloxanes, the polyarylsiloxanes such as the polyphenylsiloxanes, and the polyaralkylsiloxanes such as the polymethylphenylsiloxanes.

Among the modified polyorganosiloxanes, we may notably mention the polydimethylsiloxanes with polyoxyalkylene and/or siloxy and/or silanol and/or amine and/or imine and/or fluoroalkyl groups.

Among the polyoxyalkylene groups, we may notably mention the polyoxyethylene groups and the polyoxypropylene groups having preferably 1 to 200 oxyalkylenated units.

Among the mono- or polyfluoroalkyl groups, we may notably mention groups such as

-(CH₂)n-(CF₂)m-CF₃ or -(CH₂)n-(CF₂)_m-CHF2 with n=1 to 20 and m= 1 to 20.

The substituents R1 to R4 can optionally be substituted with a group having cosmetic activity. The cosmetic activities that are used in particular are obtained from groups with colouring, antioxidant, UV-filter and conditioning functions.

As examples of groups with a colouring function, we may notably mention the azo, quinone, methine, cyanomethine and triarylmethane groups.

As examples of groups with an antioxidant function, we may notably mention groups of the type butylhydroxyanisole (BHA), butylhydroxytoluene (BHT) or vitamin E.

As examples of groups with a UV-filter function, we may notably mention groups such as benzophenones, cinnamates, benzoates, benzylidene-camphors and dibenzoylmethanes.

As examples of groups with a conditioning function, we may notably mention the cationic groups and groups of the aliphatic ester type. Among the electrophilic monomers corresponding to formula (A), we may mention for example:

the benzylidene malononitrile derivatives of formula

2-(4-chloro~benzylidene)-malononitrile of formula

2-cyano-3-phenyl ethyl acrylate,

2-cyano-3-(4-chloro-phenyl) ethyl acrylate

described in Sayyah, J. Polymer Research, 2000, p 97,

the derivatives of methylidene malonates such as:

^■ diethyl 2-methylene-malonate described in the following references by Hopff, Makromoleculare Chemie, 1961, p95, De Keyser, J. Pharm. Sci, 1991, p67 and Klemarczyk, Polymer, 1998, p173

2-ethoxycarbonylmethyleneoxycarbonyl ethyl acrylate described in the following references by Breton, Biomaterials, 1998, p271 and Couvreur, Pharmaceutical Research, 1994, p1270.

- the itaconate derivatives such as :

^■ dimethyl itaconate described in the following reference by Bachrach, European Polymer Journal, 1976, p563

- the derivatives methyl α-(methylsulphonyl)acrylates (K), ethyl α- (methylsulphonyl)acrylates (L), methyl α-(tert-butylsulphonyl)acrylates (M), tert-butyl α- (methylsulphonyl)acrylates (N), tert-butyl α-(tert-butylsulphonyl)acrylates (O) described by Gipstein, J.Org.Chem, 1980, p1486 and - the derivatives 1 ,1-bis-(methylsulphonyl)ethylene (P), 1-acetyl-1 -methyl sulphonyl ethylene (Q), methyl α-(methylsulphonyl) vinyl sulphonate (R), α- methylsulphonylacrylonitrile (S) described by Shearer, US patent US2748050:

The electrophilic monomer or monomers present in the composition of the invention can be selected from:

- methyl vinyl sulphone and phenyl vinyl sulphone notably described by Boor, J. Polymer Science, 1971, p249 -^SO₂Me ^SO₂Ph

- phenyl vinyl sulphoxide notably described by Kanga, Polymer preprints (ACS, Division of Polymer Chemistry), 1987, p322

- 3-methyl-N-(phenylsulphonyl)-1-aza-1 ,3-butadiene notably described by Bonner, Polymer Bulletin, 1992, p517

- the acrylamide monomers such as:

■ n-propyl-n-β-triisopropoxysilylpropyOacrylamide and n-propyl-n~(3- triethoxysilylpropyl)acrylamide notably described by Kobayashi, Journal of Polymer

Science, Part A: Polymer Chemistry, 2005, p2754.

- the acrylate monomers such as:

■ 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate

» n-butyl acrylate

^■ tert-butyl acrylate

- the itaconimide monomers selected from:

^■ n-butyl itaconimide (F), n-(4-tolyl) itaconimide (G), n-(2-ethylphenyl) itaconimide (H), N-(2,6-diethylphenyl) itaconimide (I) notably described in the following reference by Watanabe, J. Polymer Science: Part A: Polymer chemistry, 1994, p2073 R= Bu (F), 4-ethylphenyl (H), 2,6-diethylkphenyl (I)

According to a preferred embodiment, the electrophilic monomer is a monomer of the class of the cyanoacrylates and their derivatives of formula (B):

R1 C=N

I I

C = C (B) i I R2 COXR'3

X denoting NH, S or O,

R1 and R2 having the same meanings as previously, preferably R1 and R2 representing a hydrogen atom, R'3 representing a hydrogen atom or R as defined in formula (A).

Preferably, X denotes O. As compounds of formula (B), we may mention the monomers: a) belonging to the class of the C₁-C₂₀ polyfluoroalkyl 2-cyanoacrylates such as: the 2,2,3,3-tetrafluoropropyl ester of 2-cyano-2-propenoic acid of formula: C≡N

I

CH₂= C

I

COO-CH₂-CF₂-CHF₂ or the 2,2,2-trifluoroethyl ester of 2-cyano-2-propenoic acid of formula:

CsN

I

CH₂= C I

COO-CH₂-CF₃

b) the Ci-C₁₀ alkyl or (CrC₄ alkoxy) C₁-Ci₀ alkyl cyanoacrylates. We may mention more particularly ethyl 2-cyanoacrylate, methyl 2-cyanoacrylate, n- propyl 2-cyanoacrylate, isopropyl 2-cyanoacrylate, tert-butyl 2-cyanoacrylate, n-butyl 2- cyanoacrylate, isobutyl 2-cyanoacrylate, 3-methoxybutyl cyanoacrylate, n-decyl cyanoacrylate, hexyl 2-cyanoacrylate, 2-ethoxyethyl 2-cyanoacrylate, 2-methoxyethyl 2- cyanoacrylate, 2-octyl 2-cyanoacrylate, 2-propoxyethyl 2-cyanoacrylate, n-octyl 2- cyanoacrylate and iso-amyl cyanoacrylate,

c) the benzylidene malononitrile derivatives of formula

2-(4-chloro-benzylidene)-malononitrile of formula

and mixtures thereof.

Within the scope of the invention, it is preferred to use the monomers b). According to a preferred embodiment, the cyanoacrylate monomer or monomers are selected from the C₆-C₁₀ alkyl cyanoacrylates.

The particularly preferred monomers are the octyl cyanoacrylates of formula F and mixtures thereof:

C≡N

I

CH2= C (F)

I COO-R's in which: R'₃ is selected from =-(CH₂)₇-CH₃,

-CH₂-CH(C₂Hs)-(CH₂)S-CH₃, -(CH₂)₅-CH(CH₃)-CH₃, -(CH₂)₄-CH(C₂H₅)-CH₃, and mixtures thereof. The cyanoacrylate monomer particularly preferred according to the invention is octyl 2- cyanoacrylate, linear or branched, sold under the trade designation RITELOK CDN 1064 by the company Chemence.

The monomers used according to the invention can be fixed covalently to supports such as polymers, oligomers or dendrimers. The polymer or the oligomer can be linear, branched, comb-shaped or block. The distribution of the monomers of the invention on the polymeric, oligomeric or dendritic structure can be random, terminal or in the form of blocks.

The cyanoacrylate monomers of formula (B) according to the present invention can be synthesized according to known methods described in the prior art. In particular, the cyanoacrylate monomers can be synthesized according to the teaching of patents US 3 527 224, US 3 591 767, US 3 667 472, US 3 995 641 , US 4 035 334 and US 4 650 826.

In the first composition, the quantity of electrophilic monomer can range from 0.1 to 100 wt.% of the total of the composition containing it, preferably from 1 to 80%, more preferably from 2 to 50% and even more preferably from 5 to 40 wt.% relative to the total weight of the composition containing it.

Nucleophilic agents

The nucleophilic agents that can initiate anionic polymerization are systems that are well known, capable of generating a carbanion in contact with an electrophilic monomer. The nucleophilic agents can notably comprise the hydroxyl ions contained in water.

The nucleophilic agent can be a molecular compound, an oligomer, a dendrimer or a polymer possessing nucleophilic functions. Non-limitatively, we may mention as nucleophilic functions the functions: OH^", R₂N^", NH₂ ^", Ph₃C^", R₃C^", PhNH^", pyridine, ArS^", R-C^SC^", RS^", SH^", RO^", R₂NH, ArO^", N₃ ^", ArNH₂, NH₃, I^", Br^", Cl^", RCOO^", SCN^", ROH, RSH, NCO^", CN^", NO₃ ^", CIO₄ ^", H₂O, with Ph representing a phenyl group; Ar representing an aryl group and R representing a C₁-C₁₀ alkyl group.

Particularly preferred nucleophilic agents are the hydroxyl ions, notably those present in water. The water containing nucleophilic hydroxyl ions can be in particular the residual water of the skin, of the lips and/or of the eyelashes, or water supplied by an external source, for example by prior moistening of the keratinous materials (for example with a facial mister, with natural or artificial tears). It can also be added directly to the composition containing the electrophilic monomer before application or can be present in the composition not containing the electrophilic monomer, for example when the composition contains an aqueous phase.

According to a preferred embodiment, the composition containing the electrophilic monomer does not contain any nucleophilic agent.

According to another preferred embodiment, the nucleophilic agent is supplied by a second composition, applied on top of or underneath the deposit formed by application of the composition containing the electrophilic monomer.

Thus, according to one embodiment, the method according to the invention comprises applying, to keratinous materials, at least one layer of a first composition containing an electrophilic monomer of formula (A) described above, then applying to said layer, at least one layer of a second composition containing an aqueous phase. According to another embodiment, the method according to the invention comprises the application, on keratinous materials, of at least one layer of a first composition containing an aqueous phase, then the application, on said layer, of at least one layer of a second composition containing an electrophilic monomer of formula (A).

The nucleophilic agent can be used pure, in solution, in dispersion in the form of an emulsion, or it can be encapsulated.

The composition of the invention can also include inhibitors of polymerization, and more particularly inhibitors of anionic and/or radical polymerizations, for the purpose of increasing the stability of the composition over time. Non-limitatively, we may mention the following inhibitors of polymerization: sulphur dioxide, nitric oxide, organic acids such as a sulphonic acid or phosphoric acid, acetic acid, lactone, boron trifluoride, hydroquinone and its derivatives such as hydroquinone monethylether, tert-butylhydroquinone, benzoquinone and its derivatives such as duroquinone, catechol and its derivatives such as t-butyl catechol and methoxycatechol, anisole and its derivatives such as methoxyanisole or hydroxyanisole, pyrogallol and its derivatives, p-methoxyphenol, hydroxybutyl toluene, alkyl sulphates, alkyl sulphites, alkyl sulphones, alkyl sulphoxides, alkyl sulphides, mercaptans, and mixtures thereof. Alkyl groups preferably denote groups having 1 to 6 carbon atoms.

The concentration of inhibitor in the composition of the invention can be from 10 ppm to 10%, and more preferably from 50 ppm to 5 wt.%.

Liquid oil phase

The first composition and/or the second composition advantageously contains a liquid oil phase.

By liquid oil phase, in the sense of the application, we mean an oil phase that is liquid at room temperature (25⁰C) and atmospheric pressure (760 mmHg), composed of one or more non-aqueous fats that are liquid at room temperature, also called oils or organic solvents.

The oil can be selected from the volatile oils and/or the non-volatile oils, and mixtures thereof.

The oil or oils can be present in the composition according to the invention at a content in the range from 1 to 80 wt.%, preferably from 5 to 50 wt.% relative to the total weight of the composition.

By "volatile oil", we mean, in the sense of the invention, an oil that can evaporate in contact with the skin or keratin fibre in less than an hour, at room temperature and atmospheric pressure. The volatile organic solvent or solvents and the volatile oils of the invention are organic solvents and cosmetic volatile oils, liquid at room temperature, having a non-zero vapour pressure, at room temperature and atmospheric pressure, ranging in particular from 0.13 Pa to 40 000 Pa (10^"3 to 300 mmHg), in particular from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg), and more particularly from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg).

By "non-volatile oil", we mean an oil that remains on the skin or keratin fibre at room temperature and atmospheric pressure for at least several hours and notably has a vapour pressure below 10^"3mmHg (0.13 Pa). These oils can be hydrocarbon oils, silicone oils, fluorinated oils, or mixtures thereof. By "hydrocarbon oil", we mean an oil mainly containing hydrogen and carbon atoms and optionally atoms of oxygen, nitrogen, sulphur, or phosphorus. The volatile hydrocarbon oils can be selected from the hydrocarbon oils having from 8 to 16 carbon atoms, and notably the C₈-Ci₆ branched alkanes such as the C₈-Ci₆ isoalkanes 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 lsopars or Permetyls, the C₈-C₁₆ branched esters, iso-hexyl neopentanoate, and mixtures thereof. Other volatile hydrocarbon oils such as the petroleum distillates, notably those sold under the name Shell SoIt by the company SHELL, can also be used. Preferably, the volatile solvent is selected from the volatile hydrocarbon oils having from 8 to 16 carbon atoms and mixtures thereof. The volatile silicones can also be used as volatile oils, for example the linear or cyclic volatile silicone oils, notably those having a viscosity < 8 centistokes (8 10^"6 m²/s), and notably having from 2 to 7 silicon atoms, these silicones optionally containing alkyl or alkoxy groups having from 1 to 10 carbon atoms. As volatile silicone oil usable in the invention, we may mention notably octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, heptamethyl hexyltrisiloxane, heptamethyloctyl trisiloxane, hexamethyl disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane and mixtures thereof. We may also mention the volatile linear alkyltrisiloxane oils of general formula (I):

CH

CH 3/ . — SiO — Si- -o- Si ,CH _{3/ 3}

R where R represents an alkyl group containing from 2 to 4 carbon atoms and in which one or more hydrogen atoms can be substituted with a fluorine or chlorine atom.

Among the oils of general formula (I), we may mention:

3-butyl 1 ,1 ,1 ,3,5,5,5-heptamethyl trisiloxane,

3-propyl 1 ,1 ,1 ,3,5,5,5-heptamethyl trisiloxane, and 3-ethyl 1 ,1 ,1 ,3,5,5,5-heptamethyl trisiloxane, corresponding to the oils of formula (I) for which R is respectively a butyl group, a propyl group or an ethyl group.

Fluorinated volatile solvents such as nonafluoromethoxybutane or perfluoromethylcyclopentane can also be used.

The first and/or the second composition can also contain at least one non-volatile oil, notably selected from the non-volatile hydrocarbon oils and/or silicone oils and/or fluorinated oils.

As non-volatile hydrocarbon oil, we may notably mention: the hydrocarbon oils of vegetable origin such as the triesters of fatty acids and of glycerol for which the fatty acids can have chain lengths varying from C₄ to C₂₄, and the latter can be linear or branched, saturated or unsaturated; these oils are notably wheat germ oil, sunflower oil, grapeseed oil, sesame oil, maize oil, apricot oil, castor oil, karite oil, avocado oil, olive oil, soya oil, sweet almond oil, palm oil, colza oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, lucerne oil, poppy oil, Chinese okra oil, sesame oil, cucurbit oil, colza oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, kukui nut oil, passionflower oil, musk rose oil; or the triglycerides of caprylic/capric acids such as those sold by the company Stearineries Dubois or those sold under the designations 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, squalene and mixtures thereof; synthetic esters such as the oils of formula R1COOR2 in which R1 represents the residue of a linear or branched fatty acid having from 1 to 40 carbon atoms and R2 represents a hydrocarbon chain notably branched containing from 1 to 40 carbon atoms with the proviso that R1 + R2 > 10, for example Purcelline oil (ketostearyl octanoate), isopropyl myristate, isopropyl palmitate, alcohol benzoate from C₁₂ to C₁₅, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearatyl isostearate, octanoates, decanoates or ricinoleates of alcohols or of polyalcohols such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate, di-isostearyl malate; and the esters of pentaerythritol; the aliphatic alcohols that are liquid at room temperature with a branched and/or unsaturated hydrocarbon chain having from 12 to 26 carbon atoms such as octyl dodecanol, isostearyl alcohol, oleic alcohol, 2-hexyldecanol, 2-butyloctanol, 2- undecylpentadecanol; - the higher fatty acids such as oleic acid, linoleic acid, linolenic acid; carbonates, acetals, citrates, and mixtures thereof.

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

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

According to one embodiment, the oil phase advantageously contains an ester oil. This ester oil can be selected from the esters of monocarboxylic acids with monoalcohols and polyalcohols. Advantageously, said ester corresponds to the following formula (I):

R₁-CO-O-R₂ (I)

where R₁ represents a linear or branched alkyl radical with 1 to 40 carbon atoms, preferably with 7 to 19 carbon atoms, optionally containing one or more ethylenic double bonds, and optionally substituted; R₂ represents a linear or branched alkyl radical of 1 to 40 carbon atoms, preferably of 3 to 30 carbon atoms and more preferably of 3 to 20 carbon atoms, optionally containing one or more ethylenic double bonds, and optionally substituted. By "optionally substituted", we mean that R-i and/or R₂ can bear one or more substituents selected, for example, from the groups comprising one or more heteroatoms selected from O, N and S, such as amino, amine, alkoxy, hydroxyl.

Preferably, the number total of carbon atoms of R₁ + R₂ is > 9.

Ri can represent the residue of a fatty acid, preferably higher, linear or, preferably branched containing from 1 to 40 and more preferably from 7 to 19 carbon atoms and R₂ can represent a hydrocarbon chain, linear or preferably branched, containing from 1 to 40, preferably from 3 to 30 and more preferably from 3 to 20 carbon atoms. Once again, preferably, the number of carbon atoms of R₁ + R₂ is > 9.

Examples of groups R-i are those derived from fatty acids selected from the group comprising acetic, propionic, butyric, caproic, caprylic, pelargonic, capric, undecanoic, lauric, myristic, palmitic, stearic, isostearic, arachidic, behenic, oleic, linolenic, linoleic, elaeostearic, arachidonic, and erucic acids, and mixtures thereof. Examples of esters are, for example, Purcelline oil (ketostearyl octanoate), isononyl isononanoate, isopropyl myristate, ethyl-2-hexyl palmitate, octyl 2-dodecyl stearate, octyl 2-dodecyl erucate, isostearyl isostearate, and the heptanoates, octanoates, decanoates or ricinoleates of alcohols or of polyalcohols, for example of aliphatic alcohols. Advantageously, the esters are selected from the compounds of the aforementioned formula (1), in which Ri represents an unsubstituted linear or branched alkyl group, optionally containing one or more ethylenic double bonds, of 1 to 40 carbon atoms, preferably 7 to 19 carbon atoms, and R₂ represents an unsubstituted linear or branched alkyl group, optionally containing one or more ethylenic double bonds, of 1 to 40 carbon atoms, preferably 3 to 30 carbon atoms, and more preferably 3 to 20 carbon atoms.

Preferably, R₁ is a branched unsubstituted alkyl group with 4 to 14 carbon atoms, preferably 8 to 10 carbon atoms and R₂ is a branched unsubstituted alkyl group with 5 to 15 carbon atoms, preferably 9 to 11 carbon atoms. Preferably in formula (I), R₁-CO- and R₂ have the same number of carbon atoms and are derived from the same radical, preferably branched unsubstituted alkyl, for example isononyl, i.e. advantageously the ester oil molecule is symmetrical. The ester oil will preferably be selected from the following compounds: isononyl isononanoate, ketostearyl octanoate, - isopropyl myristate, ethyl-2-hexyl palmitate, octyl 2-dodecyl stearate, octyl 2-dodecyl erucate, isostearyl isostearate.

In the case when the compositions are intended to be applied to the lips, in particular a so-called viscous oil can be used, i.e. an oil whose viscosity at 25°C is advantageously greater than or equal to 200 cSt, notably greater than or equal to 500 cSt, or even greater than or equal to 1000 cSt. The viscous oil advantageously has a molecular weight greater than or equal to 600 g/mol, for example greater than or equal to 700, or 800, or even 900 g/mol.

The dynamic viscosity at 25°C of the viscous oil can be measured with a METTLER RM 180 rotary viscometer, taking into account the density of the oil for performing the conversion to cSt. The METTLER RM 180 instrument (Rheomat) can be fitted with different rotors depending on the order of magnitude of the viscosity that is to be measured. For a viscosity between 0.18 and 4.02 Pa.s, the instrument is fitted with a rotor 3. For a viscosity between 1 and 24 Pa.s, the instrument is fitted with a rotor 4, and for a viscosity between 8 and 122 Pa.s, the instrument is fitted with a rotor 5. The viscosity is read on the instrument as the deflection. Then nomograms supplied with the measuring instrument are consulted to obtain the corresponding value in poises, and then perform the conversion to stokes. The speed of rotation of the rotor is 200 rev/min.

Once the rotor has been started, setting a constant speed of rotation (in the present case 200 rev/min), the viscosity value of the oil can vary over time. Measurements are taken at regular time intervals until they become constant. The value of viscosity that has become constant over time is taken as the value of the dynamic viscosity of the viscous oil.

This oil can be selected from: a) silicone oils such as - the polydimethylsiloxanes (PDMS), optionally having a C₃-C₄₀ alkyl chain, or C₃-C₄₀ alkoxy chain, or a phenylated radical; the polydimethylsiloxanes with phenylated radicals can be selected from the phenyltrimethicones;

- the polyalkylmethylsiloxanes, optionally fluorinated such as the polymethyltrifluoro- propyldimethylsiloxanes, - the polyalkylmethylsiloxanes substituted with functional groups such as hydroxyl, thiol and/or amine groups;

- the polysiloxanes modified with fatty acids, aliphatic alcohols or polyoxyalkylenes,

- mixtures thereof, b) apolar hydrocarbon oils such as squalene, linear or branched hydrocarbons such as paraffin oils, petroleum jelly and naphthalene, hydrogenated or partially hydrogenated polyisobutene, isoeicosane, squalane, decene/butene copolymers, polybutene/polyisobutene copolymers notably lndopol L-14, polydecenes such as PURESYN 10, and mixtures thereof.

The oil phase can represent from 5 to 80 wt.% relative to the total weight of the composition, preferably from 10 to 60% and even more preferably from 15 to 50 wt.%.

According to one embodiment, the first and second compositions employed in the method according to the invention are anhydrous, i.e. free from water other than the residual water supplied by certain compounds. Aqueous phase

The first and/or the second composition can contain an aqueous phase.

The aqueous phase can be constituted essentially of water; it can also comprise a mixture of water and water-miscible solvent (miscibility with water greater than 50 wt.% at 25°C) such as lower monoalcohols having from 1 to 5 carbon atoms such as ethanol, isopropanol, glycols having from 2 to 8 carbon atoms such as propylene glycol, ethylene glycol, 1 ,3-butylene glycol, dipropylene glycol, C₃-C₄ ketones, C₂-C₄ aldehydes and mixtures thereof.

The aqueous phase (water and optionally the water-miscible solvent) can be present at a content in the range from 0.1 to 100 wt.%, relative to the total weight of the composition, preferably from 1 to 90 wt.% and more preferably from 2 to 80%.

The aqueous phase can in this case represent from 5 to 95 wt.% relative to the total weight of the composition containing it, preferably from 10 to 85 wt.%.

According to one embodiment, the first composition is anhydrous and the second composition contains an aqueous phase.

According to another embodiment, one of the first and second compositions does not contain electrophilic monomer and contains an aqueous phase.

Solid or pasty fats

The composition according to the invention can also include at least one fat that is solid at room temperature, notably selected from waxes, pasty fats and mixtures thereof. These fats can be of animal, vegetable, mineral or synthetic origin.

Wax

The composition according to the invention can include a wax or a mixture of waxes. The wax considered within the scope of the present invention is generally a lipophilic compound, solid at room temperature (25⁰C), with reversible solid/liquid change of state, having a melting point greater than or equal to 30⁰C and up to 120°C. By reducing the wax to the liquid state (melting), it is possible to make it miscible with oils and to form a microscopically homogeneous mixture, but when the temperature of the mixture returns to room temperature there is recrystallization of the wax in the oils of the mixture. In particular, waxes suitable for the invention can have a melting point above approx. 45°, and in particular above 55°C.

The melting point of the wax can be measured using a differential scanning calorimeter (D.S.C.), for example the calorimeter sold under the designation DSC 30 by the company METLER. The measurement procedure is as follows:

A 15 mg sample of product is placed in a crucible and is submitted to a first temperature rise from 0⁰C to 120⁰C, at a rate of heating of 10°C/minute, then it is cooled from 120⁰C to 0⁰C at a rate of cooling of 10°C/minute and finally it is submitted to a second temperature rise from 0°C to 12O⁰C at a rate of heating of 5°C/minute. During the second temperature rise, the variation of the difference in power absorbed by the empty crucible and by the crucible containing the sample of product is measured in relation to the temperature. The melting point of the compound is the temperature value corresponding to the top of the peak of the curve representing the variation of the difference in power absorbed as a function of the temperature.

The waxes that can be used in the compositions according to the invention are selected from solid waxes, deformable or not at room temperature, of animal, vegetable, mineral or synthetic origin, and mixtures thereof. The wax can also have a hardness in the range from 0.05 MPa to 30 MPa, and preferably in the range from 6 MPa to 15 MPa. The hardness is determined by measuring the compressive force at 20⁰C using the texturometer sold under the designation TA-TX2i by the company RHEO, fitted with a stainless steel cylinder with a diameter of 2 mm moving at a speed of measurement of 0.1 mm/s, and penetrating the wax to a penetration depth of 0.3 mm. The measurement procedure is as follows:

The wax is melted at a temperature equal to the melting point of the wax + 20°C. The molten wax is poured into a container with a diameter of 30 mm and depth of 20 mm. The wax is recrystallized at room temperature (25°C) for 24 hours, then the wax is stored for at least 1 hour at 2O⁰C before measuring the hardness. The value of the hardness is the maximum compressive force measured divided by the surface area of the cylinder of the texturometer in contact with the wax. Notably, the hydrocarbon waxes can be used, such as beeswax, lanolin wax, and Chinese insect waxes; rice wax, Carnauba wax, Candellila wax, Ouricury wax, Alfa wax, cork fibre wax, sugarcane wax, Japan wax and sumac wax; montan wax, microcrystalline waxes, paraffins and ozokerite; polyethylene waxes, waxes obtained by the Fischer-Tropsch synthesis and the waxy copolymers and esters thereof.

We may also mention the waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched, C₈-C₃₂ aliphatic chains. Among the latter, we may notably mention hydrogenated joboba oil, isomerized joboba oil such as the partially hydrogenated, trans-isomerized joboba oil manufactured or marketed by the company Desert Whale under the trade reference ISO-JOJOBA-50^®, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated copra oil and hydrogenated lanolin oil, di-(trimethylol-1 ,1 ,1 propane) tetrastearate sold under the designation "HEST 2T-4S" by the company HETERENE, di-(trimethylol-1 ,1,1 propane) tetrabehenate sold under the designation HEST 2T-4B by the company HETERENE.

We may also mention the silicone waxes such as alkyl or alkoxy-dimethicone having from 16 to 45 carbon atoms, and the fluorinated waxes.

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

According to a particular embodiment, the compositions according to the invention can include at least one wax called sticky wax, i.e. possessing a stickiness 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 can notably permit a cosmetic composition to be obtained which can be applied easily to keratin fibres, having good bonding to keratin fibres and which leads to the formation of a smooth, homogeneous and thickening make-up. The sticky wax used can notably have a stickiness in the range from 0.7 N.s to 30 N.s, in particular greater than or equal to 1 N.s, notably in the range from 1 N.s to 20 N.s, in particular greater than or equal to 2 N.s, notably in the range from 2 N.s to 10 N.s, and in particular in the range from 2 N.s to 5 N.s.

The stickiness of the wax is determined by measuring the variation of the force (compressive force or pulling force) as a function of time, at 20⁰C using the texturometer sold under the designation "TA-TX2i^®" by the company RHEO, fitted with an acrylic polymer rotor in the shape of a cone forming an angle of 45°.

The measurement procedure is as follows:

The wax is melted at a temperature equal to the melting point of the wax + 10⁰C. The molten wax is poured into a container with a diameter of 25 mm and a depth of 20 mm. The wax is recrystallized at room temperature (25°C) for 24 hours so that the surface of the wax becomes flat and smooth, then the wax is stored for at least 1 hour at

20⁰C before measuring the stickiness.

The rotor of the texturometer is displaced at a speed of 0.5 mm/s, and penetrates the wax to a penetration depth of 2 mm. When the rotor has penetrated the wax to the depth of

2 mm, the rotor is held fixed for 1 second (corresponding to the relaxation time) and is then withdrawn at a speed of 0.5 mm/s.

During the relaxation time, the force (compressive force) decreases rapidly until it reaches zero, then, on withdrawal of the rotor, the force (pulling force) becomes negative and then increases again to the value 0. The stickiness corresponds to the integral of the curve of the force as a function of time for the portion of the curve corresponding to the negative values of the force (pulling force). The value of the stickiness is expressed in N.s.

The sticky wax that can be used generally has a hardness less than or equal to 3.5 MPa, in particular in the range from 0.01 MPa to 3.5 MPa, notably in the range from 0.05 MPa to 3 MPa, especially in the range from 0.1 MPa to 2.5 MPa.

The hardness is measured according to the procedure described previously.

A C₂₀-C₄₀ alkyl (hydroxystearyloxy)stearate (with the alkyl group containing from 20 to 40 carbon atoms), alone or in a mixture, in particular a C₂₀-C₄₀ alkyl 12-(12'- hydroxystearyloxy)stearate, can be used as sticky wax. Such a wax is notably sold under the designations "Kester Wax K 82 P^®" and "Kester

Wax K 80 P^®" by the company KOSTER KEUNEN.

The waxes mentioned above generally have an initial melting point below 45°C.

The wax or waxes can be present in the form of an aqueous microdispersion of wax. By aqueous microdispersion of wax, we mean an aqueous dispersion of wax particles, in which the size of said wax particles is less than or equal to about 1 μm.

Wax microdispersions are stable dispersions of colloidal wax particles, and are notably described in "Microemulsions Theory and Practice", LM. Prince Ed., Academic Press (1977) pages 21-32. In particular, these wax microdispersions can be obtained by melting the wax in the presence of a surfactant, and optionally a portion of water, then progressively adding hot water, with stirring. We observe the intermediate formation of an emulsion of the water-in- oil type, followed by phase inversion, finally obtaining a microemulsion of the oil-in-water type. On cooling, a stable microdispersion of solid colloidal wax particles is obtained.

Wax microdispersions can also be obtained by agitation of a mixture of wax, surfactant and water by agitating means such as ultrasound, a high-pressure homogenizer, or turbines.

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

These particles are constituted essentially of a wax or of a mixture of waxes. They can however contain a minor proportion of oily and/or pasty fat additives, a surfactant and/or a usual fat-soluble additive/active.

By pasty fat, we mean a lipophilic fat compound containing, at a temperature of 23°C, a liquid fraction and a solid fraction.

Said pasty compound preferably has a hardness at 2O⁰C in the range from 0.001 to 0.5 MPa, preferably from 0.002 to 0.4 MPa.

The hardness is measured by a method of penetration of a probe into a sample of the compound and in particular using a texture analyser (for example the TA-XT2i from Rheo) fitted with a stainless steel cylinder with a diameter of 2 mm. The hardness is measured at 2O⁰C at the centre of 5 samples. The cylinder is inserted into each sample at an initial speed of 1 mm/s then at a measurement speed of 0.1 mm/s, the depth of penetration being 0.3 mm. The hardness value read is that of the maximum peak. The liquid fraction of the pasty compound measured at 23°C preferably represents 9 to 97 wt.% of the compound. This liquid fraction at 23⁰C preferably represents between 15 and 85 wt.%, and more preferably between 40 and 85 wt.%. The liquid fraction by weight of the pasty compound at 23⁰C is equal to the ratio of the enthalpy of fusion consumed at 23⁰C to the enthalpy of fusion of the pasty compound.

The enthalpy of fusion of the pasty compound is the enthalpy consumed by the compound in passing from the solid state to the liquid state. The pasty compound is said to be in the solid state when all of its mass is in solid crystalline form. The pasty compound is said to be in the liquid state when all of its mass is in liquid form. The enthalpy of fusion of the pasty compound is equal to the area under the curve of the thermogram obtained using the differential scanning calorimeter (DSC), such as the calorimeter sold under the designation MDSC 2920 by the company TA instrument, with a temperature rise of 5 or 10°C per minute, according to standard ISO 11357-3:1999. The enthalpy of fusion of the pasty compound is the amount of energy required to cause the compound to change from the solid state to the liquid state. It is expressed in J/g. The enthalpy of fusion consumed at 23°C is the amount of energy absorbed by the sample on passing from the solid state to the state that it has at 23°C, comprising a liquid fraction and a solid fraction. The liquid fraction of the pasty compound measured at 32°C preferably represents from 30 to 100 wt.% of the compound, preferably from 80 to 100%, more preferably from 90 to 100 wt.% of the compound. When the liquid fraction of the pasty compound measured at 32⁰C is equal to 100%, the temperature of the end of the melting range of the pasty compound is less than or equal to 32⁰C. The liquid fraction of the pasty compound measured at 32°C is equal to the ratio of the enthalpy of fusion consumed at 32⁰C to the enthalpy of fusion of the pasty compound. The enthalpy of fusion consumed at 32°C is calculated in the same way as the enthalpy of fusion consumed at 23°C.

The pasty substances are generally hydrocarbon compounds such as lanolins and their derivatives or they are PDMSs.

The nature and the amount of the solid substances depend on the required mechanical properties and textures. As a guide, the composition can contain from 0.1 to 70 wt.% of waxes, relative to the total weight of the composition, preferably from 1 to 60% and more preferably from 5 to 40 wt.%.

Film-forming polymer

The composition can include a film-forming polymer. According to the present invention, by "film-forming polymer" we mean a polymer that is able to form, on its own or in the presence of a film-forming auxiliary, a continuous film that adheres to a substrate, notably to keratinous materials.

The film-forming polymer can be present in the composition according to the invention at a content of dry matter (or active matter) in the range from 0.1 to 30 wt.% relative to the total weight of the composition, preferably from 0.5 to 20 wt.%, and more preferably from 1 to 15 wt.%.

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

By film-forming radical polymer, we mean a polymer obtained by polymerization of monomers with an unsaturation, notably ethylenic, each monomer being capable of homopolymerizing (in contrast to the polycondensates). The film-forming polymers of the radical type can notably be vinylic polymers or copolymers, notably acrylic polymers.

The film-forming vinyl polymers can result from the polymerization of monomers with ethylenic unsaturation having at least one acid group and/or esters of these acid monomers and/or amides of these acid monomers. As the monomer bearing an acid group, it is possible to use α,β-ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid. Preferably (meth)acrylic acid and crotonic acid are used, and more preferably

(meth)acrylic acid.

The esters of acid monomers are advantageously selected from the esters of (meth)acrylic acid (also called (meth)acrylates), notably alkyl (meth)acrylates, in particular

C₁-C₃₀ alkyl, preferably C₁-C₂Ol aryl (meth)acrylates, in particular C₆-C₁₀ aryl; hydroxyalkyl

(meth)acrylates, in particular C₂-C₆ hydroxyalkyl.

Among the alkyl (meth)acrylates, we may mention methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, ethyl-2 hexyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate.

Among the hydroxyalkyl (meth)acrylates, we may mention hydroxyethyl acrylate, 2- hydroxypropyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate.

Among the aryl (meth)acrylates, we may mention benzyl acrylate and phenyl acrylate.

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

As amides of the acid monomers, we may mention for example the (meth)acrylamides, and notably the N-alkyl (meth)acrylamides, in particular C₂-C₁₂ alkyl. Among the N-alkyl (meth)acrylamides, we may mention N-ethyl acrylamide, N-t-butyl acrylamide, N-t-octyl acrylamide and N-undecylacrylamide. The film-forming vinyl polymers can also result from the homopolymerization or copolymerization of monomers selected from vinyl esters and styrene monomers. In particular, these monomers can be polymerized with acid monomers and/or their esters and/or their amides, such as those mentioned above. As examples of vinyl esters, we may mention vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butyl benzoate. As styrene monomers, we may mention styrene and alpha-methyl styrene. Among the film-forming polycondensates, we may mention polyurethanes, polyesters, polyester amides, polyamides, and epoxyester resins, polyureas. The polyurethanes can be selected from the anionic, cationic, non-ionic or amphoteric polyurethanes, the acrylic polyurethanes, the polyvinylpyrrolidone polyurethanes, the polyester-polyurethanes, the polyether-polyurethanes, the polyureas, the polyurea- polyurethanes, and mixtures thereof. The polyesters can be obtained, in a known manner, by polycondensation of dicarboxylic acids with polyols, notably diols.

The dicarboxylic acid can be aliphatic, alicyclic or aromatic. We may mention as examples of such acids: oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2,2-dimethylglutaric acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, 1 ,3- cyclohexanedicarboxylic acid, 1 ,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2,5-norbornane dicarboxylic acid, diglycolic acid, thiodipropionic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid. These dicarboxylic acid monomers can be used alone or in combination with at least two dicarboxylic acid monomers. Among these monomers, more preferably phthalic acid, isophthalic acid, and terephthalic acid are selected.

The diol can be selected from the aliphatic, alicyclic, and aromatic diols. The diol used is preferably selected from: ethylene glycol, diethylene glycol, triethylene glycol, 1 ,3- propanediol, cyclohexane dimethanol, 4-butanediol. As other polyols, it is possible to use glycerol, pentaerythritol, sorbitol, trimethylol propane. The polyester amides can be obtained in a similar way to the polyesters, by polycondensation of diacids with diamines or amino alcohols. As diamine, we can use ethylenediamine, hexamethylenediamine, meta- or para-phenylenediamine. As aminoalcohol, we can use monoethanolamine. The polyester can in addition contain at least one monomer bearing at least one -SO₃M group, with M representing a hydrogen atom, an ammonium ion NH₄ ⁺ or a metal ion, for example an Na⁺, Li⁺, K⁺, Mg²⁺, Ca²⁺, Cu²⁺, Fe²⁺, Fe³⁺ ion. Notably a bifunctional aromatic monomer containing said group -SO₃M can be used.

The aromatic nucleus of the bifunctional aromatic monomer additionally bearing an -SO₃M group as described above can be selected for example from the benzene, naphthalene, anthracene, diphenyl, oxydiphenyl, sulphonyldiphenyl, methylenediphenyl rings. The following may be mentioned as examples of bifunctionai aromatic monomer additionally bearing an -SO₃M group: sulphoisophthalic acid, sulphoterephthalic acid, sulphophthalic acid, 4-sulphonaphthalene-2,7-dicarboxylic acid.

It is preferable to use copolymers based on isophthalate/sulphoisophthalate, and more particularly copolymers obtained by condensation of di-ethyleneglycol, cyclohexane di- methanol, isophthalic acid, sulphoisophthalic acid.

The polymers of natural origin, optionally modified, can be selected from shellac, sandarac gum, damars, elemis, copals, cellulosic polymers, and mixtures thereof.

According to a first embodiment of the composition according to the invention, the film- forming polymer can be a water-soluble polymer and can be present in an aqueous phase of the composition; therefore the polymer is dissolved in the aqueous phase of the composition.

According to another variant of realization of the composition according to the invention, the film-forming polymer can be a polymer dissolved in a liquid oil phase comprising oils or organic solvents such as those described previously (the film-forming polymer is then said to be a fat-soluble polymer). Preferably, the liquid oil phase contains a volatile oil, optionally mixed with a non-volatile oil, and the oils can be selected from the oils mentioned previously. As examples of fat-soluble polymer, we may mention the vinyl ester copolymers (the vinyl group being joined directly to the oxygen atom of the ester group and the vinyl ester having a saturated, linear or branched hydrocarbon radical, with 1 to 19 carbon atoms, joined to the carbonyl of the ester group) and at least one other monomer which can be a vinyl ester (different from the vinyl ester already present), an α-olefin (having from 8 to 28 carbon atoms), an alkylvinylether (the alkyl group of which has from 2 to 18 carbon atoms), or an allylic or methallylic ester (having a saturated, linear or branched hydrocarbon radical, of 1 to 19 carbon atoms, joined to the carbonyl of the ester group). These copolymers can be crosslinked by means of crosslinking agents, which can either be of the vinylic type, or of the allylic or methallylic type, such as tetraallyloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate, and divinyl octadecanedioate. As examples of these copolymers, we may mention the following copolymers: vinyl acetate/allyl stearate, vinyl acetate/vinyl laurate, vinyl acetate/vinyl stearate, vinyl acetate/octadecene, vinyl acetate/octadecylvinylether, vinyl propionate/allyl laurate, vinyl propionate/vinyl laurate, vinyl stearate/octadecene-1 , vinyl acetate/dodecene-1 , vinyl stearate/ethylvinylether, vinyl propionate/cetyl vinyl ether, vinyl stearate/allyl acetate, dimethyl-2, vinyl 2 octanoate/vinyl laurate, allyl dimethyl-2, 2 pentanoate/vinyl laurate, dimethyl vinyl propionate/vinyl stearate, allyl dimethyl propionate/vinyl stearate, vinyl propionate/vinyl stearate, crosslinked with 0.2% divinyl benzene, vinyl dimethyl propionate/vinyl laurate, crosslinked with 0.2% divinyl benzene, vinyl acetate/octadecyl vinyl ether, crosslinked with 0.2% tetraallyloxyethane, vinyl acetate/allyl stearate, crosslinked with 0.2% divinyl benzene, vinyl acetate/octadecene-1 crosslinked with 0.2% divinyl benzene and allyl propionate/allyl stearate crosslinked with 0.2% divinyl benzene. As fat-soluble film-forming polymers, we may also mention the fat-soluble copolymers, and in particular those resulting from copolymerization of vinyl esters having from 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, the alkyl radicals having from 10 to 20 carbon atoms.

Such fat-soluble copolymers can be selected from the copolymers of vinyl polystearate, of vinyl polystearate crosslinked with divinylbenzene, of diallylether or of diallyl phthalate, the copolymers of stearyl poly(meth)acrylate, of vinyl polylaurate, of lauryl poly(meth)acrylate; these poly(meth)acrylates can be crosslinked using dimethacrylate of ethylene glycol or of tetraethylene glycol.

The fat-soluble copolymers defined previously are known and notably are described in application FR-A-2232303; they can have a weight-average molecular weight in the range from 2000 to 500 000 and preferably from 4000 to 200 000. We may also mention the fat-soluble 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, the alkyl radicals having from 2 to 24 carbon atoms. As examples of fat-soluble homopolymers, we may mention notably: vinyl polylaurate and lauryl poly(meth)acrylates; these poly(meth)acrylates can be crosslinked using dimethacrylate of ethylene glycol or of tetraethylene glycol.

According to an advantageous embodiment, the first composition of the method according to the invention includes at least one vinyl polylaurate film-forming polymer.

As fat-soluble film-forming polymers that can be used in the invention, we may also mention the polyalkylenes and notably the copolymers of C₂-C₂₀ alkenes, such as polybutene, the alkylcelluloses with a linear or branched, saturated or unsaturated C₁-C₈ alkyl radical, such as ethylcellulose and propylcellulose, the copolymers of vinylpyrrolidone (VP) and notably the copolymers of vinylpyrrolidone and C₂-C₄O and preferably C₃-C₂₀ alkene. As examples of VP copolymers that can be used in the invention, we may mention the VP/vinyl acetate, VP/ethyl methacrylate, butylated polyvinylpyrrolidone (PVP), VP/ethyl methacrylate/methacrylic acid, VP/eicosene, VP/hexadecene, VP/triacontene, VP/styrene, VP/acrylic acid/lauryl methacrylate copolymers.

We may also mention the silicone resins, generally soluble or swellable in silicone oils, which are polymers of crosslinked polyorganosiloxanes. The class of silicone resins is known by the name "MDTQ", the resin being described on the basis of the various siloxane monomer units that it contains, each of the letters "MDTQ" identifying a type of unit.

As examples of commercially available polymethylsilsesquioxane resins, we may mention those marketed: by the company Wacker under the reference Resin MK such as Belsil PMS

MK: by the company SHIN-ETSU under the references KR-220L.

As siloxysilicate resins, we may mention the trimethylsiloxysilicate (TMS) resins such as those marketed under the reference SR1000 by the company General Electric or under the reference TMS 803 by the company Wacker. We may also mention the timethylsiloxysilicate resins marketed in a solvent, such as the cyclomethicone sold under the designation "KF-7312J" by the company Shin-Etsu, "DC 749", "DC 593" by the company Dow Corning. We may also mention copolymers of silicone resins such as those mentioned above with polydimethylsiloxanes, such as the pressure-sensitive adhesive copolymers marketed by the company Dow Corning under the reference BIO-PSA and described in document US 5 162 410 or the silicone copolymers resulting from the reaction of a silicone resin, such as those described above, and a diorganosiloxane as described in document WO 2004/073626.

It is also possible to use the siliconized polyamides of the polyorganosiloxane type such as those described in documents US-A-5 874 069, US-A-5,919,441 , US-A-6,051 ,216 and US-A-5,981 ,680.

These silicone polymers can belong to the following two classes: polyorganosiloxanes having at least two groups capable of establishing hydrogen interactions, these two groups being located in the polymer chain, and/or polyorganosiloxanes having at least two groups capable of establishing hydrogen interactions, these two groups being located on of the grafts or branchings. According to one embodiment of the invention, the film-forming polymer is a linear- sequenced film-forming ethylenic polymer, which preferably has at least one first sequence and at least one second sequence having different glass transition temperatures (Tg), said first and second sequences being joined together by an intermediate sequence comprising at least one monomer that is a constituent of the first sequence and at least one monomer that is a constituent of the second sequence. Advantageously, the first and second sequences of the sequenced polymer are incompatible with one another.

Such polymers are described for example in documents EP 1411069 or WO 04/028488.

The film-forming polymer can also be present in the composition in the form of particles dispersed in an aqueous phase or in a non-aqueous solvent phase, generally known as a latex or pseudolatex. The techniques for preparation of these dispersions are well known by a person skilled in the art.

It is possible to use, as aqueous dispersion of film-forming polymer, the acrylic dispersions sold under the designations Neocryl XK-90^®, Neocryl A-1070^®, Neocryl A- 1090^®, Neocryl BT-62^®, Neocryl A-1079^® and Neocryl A-523^® by the company AVECIA- NEORESINS, Dow Latex 432^® by the company DOW CHEMICAL, Daitosol 5000 AD^® or Daitosol 5000 SJ^® by the company DAITO KASEY KOGYO; Syntran 5760^® by the company Interpolymer, Allianz OPT by the company ROHM & HAAS, the aqueous dispersions of acrylic or styrene/acrylic polymers sold under the trade name JONCRYL^® by the company JOHNSON POLYMER or the aqueous dispersions of polyurethane sold under the designations Neorez R-981^® and 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^® and Sancure 2060^® by the company GOODRICH, lmpranil 85^® by the company BAYER, Aquamere H-1511^® by the company HYDROMER; the sulphopolyesters sold under the trade name Eastman AQ^® by the company Eastman Chemical Products, the vinylic dispersions such as Mexomer PAM^® from the company CHIMEX and mixtures thereof.

As examples of non-aqueous dispersions of film-forming polymer, we may mention the acrylic dispersions in isododecane such as Mexomer PAP^® from the company CHIMEX, the dispersions of particles of an ethylenic, preferably acrylic, graft polymer in a liquid oil phase, the ethylenic polymer advantageously being dispersed in the absence of additional particle surface stabilizer as described notably in document WO 04/055081. The composition according to the invention can include a plasticizer which promotes the formation of a film with the film-forming polymer. Such a plasticizer can be selected from all the compounds known by a person skilled in the art as being able to fulfil the required function.

Colouring matter

The first and second compositions employed in the method according to the invention can contain at least one colouring matter selected for example from pigments, nacres, colorants, materials for special effects and mixtures thereof.

These colouring materials can be present at a content in the range from 0.01 to 50 wt.%, preferably of 0.01 to 30% relative to the weight of each first and second composition.

According to one embodiment of the invention, the composition containing the electrophilic monomer does not contain pigments based on metal oxide, notably iron, without surface treatment, in particular without surface treatment by an organic and/or hydrophobic agent, or not coated with an organic layer, on account of the reactivity of the electrophilic monomer with this type of colouring matter. According to a particular embodiment, the composition containing the electrophilic monomer does not contain pigments without surface treatment. Even more particularly, the composition containing the electrophilic monomer does not contain pigments and fillers without surface treatment. The surface-treated pigments or fillers are pigments or fillers which have undergone, completely or partially, a surface treatment of a chemical, electronic, electrochemical, mechano-chemical or mechanical nature, with an agent such as those described notably in Cosmetics and Toiletries, February 1990, Vol. 105, p. 53-64.

According to another embodiment, the composition containing the electrophilic monomer does not contain pigments, more particularly pigments and fillers.

According to another embodiment, the composition containing the electrophilic monomer according to the invention contains a pigment that has been surface-treated, in particular with an organic and/or hydrophobic agent, or coated with an organic layer. Preferably, the composition not containing electrophilic monomer advantageously contains at least one colouring matter.

The pigments for use in the present invention can be in the form of powder or of pigment paste.

"Colorants" is to be understood as meaning compounds, generally organic, that are soluble in at least one oil or in an aqueous-alcoholic phase.

"Pigments" is to be understood as meaning white or coloured particles, mineral or organic, insoluble in the aqueous medium, intended to colour and/or opacify the resultant film.

"Nacres" or nacreous pigments, is to be understood as meaning coloured particles of any shape, iridescent or not, notably produced in the shell of certain molluscs or alternatively manufactured synthetically, and which display a colouring effect by optical interference.

The pigments can be dispersed in the product by means of a dispersant. The dispersant protects the dispersed particles against agglomeration or flocculation. The dispersant can be a surfactant, an oligomer, a polymer or a mixture of several of them together, bearing one or more functionalities having a strong affinity for the surface of the particles to be dispersed. In particular, they can attach physically or chemically to the surface of the pigments. These dispersants have, in addition, at least one functional group that is compatible or soluble in the continuous medium. In particular, the esters of hydroxy-12 stearic acid are used, and of C₈-C₂Q fatty acid and of polyol such as glycerol, diglycerol, such as the stearate of poly(12-hydroxystearic) acid with molecular weight of about 750 g/mol such as that sold under the name Solsperse 21 000 by the company Avecia, polygyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel or polyhydroxystearic acid such as that sold under the reference Arlacel P100 by the company Uniqema and mixtures thereof. Other dispersants that can be used in the composition of the invention that we may mention are the quaternary ammonium derivatives of polycondensed fatty acids such as Solsperse 17 000 sold by the company Avecia, and mixtures of polydimethylsiloxane/oxypropylene such as those sold by the company Dow Corning under the references DC2-5185, DC2-5225 C. Polydihydroxystearic acid and the esters of hydroxy12-stearic acid are preferably intended for a hydrocarbon or fluorinated medium, whereas the oxyethylene/oxypropylene dimethylsiloxane mixtures are preferably intended for a siliconized medium. We may mention, among the mineral pigments, titanium dioxide, optionally surface- treated, oxides of zirconium or of cerium, as well as the oxides of zinc, of iron (black, yellow or red) or of chromium, manganese violet, ultramarine, chromium hydrate and ferric blue, and metallic powders such as aluminium powder, copper powder.

Among the organic pigments, we may mention carbon black, D & C type pigments, and lakes based on carmine, barium, strontium, calcium, aluminium.

We may also mention the special-effect pigments such as particles having an organic or mineral, natural or synthetic substrate, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas, said substrate being coated or not with metallic substances such as aluminium, gold, silver, platinum, copper, bronze, or metal oxides such as titanium dioxide, iron oxide, chromium oxide and mixtures thereof.

The nacreous pigments can be selected from mica coated with titanium dioxide or bismuth oxychloride, titanium mica coated with iron oxides, titanium mica notably coated with ferric blue or chromium oxide, titanium mica coated with an organic pigment of an aforementioned type as well as nacreous pigments based on bismuth oxychloride. Interference pigments can also be used, notably with liquid crystals or multilayered.

The compositions according to the invention can contain at least one filler, notably at a content in the range from 0.01 to 50 wt.%, relative to the total weight of each composition, preferably in the range from 0.01 to 30 wt.%. The fillers can be mineral or organic of any shape, plate-like, spherical or oblong, whatever the crystallographic form (for example lamellar, cubic, hexagonal, orthorhombic, etc). We may mention talc, mica, silica, kaolin, powders of polyamide (Nylon®) (Orgasol® from Atochem), of poly-β-alanine and of polyethylene, powders of tetrafluoroethylene polymers (Teflon®), lauroyl-lysine, starch, boron nitride, hollow polymer microspheres such as those of polyvinylidene chloride/acrylonitrile such as Expancel® (Nobel Industrie), of copolymers of acrylic acid (Polytrap® of Company Dow Corning) and microbeads of silicone resin (Tospearls® from Toshiba, for example), particles of polyorganosiloxane elastomers, precipitated calcium carbonate, magnesium carbonate and hydro-carbonate, hydroxyapatite, hollow silica microspheres (Silica Beads® from Maprecos), glass or ceramic microcapsules, metal soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example stearate of zinc, magnesium or lithium, zinc laurate, magnesium myristate.

The compositions according to the invention can also contain ingredients commonly used in cosmetics, such as vitamins, thickeners, gelling agents, trace elements, emollients, sequestering agents, perfumes, alkalizing or acidifying agents, preservatives, sun filters, surfactants, antioxidants, fibres, care agents, cyanoacrylate stabilizers or mixtures thereof.

The gelling agents that can be used in the compositions according to the invention can be hydrophilic, lipophilic, organic or mineral, polymeric or molecular gelling agents.

As mineral lipophilic gelling agents, we may mention the clays, optionally modified, such as the hectorites modified with ammonium chloride of C₁₀-C₂₂ fatty acid, such as hectorite modified with distearyl dimethyl ammonium chloride, for example, that marketed with the designation "Bentone 38V^®" by the company ELEMENTIS.

We may also mention dry-distilled silica optionally with hydrophobic surface treatment, with particle size less than 1 μm. It is in fact possible for the surface of silica to be modified chemically, by a chemical reaction that leads to a decrease in the number of silanol groups present on the surface of the silica. Notably, the silanol groups can be replaced with hydrophobic groups: a hydrophobic silica is then obtained. The hydrophobic groups can be:

- trimethylsiloxyl groups, which are notably obtained by treatment of dry- distilled silica in the presence of hexamethyldisilazane. Silicas treated in this way are called "Silica silylate" according to the CTFA (6^th edition, 1995). They are for example marketed under the references "Aerosil R812^®" by the company DEGUSSA, "CAB-O-SIL TS-530^®" by the company CABOT,

- dimethylsilyloxyl or polydimethylsiloxane groups, which are notably obtained by treatment of dry-distilled silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas treated in this way are called "Silica dimethyl silylate" according to the CTFA (6^th edition, 1995). They are for example marketed under the references "Aerosil R972^®", and "Aerosil R974^®" by the company DEGUSSA, "CAB-O-SIL TS-610^®" and "CAB-O-SIL TS-720^®" by the company CABOT.

The dry-distilled hydrophobic silica has in particular a particle size that can range from nanometric to micrometric, for example ranging from about 5 to 200 nm. The lipophilic organic polymeric gelling agents are for example elastomeric organopolysiloxanes, partially or fully crosslinked, of three-dimensional structure, such as those marketed under the designations "KSG6^®", "KSG16^®" and "KSG18^®" by the company SHIN-ETSU, "Trefil E-505C^®" and "Trefil E-506C^®" by the company DOW- CORNING, "Gransil SR-CYC^®", ¹¹SR DMF10^®", "SR-DC556^®", "SR 5CYC gel^®", "SR DMF 10 gel^®" and ¹¹SR DC 556 gel^®" by the company GRANT INDUSTRIES, "SF 1204^®" and "JK 113^®" by the company GENERAL ELECTRIC; ethylcellulose such as that sold under the designation "Ethocel^®" by the company DOW CHEMICAL; galactomannans having from one to six, and in particular from two to four, hydroxyl groups per monosaccharide unit, substituted with a saturated or unsaturated alkyl chain, such as guar gum alkylated by Ci to C₆, and in particular C₁ to C₃ alkyl chains, and mixtures thereof. The sequenced copolymers of the "diblock" or "triblock" type such as polystyrene/polyisoprene, polystyrene/polybutadiene e.g. those marketed under the designation "Luvitol HSB^®" by the company BASF, of the polystyrene/copoly(ethylene-propylene) type such as those marketed under the designation "Kraton^®" by the company SHELL CHEMICAL CO or of the polystyrene/copoly(ethylene-butylene) type.

Among the lipophilic gelling agents that can be used in the compositions according to the invention, we may also mention the esters of dextrin and fatty acid, such as the dextrin palmitates, notably such as those marketed under the designations "Rheopearl TL^®" or "Rheopearl KL^®" by the company CHIBA FLOUR.

The lipophilic gelling agents can be present in the compositions according to the invention at a content in the range from 0.05 to 40 wt.% relative to the total weight of each composition, preferably from 0.5 to 20% and more preferably from 1 to 15 wt.%.

As hydrophilic or water-soluble gelling agent, we may mention: homo- or copolymers of acrylic or methacrylic acids or their salts and their esters and in particular the products sold under the designations "VERSICOL F" or "VERSICOL K" by the company ALLIED COLLOID,

"UTRAHOLD 8" by the company CIBA-GEIGY, the polyacrylic acids of the SYNTHALEN

K type, copolymers of acrylic acid and acrylamide sold in the form of their sodium salt under the designations "RETEN" by the company HERCULES, sodium polymethacrylate sold under the designation "DARVAN N°7" by the company

VANDERBILT, sodium salts of polyhydroxycarboxylic acids sold under the designation ¹¹HYDAGEN F" by the company HENKEL, polyacrylic acid/alkyl acrylate copolymers of the PEMULEN type,

AMPS (polyacrylamidomethyl propane sulphonic acid partially neutralized with ammonia and highly crosslinked) marketed by the company CLARIANT, - AMPS/acrylamide copolymers of the SEPIGEL or SIMULGEL type marketed by the company SEPPIC, and polyoxyethylenated AMPS/alkyl methacrylate copolymers (crosslinked or not) and mixtures thereof.

As other examples of water-soluble polymer gelling agents, we may mention: proteins, such as proteins of vegetable origin such as wheat proteins and soya protein; proteins of animal origin such as keratins, for example keratin hydrolysates and sulphonic keratins; the anionic, cationic, amphoteric or non-ionic polymers of chitin or of chitosan; the polymers of cellulose such as hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, as well as the quaternized cellulose derivatives; vinyl polymers, such as polyvinylpyrrolidones, copolymers of methylvinyl ether and malic anhydride, copolymer of vinyl acetate and crotonic acid, copolymers of vinylpyrrolidone and vinyl acetate; copolymers of vinylpyrrolidone and caprolactam; polyvinyl alcohol; the associative polyurethanes such as the polymer Ci₆-OE₁₂O-C₁₆ from the company SERVO DELDEN (marketed under the name SER AD FX1100, molecule with urethane function and weight-average molecular weight of 1300), OE being an oxyethylenated unit, Rheolate 205 with urea function sold by the company RHEOX or

Rheolate 208 or 204 (these polymers being sold in the pure form) or DW 1206B from

ROHM & HAAS with a C₂₀ alkyl chain with a urethane bond, sold at 20% of dry matter in water. It is also possible to use solutions or dispersions of these associative polyurethanes notably in water or in aqueous-alcoholic medium. As examples of such polymers we may mention: SER AD FX1010, SER AD FX1035 and SER AD 1070 from the company

SERVO DELDEN, and Rheolate 255, Rheolate 278 and Rheolate 244 sold by the company RHEOX. It is also possible to use the products DW 1206F and DW 1206J₁ as well as Acrysol RM 184 or Acrysol 44 from the company ROHM & HAAS, or Borchigel LW 44 from the company BORCHERS₁ the polymers of natural origin, optionally modified, such as: gum arabic, guar gum, xanthan derivatives, gum karaya; alginates and carrageenans; glycoaminoglycans, hyaluronic acid and its derivatives; shellac, sandarac gum, damars, elemis, copals; - deoxyribonucleic acid; mucopolysaccharides such as hyaluronic acid, chondroitin sulphates, and mixtures thereof.

The hydrophilic gelling agents can be present in the compositions according to the invention at a content in the range from 0.05 to 20 wt.% relative to the total weight of each composition, preferably from 0.5 to 10% and more preferably from 0.8 to 5 wt.%.

The compositions according to the invention can contain emulsifying surfactants notably in a proportion in the range from 0.1 to 30 wt.% relative to the total weight of each composition, preferably from 1 to 15% and more preferably from 2 to 10%. These surfactants can be selected from anionic, cationic, non-ionic, amphoteric or zwitterionic surfactants. Reference may be made to the document "Encyclopedia of Chemical Technology, KIRK-OTHMER", volume 22, p.333-432, 3rd edition, 1979, WILEY, for the definition of the properties and functions (emulsifying) of the surfactants, in particular p.347-377 of this reference, for the anionic and non-ionic surfactants.

The surfactants preferably used in the compositions according to the invention are selected from: a) non-ionic surfactants of HLB greater than or equal to 8 at 25⁰C, used alone or in a mixture; we may mention notably: the oxyethylenated and/or oxypropylenated ethers (which can contain from 1 to 150 oxyethylene and/or oxypropylene groups) of glycerol; the oxyethylenated and/or oxypropylenated ethers (which can contain from 1 to 150 oxyethylene and/or oxypropylene groups) of aliphatic alcohols (notably of C₈-C₂₄, and preferably C₁₂-C₁₈ alcohol) such as the oxyethylenated ether of cetearyl alcohol with 30 oxyethylene groups (CTFA name "Ceteareth-30") and the oxyethylenated ether of the mixture of Ci₂-C₁₅ aliphatic alcohols containing 7 oxyethylene groups (CTFA name "C12-15 Pareth-7" marketed under the designation "NEODOL 25-7^®" by SHELL

CHEMICALS; - the esters of fatty acid (notably of C₈-C₂₄, and preferably C₁₆-C₂₂ acid) and of polyethylene glycol (which can contain from 1 to 150 ethyleneglycol units) such as the stearate of PEG-50 and the monostearate of PEG-40 marketed under the name MYRJ

52P by the company ICI UNICMA; the esters of fatty acid (notably of C₈-C₂₄, and preferably C₁₆-C₂₂ acid) and of the oxyethylenated and/or oxypropylenated glycerol ethers (which can contain from 1 to 150 oxyethylene and/or oxypropylene groups), such as the monostearate of PEG-200 glyceryl sold under the designation "Simulsol 220 TM" by the company SEPPIC; the polyethoxylated glyceryl stearate with 30 ethylene oxide groups such as the product

TAGAT S sold by the company GOLDSCHMIDT, the polyethoxylated glyceryl oleate with

30 ethylene oxide groups such as the product TAGAT O sold by the company GOLDSCHMIDT, the polyethoxylated glyceryl cocoate with 30 ethylene oxide groups such as the product VARIONIC LI 13 sold by the company SHEREX, the polyethoxylated glyceryl isostearate with 30 ethylene oxide groups such as the product TAGAT L sold by the company GOLDSCHMIDT and the polyethoxylated glyceryl laurate with 30 ethylene oxide groups such as the product TAGAT I from the company GOLDSCHMIDT; - the esters of fatty acid (notably of C₈-C₂₄, and preferably C₁₆-C₂₂ acid) and oxyethylenated and/or oxypropylenated sorbitol ethers (which can contain from 1 to 150 oxyethylene and/or oxypropylene groups), such as polysorbate 60 sold under the designation "Tween 60" by the company UNICMA; dimethicone copolyol, such as that sold under the designation "Q2-5220" by the company DOW CORNING;

- dimethicone copolyol benzoate (FINSOLV SLB 101 and 201 from the company FINTEX); copolymers of propylene oxide and ethylene oxide, also called OE/Op polycondensates, for example the polyethylene glycol/polypropylene glycol/polyethylene glycol triblock polycondensates sold under the designations "SYNPERONIC" such as

"SYNPERONIC PE/ L44" and "SYNPERONIC PE/F127" by the company ICI, and mixtures thereof. and mixtures thereof. b) non-ionic surfactants with HLB less than 8 at 25⁰C, optionally combined with one or more non-ionic surfactants with HLB greater than 8 at 25⁰C, as mentioned above, such as: the esters and ethers of monosaccharides such as sucrose stearate, sucrose cocoate, sorbitan stearate and mixtures thereof such as Arlatone 2121 marketed by the company ICI; - the esters of fatty acids (notably of C₈-C₂₄, and preferably C₁₆-C₂₂ acid) and of polyol, notably of glycerol or of sorbitol, such as glyceryl stearate, sorbitan stearate such as the product sold under the designation TEGIN M by the company GOLDSCHMIDT, glyceryl laurate such as the product sold under the designation IMWITOR 312 by the company HULS, poIyglyceryl-2 stearate, sorbitan tristearate, glyceryl ricinoleate; - the mixture of cyclomethicone/dimethicone copolyol sold under the designation "Q2-3225C" by the company DOW CORNING, c) The anionic surfactants such as : the salts of C₁₆-C₃₀ fatty acids, notably those derived from amines, such as triethanolamine stearate; - the salts of polyoxyethylenated fatty acids, notably those derived from amines or alkaline salts, and mixtures thereof; the phosphoric esters and their salts such as "DEA oleth-10 phosphate" (Crodafos N 1ON from the company CRODA), cetyl phosphate (Amphisol K from the company DSM Nutritional Products) ; - the sulphosuccinates such as "Disodium PEG-5 citrate lauryl sulphosuccinate" and "Disodium ricinoleamido MEA sulphosuccinate" the alkylethersulphates such as sodium lauryl ether sulphate; the isethionates; the acylglutamates such as "Disodium hydrogenated tallow glutamate" (AMISOFT HS-21 R marketed by the company AJINOMOTO) and mixtures thereof.

Triethanolamine stearate is particularly suitable for the invention. It is generally obtained by simple mixing of stearic acid and triethanolamine.

Preferably, surfactants are used that permit an oil-in-water or wax-in-water emulsion to be obtained.

"Fibre" is to be understood as meaning an object of length L and diameter D such that L is much greater than D, D being the diameter of the circle in which the cross section of the fibre is inscribed. In particular, the ratio L/D (or form factor) is selected in the range from 3.5 to 2500, preferably from 5 to 500, and more preferably from 5 to 150. Notably these can be fibres used in the manufacture of textiles and notably of fibres of silk, cotton, wool, flax; fibres of cellulose, notably extracted from wood, vegetables or algae; rayon, polyamide (Nylon^®), viscose, acetate notably of rayon acetate, poly-(p- phenylene-terephthalamide) (or aramid) notably Kevlar^®, of acrylic polymer notably of polymethyl methacrylate or of poly 2-hydroxyethyl methacrylate, of polyolefin and notably of polyethylene or of polypropylene, of glass, of silica, of carbon notably in the form of graphite, of polytetrafluoroethylene (such as Teflon^®), of insoluble collagen, of polyesters, of polyvinyl chloride or of vinylidene, of polyvinyl alcohol, of polyacrylonitrile, of chitosan, of polyurethane, of polyethylene phthalate, of fibres formed from a mixture of polymers such as those mentioned above, such as polyamide/polyester fibres.

Of course, a person skilled in the art will take care to select this or these optional supplementary compounds, and/or their amount, in such a way that the advantageous properties of the corresponding composition according to the invention are not, or are not substantially, adversely affected by the addition envisaged.

Each of the first, second and optionally third compositions according to the invention can notably be in the form of suspension, of dispersion, of solution, of gel, of emulsion, notably oil-in-water (O/W), wax-in-water or water-in-oil (W/O), or multiple (W/O/W or polyol/O/W or 0/W/O) emulsion, in the form of cream, of foam, of dispersion of vesicles notably of ionic or non-ionic lipids, of biphase or multiphase lotion, of spray, of powder, of paste, notably of soft paste. Each composition is preferably a non-rinsed composition.

The method according to the invention can be used advantageously for make-up of the skin and/or of the lips and/or of the appendages according to the nature of the ingredients used. In particular, the first, second and optionally third compositions can be in the form, independently, of solid foundation, lipstick or lip paste, anti-ring product, or contours of the eyes, eyeliner, mascara, eye shadow, make-up product for the body or a product for colouring the skin.

According to one embodiment, the first, second and optionally third compositions are compositions of lipstick.

According to another embodiment, the first, second and optionally third compositions are compositions for coating keratin fibres such as the eyelashes, the eyebrows or the hair, and more particularly mascaras.

A person skilled in the art will be able to select the appropriate galenical form, as well as its method of preparation, on the basis of his general knowledge, taking into account, on the one hand, the nature of the constituents used, notably their solubility in the carrier, and on the other hand the application envisaged for each composition.

The invention is illustrated in more detail by the examples presented below. Unless indicated otherwise, the amounts stated are expressed as percentages by weight. Example 1: Kit for lipstick

1) First composition

2) Second composition

Procedure:

The dry resistance of the film of make-up obtained is measured according to the following procedure: Three glass slides are prepared, each coated with a collagen sheet as follows. At a temperature of 28°C, a collagen sheet (Naturin artificial gut, thickness 0.06 mm, a. 0.10 mm, d. 120 mm) is prepared with the dimensions 5 cm x 10 cm and it is conditioned for at least two hours at 90% relative humidity (RH). The collagen sheet is returned to the open air and is fixed immediately, firmly and completely, on a glass slide 4.6 cm x 7.6 cm. The collagen sheet is attached to the back of the slide with Scotch tape (made by 3M). The surface of the collagen must be flat and without creases. Each slide is left in ambient conditions for 24 hours, before carrying out the test.

The first composition (or the second composition) is applied to each glass slide using a mechanical applicator of 15 μm, then it is left to dry for 24 hours. Then the second composition (or the first composition) is applied on top of the first deposit using a mechanical applicator of 15 μm, and it is left to dry for 30 minutes.

3 discs of white Styrofoam (type Amoco Selectables Plastics DL Tableware) with diameter of 4 cm are cut out. The disc of white Styrofoam is attached firmly on both faces at the end of a 2 kg weight.

The dry resistance is measured in the following way immediately after depositing the product. The dry resistance is also measured after the product has dried for 30 minutes in ambient conditions.

Each measurement is taken at a pressure of 175 g/cm²; the weight is placed gently on the surface of a plate (product side) and, in 3 to 5 seconds, the weight is rotated one-and-a- half turns on itself, while maintaining the initial pressure. The weight is lifted off and the Styrofoam disc is retrieved. The measurement is carried out for each glass slide with a clean Styrofoam disc.

Then measurements are taken of the percentage reflectance: o of the deposit of product applied on the rectangular sample of Styrofoam (referenced A), o of the clean disc of white Styrofoam (referenced B) o of the disc detached from the weight after applying pressure to the slide coated with cosmetic product (referenced C) The reflectance is measured over a wavelength range between 400 and 700 nm using a spectrum analyser (opening 25 mm diameter) with an illuminant D65/1 Odegrees. The wavelength of the minimum reflectance is selected for the "stained" disc. At this wavelength, the resistance is calculated according to the equation

100 * (1 - [(C-B)/(A-B)] )

The dry resistance is equal to the mean of the three measurements, each performed with a clean Styrofoam disc.

For reference, the dry resistance of the film obtained by depositing the second composition alone was also measured, according to the procedure described above, the composition being applied on each glass slide using a mechanical applicator of 15 μm, then leaving to dry for 24 hours.

The results are presented in the following table:

Example 2: Kit for lipstick

1) First composition

2) Second composition: wt.%

Pigment paste:

LAKE OF DISODIUM ALUMINIUM SALT OF PHLOXINE B ON ALUMINA, ALUMINIUM BENZOATE (Cl: 45410:2 + 77002) 2.2% CALCIUM SALT OF RED LITHOL B 4.2% FLAMING RED (Cl: 12085) 1.13% BLACK IRON OXIDE (Cl: 77499) 0.07% BROWN IRON OXIDE (Cl: 77491) 2.40% lsododecane 90%

The dry resistance of the film of make-up obtained by deposition of the first and then of the second composition on the collagen slides is greater than 95%.

Example 3: Mascaras

1) First composition (A, A' or A")

Procedure

Heat the waxes and the isononyl isononanoate at about 95°C, while stirring in the Rayneri, for about 20 minutes. Then add the bentone gel, the octyl cyanoacrylate and the vinyl polylaurate if present. Cool the mixture to 40⁰C, with mechanical stirring, then add the remainder of the isododecane.

2) Second composition (B)

- Black iron oxide 5

- Hydroxyethyl cellulose 3.1

- preservatives qs

- water qsf 100%

The water resistance and resistance to rubbing of the film of make-up obtained by application of composition B and then of composition A were measured according to the following methods:

A layer of the second composition (B) is applied, then on top of that a layer of the first composition (A), on 3 test specimens of straight Caucasian hair 30 knots (60 eyelashes with length of 1 cm), length of fringe 1.9 cm, making 3 x 10 passes at intervals of 2 minutes for each composition with product renewal between each series of 10. Each test specimen is then dried at room temperature for a drying time of one hour.

A) Dry rubbing resistance

This test is carried out on one of the made-up test specimens. The test specimen is rubbed 30 times with a hard brush, the debris is recovered on adhesive paper and evaluated visually according to the following scale: 0 = no particles

1 = very few particles

2 = few particles

3 = quite a number of particles

4 = many particles 5 = numerous particles B) Water resistance

On each of the other 3 test specimens, the following 2 operations are carried out in succession: - pass the test specimen under cold running water (about 23°) for 1 minute then move the test specimen to and fro on a blotter. The marks are evaluated visually. the same test specimen is immersed in water for 1 hour then rubbed on a blotter 10 times. The marks are evaluated visually according to the following scale:

0 = no marks 1 = very few marks

2 = few marks

3 = quite a number of marks

4 = many marks

5 = numerous marks

The same measurements are carried out in parallel on the film of make-up deposited on test specimens on which a layer of the second composition was applied, then on top of that, a layer of the following composition Y of waterproof mascara (not part of the invention):

Composition Y:

Beeswax 4.9

Carnauba wax 4.7

Paraffin wax 2.3

Polyolefin wax 0.1

Esters of acids and C₁₆/C₃₆ linear alcohols (Cyclochem 326 A from 3.4

Goldschmidt)

Polyethylene wax (Performalene 655 from NEW PHASE 2

TECHNOLOGIES)

Candellila wax esterified with polyalkoxylated polydimethylsiloxane 1

Hydroxyethylcellulose crosslinked with epichlorohydrin quaternized with 0.1 trimethylamine (JR 400 from the company UNION CARBIDE)

Sodium polymethacrylate (Darvan 7 from the company VANDERBILT) 0.25 MA

Vinyl acetate/allyl stearate copolymer 65/35 (Mexomer PQ from 2.21

CHIMEX)

Vinyl polylaurate (Mexomer PP from CHIMEX) 0.75 Polybutene (PM 2060) 1 Propylene carbonate 1.9

Vinylpyrrolidone/1 -eicosene copolymer 2

Hectorite modified with distearyl dimethyl ammonium 5.8

(Bentone 38 V from Elementis)

Oxyethylenated (20 OE)/oxypropylenated (20 OP) polydimethylsiloxane 0.1 (DC Q 2-5220 Resin Modifier from DOW CORNING)

Rice starch 1.5

Water 2.9

Ethanol 2

Black iron oxide 4.2

Preservatives qs lsododecane Qsf 100

The following results are obtained:

The film of make-up obtained by applying the 2 compositions of the method according to the invention displays higher resistance to water and to rubbing than that obtained according to the state of the art.

Example 4:

The first composition A and the second composition from example 3 above are mixed in proportions of 50/50 immediately before use, the mixture obtained is conditioned in a boiler then the mixture is applied to 4 test specimens of straight Caucasian hair 30 knots (60 eyelashes with a length of 1 cm), length of the fringe 1.9 cm, making 3 x 10 passes at intervals of 2 minutes with product renewal between each series of 10.

Each test specimen is then dried at room temperature for a drying time of one hour.

The resistance to water and to rubbing of the film of make-up obtained by application of the mixture of the first composition A and of composition B were measured by the following method:

A layer of the mixture is applied to 3 test specimens of straight Caucasian hair 30 knots

(60 eyelashes with a length of 1 cm), length of the fringe 1.9 cm, making 3 x 10 passes at intervals of 2 minutes with product renewal between each series of 10.

Each test specimen is then dried at room temperature for a drying time of one hour.

The resistance to water and to rubbing of the film are measured according to the procedures described in example 3.

The following result is obtained:

Claims

1. Cosmetic method of make-up or of non-therapeutic care of keratinous materials selected from the skin, the lips, and the eyelashes, the method comprising: a. depositing at least one layer of a first composition on said keratinous materials; b. depositing at least one layer of a second composition on the layer or layers of said first composition; at least one of said first and second compositions containing at least one electrophilic monomer.

2. Method according to Claim 1 , characterized in that the first composition contains an electrophilic monomer.

3. Method according to Claim 1 , characterized in that the second composition contains an electrophilic monomer.

4. Cosmetic method of make-up or of non-therapeutic care of keratinous materials selected from the skin, the lips and the eyelashes comprising application on said keratinous materials comprising: a. mixing, at the time of use:

- at least one first composition containing a cosmetically acceptable medium and at least one electrophilic monomer, and - at least one second composition containing a cosmetically acceptable medium then b. applying to the skin, the lips, or the eyelashes at least one layer of said mixture.

5. Method according to one of the Claims 1 to 4, characterized in that the electrophilic monomer or monomers are selected from the compounds of formula:

I I

C = C (A) I I

R2 R₄ in which:

Ri and R₂ each denote, independently of one another, a group with low or zero electron-accepting properties selected from: - a hydrogen atom,

- a saturated or unsaturated hydrocarbon group, linear, branched or cyclic, having from 1 to 20 carbon atoms, and optionally containing one or more nitrogen, oxygen or sulphur atoms, and optionally substituted with one or more groups selected from -OR, -COOR, -COR, -SH, -SR, -OH, and the halogen atoms,

- a modified or unmodified polyorganosiloxane residue,

- a polyoxyalkylene group,

R₃ and R₄ each denote, independently of one another, an electron- accepting group preferably selected from the groups -N(R)₃ ⁺, -S(R)₂ ⁺, -SH₂ ⁺, -NH₃ ⁺, -NO₂, -SO₂R, -CsN, -COOH, -COOR, -COSR, -CONH₂,

-CONHR, -F, -Cl, -Br, -I₁ -OR, -COR, -SH, -SR, -OH, the linear or branched alkenyl groups, the linear or branched alkynyl groups, the C₁-C₄ mono- or polyfluoroalkyl groups, the aryl and aryloxy groups,

R denotes a saturated or unsaturated hydrocarbon group, linear, branched or cyclic, having from 1 to 20 carbon atoms, and optionally containing one or more nitrogen, oxygen or sulphur atoms, and optionally substituted with one or more groups selected from -OR', -COOR', -COR'.

6. Method according to one of the preceding claims, characterized in that the electrophilic monomer or monomers are selected from the compounds of formula:

R1 C≡N

I I

C = C (B) I I

R2 COXR'3

X denoting NH, S or O,

R1 and R2 are as defined in the preceding claim, R'3 representing a hydrogen atom or a radical R as defined in the preceding claim.

7. Method according to one of the preceding claims, characterized in that the monomer or monomers are selected from the C₁-C₂O polyfluoroalkyl 2-cyanoacrylates, the (C₁-Ci₀) alkyl or (CrC₄ alkoxy) C-i-C-io alkyl cyanoacrylates.

8. Method according to one of the preceding claims, characterized in that the monomer or monomers are selected from ethyl 2-cyanoacrylate, methyl 2-cyanoacrylate, n- propyl 2-cyanoacrylate, isopropyl 2-cyanoacrylate, tert-butyl 2-cyanoacrylate, n-butyl 2-cyanoacrylate, iso-butyl 2-cyanoacrylate, 3-methoxybutyl cyanoacrylate, n-decyl cyanoacrylate, hexyl 2-cyanoacrylate, 2-ethoxyethyI 2-cyanoacrylate, 2-methoxyethyl

2-cyanoacrylate, 2-octyl 2-cyanoacrylate, 2-propoxyethyl 2-cyanoacrylate, n-octyl 2- cyanoacrylate and iso-amyl cyanoacrylate.

9. Method according to one of the preceding claims, characterized in that the electrophilic monomer or monomers correspond to the formula (F):

C≡N

CH₂= C (F) I

COO-R's in which: R'₃ is selected from =-(CH₂)₇-CH₃,

-CH₂-CH(C₂Hs)-(CH₂)_S-CHs,

-(CHa)₄-CH(C₂Hs)-CH₃, and mixtures thereof.

10. Method according to any one of the preceding claims, characterized in that the electrophilic monomer is present at a content in the range from 0.1 to 100 wt.% of the total weight of the composition containing it, preferably from 1 to 80%, more preferably from 2 to 50% and even more preferably from 5 to 40 wt.% relative to the total weight of the composition containing it.

11. Method according to any one of the preceding claims, characterized in that the monomers are fixed covalently on supports such as polymers, oligomers or dendrimers.

12. Method according to one of the preceding claims, characterized in that the first and/or the second composition includes a liquid oil phase containing at least one oil or organic solvent selected from the volatile oils, the non-volatile oils, and mixtures thereof.

13. Method according to one of the preceding claims, characterized in that the composition containing the electrophilic monomer includes a liquid oil phase containing at least one volatile hydrocarbon oil having from 8 to 16 carbon atoms.

14. Method according to Claim 12 or 13, characterized in that the oil or oils represent from 1 to 80 wt.%, preferably from 5 to 50 wt.% relative to the total weight of the first and/or of the second composition.

15. Method according to any one of the preceding claims, characterized in that the first and the second composition are anhydrous.

16. Method according to any one of the Claims 1 to 14, characterized in that one of said first and second compositions does not contain any electrophilic monomer and contains an aqueous phase.

17. Method according to Claim 16, characterized in that the aqueous phase represents from 5 to 95 wt.% relative to the total weight of the composition containing it, preferably from 10 to 85 wt.%.

18. Method according to any one of the preceding claims, characterized in that the first and/or the second composition includes at least one fat that is solid or pasty at room temperature selected from waxes, pasty compounds and mixtures thereof.

19. Method according to any one of the preceding claims, characterized in that the first and/or the second composition contains from 0.1 to 70 wt.% of waxes, relative to the total weight of the composition, preferably from 1 to 60% and more preferably from 5 to 40 wt.%.

20. Method according to any one of the preceding claims, characterized in that the first and/or the second composition contains at least one film-forming polymer.

21. Method according to Claim 20, characterized in that the film-forming polymer is present at a content of dry matter in the range from 0.1 to 30 wt.% relative to the total weight of the composition, preferably from 0.5 to 20 wt.%, and more preferably from 1 to 15 wt.%.

22. Method according to any one of the Claims 1 to 21, characterized in that the first composition and/or the second composition contains at least one colorant.

23. Method according to any one of the Claims 1 to 21, characterized in that the composition containing the electrophilic monomer does not contain pigments based on metal oxide, notably of iron, without surface treatment.

24. Method according to any one of the preceding claims, characterized in that the composition not containing the electrophilic monomer includes at least one colorant.

25. Method according to Claim 22, characterized in that the colorant is present at a content in the range from 0.01 to 50 wt.%, preferably from 0.01 to 30 wt.% of each first and/or second composition.

26. Method according to one of the preceding claims, characterized in that it includes an additional stage comprising depositing, on the layer or layers of said second composition, at least one layer of a third composition containing a film-forming polymer and an organic solvent or aqueous medium.

27. Method according to one of the preceding claims, characterized in that the first and/or the second composition and/or the third composition contains a cosmetic ingredient selected from vitamins, thickeners, gelling agents, trace elements, emollients, sequestering agents, perfumes, alkalizing or acidifying agents, preservatives, sun filters, surfactants, antioxidants, fibres, care agents, stabilizers of cyanoacrylates or mixtures thereof.

28. Method according to one of the preceding claims, characterized in that the first, second, and/or third compositions are compositions of lipstick.

29. Method according to one of the Claims 1 to 27, characterized in that the first, second, and/or third compositions are compositions of mascara.

30. Kit for make-up or for non-therapeutic care of keratinous materials selected from the skin, the lips, and the eyelashes comprising:

i) at least one first composition containing at least one electrophilic monomer and ii) at least one second composition containing a cosmetically acceptable medium.

31. Kit according to Claim 30, characterized in that the first and the second compositions are packaged separately in the same packaging article.