WO2009090243A1

WO2009090243A1 - Process for making up or caring for keratin materials, comprising the application of compounds a, b and c, which are silicone-based

Info

Publication number: WO2009090243A1
Application number: PCT/EP2009/050492
Authority: WO
Inventors: Guillaume Kergosien; Xavier Thomas; Jean-Luc Garaud
Original assignee: L'oreal
Priority date: 2008-01-17
Filing date: 2009-01-16
Publication date: 2009-07-23
Also published as: GB0800842D0

Abstract

The invention relates to a cosmetic process for coating keratin materials, which consists in applying to the said keratin materials at least one compound A, at least one compound B and at least one compound C, the compounds A, B and C being silicone compounds, the said compounds A, B and C being capable of reacting together via a hydrosilylation reaction.

Description

Process for making up or caring for keratin materials, comprising the application of compounds A, B and C, which are silicone-based

The present invention relates to a process for coating keratin materials, in particular a non-therapeutic process for making up or caring for keratin materials, which consists in applying to the said keratin materials at least three compounds A, B, and C which are capable of reacting together, the compounds being silicone-based.

The cosmetic compositions according to the invention may be compositions for making up or caring for keratin materials, in particular the skin, the lips, the eyelashes, the eyebrows or the nails.

The cosmetic composition may be a loose or compacted powder, a foundation, a makeup rouge, an eyeshadow, a concealer product, a blusher, a lipstick, a lip balm, a lip gloss, a lip pencil, an eye pencil, a mascara, an eyeliner, a body makeup product or a skin colouring product .

The care composition may be a care product for the eyelashes or the lips, or a care product for bodily and facial skin, especially an antisun product.

Lipstick and foundation compositions are commonly used to give the lips or the skin, and especially the face, an aesthetic colour. These makeup products generally contain fatty phases such as waxes and oils, pigments and/or fillers and optionally additives, for instance cosmetic or dermatological active agents. When they are applied to the skin, these cosmetic compositions have the drawback of transferring, i.e. of becoming at least partially deposited, and leaving marks, on certain supports with which they may come into contact and especially a glass, a cup, a cigarette, an item of clothing or the skin. This results in mediocre persistence of the applied film, making it necessary to regularly renew the application of the foundation or lipstick composition. Moreover, the appearance of these unacceptable marks, especially on blouse collars, may put certain women off using this type of makeup .

"Transfer-resistant" lip and skin makeup compositions are thus sought, which have the advantage of forming a deposit that does not become at least partially deposited onto the supports with which they come into contact (glass, clothing, cigarette or fabric) and show good staying power.

To limit the transfer of cosmetic compositions, it is known practice to use volatile oils. These volatile oils present in large amount render the makeup product, especially lipstick, uncomfortable for the user: the makeup deposit gives a sensation of drying-out and of tautness .

In the case of eyelash coating compositions or mascaras, anhydrous mascaras or mascaras with a low content of water and/or water-soluble solvents, known as "waterproof mascaras" are known in particular, which are formulated in the form of a dispersion of waxes in non-aqueous solvents and which show good resistance to water and/or to sebum. However, the makeup film obtained after applying these cosmetic compositions is not sufficiently resistant to water, for example when bathing or taking a shower, to tears or sweat, or to sebum. The mascara then has a tendency to wear away over time: grains are worn off and unattractive marks appear around the eyes.

The aim of the present invention is to provide a new route for formulating cosmetic compositions, especially makeup compositions, which makes it possible to obtain in situ film forming, deposited on keratin materials, which combine a fast cure, a good adhesion to substrate, a low tack surface and which shows good transfer resistance and staying power properties over time, in particular resistance to water and rubbing, and a comfortable deposit on the skin, the lips, the eyelashes or the nails.

The inventors have discovered that it is possible to obtain such properties by using a system comprising silicone compounds that polymerize in situ so as to adhere better to keratin materials. These silicone compounds also show good biocompatibility .

Particularly, the inventors have discovered that applying a thin layer of the silicone compounds avoids any problem of comfort . According to a preferred embodiment, the application has a thickness lower than 200 μm, preferably lower than 150 μm, and more preferably lower than 100 μm. Indeed, in cosmetic applications, a thin coating layer is needed to achieve satisfying make-up results.

The compounds A, B, C and D may be applied on keratin materials via several cosmetic compositions comprising the compound (s) A and/or the compound (s) B and/or the compound (s) C and/or the compound (s) D alone or in mixture, or via one cosmetic composition comprising said compound (s) A and/or compound (s) B and/or compound (s) C and/or the compound (s) D.

Accordingly, the present invention relates to a process for the making up and/or cosmetic treatment of keratinous materials comprising the step of applying on said keratinous material, via at least one composition, the compounds:

(A) a polydiorganosiloxane having at least two silicon-bonded alkenyl groups per molecule,

(B) a hydrosilicon compound having at least 3 silicon-bonded hydrogen atoms per molecule, (C) a diorganohydrogensiloxy-terminated polydiorganosiloxane,

(D) a hydrosilylation catalyst for the hydrosilylation reaction of SiH groups with Si -Alkenyl groups, and Wherein,

(1) RHAIk > 1.5 wherein RHAIk is the ratio of the number of SiH moles in B and C with respect to the number of Si -Alkenyl moles in A and D and wherein

(2) 0 < RHCE < 0.7 wherein RHCE is the ratio of the number of SiH moles in C with respect to the number of SiH moles in B and C, and further wherein the compounds A, B, C and D are applied in such a way that said hydrosilylation reaction occurs at least in part on the keratinous material to be treated and/or made up, and further wherein the compounds are applied on the keratinous materials in a coat having a thickness lower than 200 μm.

Preferably, the coat has a thickness lower than 150 μm, and more preferably lower than 100 μm.

As used herein, "cosmetic treatment" means any treatment by means of a cosmetic product as defined above hereinbelow.

As used herein, "cosmetic product" means any substance or preparation intended to be brought into contact with the various superficial parts of the human body (e.g., epidermis, body hair and hair system, lashes, nails, lips,) or with the teeth and the buccal mucosa, for the exclusive or main purpose of cleansing them, or of giving them a fragrant smell, of modifying their appearance, and/or of correcting body odors, and/or of protecting them, and/or of maintaining them in good condition. (As set forth in cosmetic directive 76/768/EEC amended) .

By way of nonlimiting examples, cosmetic products may include any product intended to reduce the signs of aging of the skin (e.g., wrinkles) and/or the hair; to moisturize the skin; to cleanse, to nourish, and/or to maintain the skin and/or the hair; to deodorize the skin; to prepare the skin for exposure to the sun; to reinforce the elasticity of the skin; and/or to enhance the softness of the skin.

More particularly, this process is performed in a way wherein the compounds A, B, C and D are applied via at least a first and a second cosmetic compositions to be mixed either extemporaneously prior to application on the keratinous materials or upon application on said keratinous materials, the compounds A, B, C and D being contained in either one of said first and second cosmetic compositions so that no hydrosilylation reaction occurs prior to said mixing of the first and second compositions. Preferably, the first cosmetic composition comprises the compounds A and D, and the second cosmetic composition comprises the compounds B and C.

More preferably, the first cosmetic composition comprises the compounds A and D, and the second cosmetic composition comprises the compounds A, B and C .

An other subject of the present invention is a cosmetic process for coating keratin materials, which consists in applying to the said keratin materials at least one coat of a mixture of at least said first composition and said second composition.

These compounds are capable of reacting together on the keratin materials or on the support so as to form, on the keratin materials, an adherent film with good staying power.

According to one advantageous embodiment, compounds A, B and C and the catalyst D are mixed together extemporaneously and the mixture is then applied to the keratin materials.

The cosmetic process for coating keratin materials described above preferably comprises the following steps : a. extemporaneously mixing together:

- at least said first composition,

- at least said second composition, the compounds A, B, C and D being contained in either one of said first and second compositions so that no hydrosilylation reaction occurs prior to said mixing of the first and second compositions, and then b. applying to the said keratin materials at least one coat of a thickness lower than 200 μm, preferably lower than 150 μm, and more preferably lower than 100 μm, of the said mixture.

According to one variant, compound A, compound B and compound C and compound D are applied via at least two different cosmetic compositions, each comprising at least one compound A and/or at least one compound B and/or at least one compound C and/or at least a catalyst D.

According to a preferred variant, compound A, compound B and compound C and compound D are applied via at least two different cosmetic compositions, one comprising at least one compound A and at least a catalyst D, and the other one comprising at least one compound B and at least one compound C and optionally the compound A.

According to an other preferred variant, compound A, compound B and compound C and compound D are applied via at least two different cosmetic compositions, one comprising at least one compound A, and the other one comprising at least one compound B and at least one compound C and at least a catalyst D. According to an other preferred variant, compound A, compound B and compound C and compound D are applied via at least two different cosmetic compositions, one comprising at least one compound A, at least one compound B, and at least one compound C, and the other one comprising at least a catalyst D.

The terms first and second cosmetic compositions do not in any way determine the order of application of said compositions on the keratinous materials.

Several coats of each of the first and second cosmetic compositions may also be applied alternately to the keratin materials.

According to another aspect, a subject of the invention is a cosmetic composition for coating keratin materials, comprising: at least one compound A, at least one compound Bat least one compound C, and at least a catalyst D, the said compounds A, B and C being capable of reacting together via a hydrosilylation reaction, when they are placed in contact with each other in the presence of the catalyst D, said compounds A, B, C, and D being formulated so that the hydrosilylation reaction is prevented from occuring until an external stimulus is provided.

For example, one or more of compounds A, B, C, and D may be encapsulated inside capsules which can be broken when the composition is applied to the keratinous material in response to the mechanical force resulting from the rubbing of said composition. The catalyst may be temporarily inhibited. In such a configuration, an external factor triggers the cure (ie by the hydrosilylation reaction) by releasing the catalyst. For instance, such factors can be, but are not limited to elevated temperature (e.g. body or skin temperature, hair dryer) , shearing effect or evaporation of certain formulation additives (e.g. liquid fatty or aqueous phase) .

Preferably, the cosmetic composition for coating keratin materials according to the present invention, comprises : (A) a polydiorganosiloxane having at least two silicon-bonded alkenyl groups per molecule,

(B) a hydrosilicon compound having at least 3 silicon-bonded hydrogen atoms per molecule,

(C) a diorganohydrogensiloxy-terminated polydiorganosiloxane,

(1) RHAIk > 1.5 wherein RHAIk is the ratio of the number of SiH moles in B and C with respect to the number of Si-Alkenyl moles in A and D and wherein

(2) 0 < RHCE < 0.7 wherein RHCE is the ratio of the number of SiH moles in C with respect to the number of SiH moles in B and C, and further wherein the compounds A, B, C and D are contained in said composition in such a way that at least part of said hydrosilylation reaction occurs at least in part on the keratinous material to be coated.

According to one embodiment, at least one additional coat of at least one third cosmetic composition comprising 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 onto the coats (s) of the composition (s) comprising compounds A, B and C and the catalyst D, in order, for example, to improve the staying power, gloss and/or comfort thereof .

According to another aspect, another subject of the present invention is a cosmetic kit comprising at least one compound A and/or at least one compound B and/or at least one compound C and/or at least a catalyst D, the said compounds A, B, and C, being capable of reacting together via a hydrosilylation reaction, when they are placed in contact with each other in the presence of the catalyst D, provided that at least the compounds A, B and the catalyst D, or the compounds A, C and the catalyst D, are not present together in the same compositions. Preferably, the cosmetic kit for coating keratin materials according to the present invention, comprises : at least a first and a second compositions, said kit comprising:

(2) 0 < RHCE < 0.7 wherein RHCE is the ratio of the number of SiH moles in C with respect to the number of SiH moles in B and C, and wherein the compounds A, B, C and D are contained in said composition in such a way that at least part of said hydrosilylation reaction occurs at least in part on the keratinous material to be coated.

According to the invention, at least a catalyst, as defined below, is applied on the keratinic materials to activate the reaction between the compound (s) A and/or the compound (s) B and/or the compound (s) C. For example, the catalyst may be present in one of the first or second composition applied on the keratinic materials, or in an additional composition, and the order of application of the composition does not matter . According to one embodiment, at least one additional reactive compound, as defined here below, may be present in any one of the first, second and eventually third composition, in all the compositions or in an additional composition and the order of application of the compositions does not matter.

According to a preferred embodiment, the first and second cosmetic compositions are as described above.

According to one embodiment, the kit also comprises a cosmetic composition for removing the coating obtained on the keratin materials by reaction of compounds A and B and C, the said composition preferably comprising at least one organic solvent or oil chosen from the organic solvents and oils described later in point II.

Each composition may be packaged separately in the same packaging article. Each composition may also be packaged in the same packaging article, the mixing of the at least two compositions being performed at the end(s) of the packaging article during the delivery of each composition. Alternatively, each of the first, second and optionally third compositions may be packaged in a different packaging article.

Indeed, the compounds A, B and C and the catalyst D can either be separated into a plurality of containers to inhibit curing prior to spreading or can be packaged into a unique container wherein the hydrosilylation catalyst is temporarily inhibited, wherein the temporary inhibition is obtained by encapsulating the hydrosilylation catalyst or by adding transient inhibitors .

In case of one part system in which the catalyst is encapsulated or temporarily inhibited, an external factor triggers the cure (ie by the hydrosilylation reaction) by releasing the catalyst. For instance, such factors can be, but are not limited to elevated temperature (e.g. body or skin temperature, hair dryer) , shearing effect or evaporation of certain formulation additives (e.g. liquid fatty or aqueous phase) .

The formulation of the invention can be applied by spreading the formulation onto the desired site, wherein said spreading can cause mixing the formulation or the mixing of the formulation is achieved prior spreading the formulation.

The activation of the catalyst can occur prior to spread the formulation, or can be caused by spreading the formulation, or can be caused by mixing the formulation, or can occur after spreading the formulation.

After spreading, the formulation cures in situ on the desired site to form a film.

According to the method of the invention, the compounds A, B, C and the catalyst D, and any other optional components, are delivered and spread onto the desired site in a manner which causes mixing of the component materials. The formulation cures after being applied and results in a non-tacky and elastic film suitable for cosmetic applications.

The delivery herein is performed by conventional techniques known in the art. For instance the delivery systems include, but not limited to can, tube, sachet, syringe, stick, pencil, brush, sponge, wet stamp and roll-on as known in the art. These delivery devices can comprise one or more than one chamber according to the need to separate the components of the formulation. Whichever of the above means of delivery is chosen, the formulation components are delivered and spread to the desired site. Mixing of the formulation components can occur either in the delivery packaging, during the delivery or during the spreading onto the desired site.

For instance, a mixing chamber can be built into the delivery packaging such that as the formulation components are drawn or forced out of their separate containers they are mixed prior to being delivered.

In an embodiment the formulation components are separated by fragile walls which can easily be broken to allow the formulation components for getting in contact together. The mixing then occurs by hand kneading or with a mixing tool as known in the art.

In another embodiment the formulation components are forced into a mixing device such as a static mixer and then delivered to the site.

In still another embodiment, the formulation components can be delivered sequentially and then be mixed on the desired site.

A subject of the invention is also the use of a kit as described above for obtaining a film deposited on keratin materials, which shows improved staying power, gloss and/or comfort properties.

Needless to say, the composition comprises a cosmetically acceptable medium, i.e. a non-toxic medium that may be applied to human keratin materials and that has a pleasant appearance, odour and feel.

I/Compounds A and B and C

The term "silicone compound" means a compound comprising at least two organosiloxane units. According to a specific embodiment, the compound A, the compound B and the compound C are silicon based.

Compounds A and B and C capable of reacting via hydrosiIyIation

According to one embodiment, the silicone compounds are capable of reacting via hydrosilylation, this reaction being able to be represented schematically, in a simplified manner, as follows:

—Si-H + CH₂=CH-W- —Si-CH₂-CH₂-W

where W represents a carbon or silicon based chain containing one or several unsaturated aliphatic groups.

According to one embodiment, compound A is a polyorganosiloxane polymer having at least two (a) groups per molecule,

Compound B is a crosslinker polyorganosiloxane compound having at least 3 (b) groups per molecule, and Compound C is a chain extender compound which is a telechelic polyorganosiloxane having terminal (b) groups, the groups (a) and (b) being either a functional group containing an alkenyl functionality, which functional group is directly bonded to a silicon atom (herein after called "SiAIk" group) or a Si -bonded hydrogen group (hereinafter called "SiH" group) , provided that when A is SiAIk, B is SiH and when A is SiH, B is SiAIk.

Preferably, compounds A, B, C and the catalyst are in such quantity that:

(1) RHAIk > 1.5 wherein RHAIk is the ratio of the number of (b) moles in compounds B and C with respect to the number of (a) moles in compound A and the catalyst D, and

(2) 0 < RHCE < 0.7 wherein RHCE is the ratio of the number of (b) moles in compound C with respect to the number of (b) moles in compounds B and C.

When the compounds A, B, C and the catalyst meet these requirements of RHAIk and RHCE, they are able to cure quickly as a film on a substrate and can provide good balance between adhesion and tackiness requirements; the film can show good adhesion to the substrate while the surface opposite to the substrate shows low tack.

It is not important whether the silicon-bonded hydrogen group or the alkenyl group is on compound A or B and C provided one is solely found on compound A and the other is predominantly found on compounds B and C.

However, commercial SiH compounds with short chain and terminal SiH are readily commercially available while long chain SiH compounds are more difficult to find on the market .

Therefore, it is preferred that the reactive group (a) is a vinyl or other alkenyl -containing functional group directly bonded to a silicon atom and group (b) is a hydrogenosiloxyl SiH group.

In the following description, compound A is described as of the SiAIk type while compounds B and C are of SiH type. More specifically, without any mention of the contrary, the term "RHAIk" corresponds to the ratio of the number of SiH moles in B and C with respect to the number of Si -Alkenyl moles in A and D. In a same way, without any mention to the contrary, the term "RH_CE" corresponds to the ratio of the number of SiH moles in C with respect to the number of

SiH moles in B and C.

Preferably, RHAlk>2, preferably RHAlk>2.5, more preferably RHAlk>3.

Preferably, compound A is a polydiorganosiloxane having at least two silicon-bonded alkenyl groups per molecule, with preferably the remaining silicon-bonded organic groups being selected from alkyl and aryl groups, said polydiorganosiloxane having a viscosity at 25⁰C from 3 mm2/s to 100,000 mm2/s.

Preferably, compound B is a linear hydrosilicon compound having at least 3 silicon-bonded hydrogen atoms per molecule, which preferably consists essentially of RHSiO- groups, R2XSiO; groups and optionally R2SiO- groups and having a viscosity at 25⁰C of no more than 1000 mm2/s, wherein R denotes an alkyl or aryl group having no more than 8 carbon atoms, and X denotes H or R.

Preferably, compound C is a diorganohydrogensiloxy- terminated polydiorganosiloxane, wherein, preferably the organic substituents are alkyl or aryl groups having no more than 8 carbon atoms .

The final composition (s) that is (are) applied on keratin materials are formulated in order to obtain RHAlk> 1.5, preferably > 2.5 wherein RHAIk is the ratio of the number of SiH moles in compounds B and C with respect to the number of Si -Alkenyl moles in compound A and the catalyst D, and

0 < RHCE <0.7, preferably RHCE < 0.5, wherein RHCE is the ratio of the number of SiH moles in compound C with respect to the number of SiH moles in compounds B and C. A RHAIk below 1 provides pressure sensitive adhesive properties on the surface of the cured film, for example, rendering it tacky to touch. In addition, the reaction speed is lower.

A RHCE of 0.7 or more provides tackiness and low cohesive strength of the cured film.

The compounds used herein preferably comprise those which have silicon-bonded hydrogen atoms (ie compounds B and C) , in combination with those that have silicon- bonded unsaturated hydrocarbon groups (ie compound A) .

These polysiloxanes undergo a hydrosilylation reaction in the presence of a catalyst to yield chain extended or cross-linked elastomeric silicone films.

Compound B can be chosen from polysiloxanes having silicon bonded hydrogen which have units according to the general formula RpHSiO (3 -p/2) in which each R represents a monovalent hydrocarbon group containing 1 to 20 carbon atoms, such as alkyl (e.g., methyl, ethyl, propyl or butyl) or phenyl groups and p is 0, 1, or 2. It is preferred that each R represents a methyl group. It is also preferred that the terminal groups have the formula R3SiOl/2 where each R represents a methyl group.

Compound B can also be chosen from polysiloxanes having silicon bonded hydrogen which form cyclics, for example pentamethylcyclopentasiloxane (D5H) .

Compound B can also be chosen from polysiloxanes having silicon bonded hydrogen which are copolymers comprising, for example, units RnSiO (4-n/2) in which R is as referred to above, and n is O, 1, 2 or 3. The polysiloxanes (b) having silicon bonded hydrogen may alternatively include a siloxane (silicone) resin structure with silicon bonded hydrogen. The siloxane resin structure may comprise R3SiOl/2 units (M units) and SiO4/2 units (Q units) wherein each R is independently a linear, branched or cyclic hydrocarbon group having 1-20 carbon atoms. R can be unsubstituted or substituted with halogen atoms. Each R can be identical or different, as desired. The hydrocarbon group of R can be exemplified by alkyl groups such as methyl, ethyl, propyl, butyl, hexyl , octyl, vinyl, hexenyl, 3 , 3 , 3-trifluoropropyl , chloromethyl , and decyl , cycloaliphatic groups such as cyclohexyl, aryl groups such as phenyl, tolyl, and xylyl , chlorophenyl , and aralkyl groups such as benzyl, styryl and alpha- methylstyryl . The resin can also contain triorganosiloxy units (T units), for example 0.5 to 1 triorganosiloxy group for every SiO4/2 unit, alternatively 0.6 to 0.9 triorganosiloxy group for every SiO4/2 unit.

The siloxane resin structure may comprise RSiO3/2 units (also known as T units) in which the groups R, which can be different in different siloxane units, are selected from hydroxyl , hydrocarbon, substituted hydrocarbon, hydrocarbonoxy and substituted hydrocarbonoxy groups. The silicone resin optionally also comprises R2SiO2/2 units (D units) and/or R3SiOl/2 units (M units), in which each R is defined as above. The hydrocarbon and hydrocarbonoxy groups each preferably contain 1 to 20, more preferably 1 to 8 , carbon atoms .

It should be noted that more than 1 resin could be included in the present invention. In this case, at least one of the resins should have the silanol content as described below but, but by the same token, one could have the silanol capped so that there is substantially no silanol present. It should also be noted that other resins can be also added to the composition of this invention. For example, organic resins could be added if desired. In one embodiment, for example, a vinyl -functional resin can be added. Resins comprising R3SiOl/2 units and SiO4/2 units are well known in the art. These copolymers are described, for example, in U.S. Pat. Nos . 3,936,582, 2,676,182, and 2,857,356. The resinous copolymers can be prepared by cohydrolysis of a mixture of silanes having four hydrolyzable groups, e.g., silicon tetrachloride, and triorganosilanes having one hydrolyzable group, e.g., trimethylchlorosilane, in the proper ratio. A specific method for the preparation of these resinous copolymers is described in U.S. Pat. No. 2,676,182, wherein a silica hydrosol is reacted under acidic conditions with a source of triorganosiloxy units such as a hexaorganodisiloxane, for example, hexamethyldisiloxane, or a hydrolysable triorganosilane, for example, trimethylchlorosilane, or mixtures thereof.

Compound B can also be chosen from mixtures of the above described polysiloxanes having silicon bonded hydrogen .

Preferably the compound B is a polysiloxane having silicon bonded hydrogen atoms which has from 0.0001mol/g to 5 mol/g hydrogen atoms based on the weight of the polymer.

Compound C can be chosen from polysiloxanes terminated with silicon bonded hydrogen which have units according to the general formula R2SiOl/2 in which each R represents a monovalent hydrocarbon group containing 1 to 20 carbon atoms, such as alkyl (e.g., methyl, ethyl, propyl or butyl) or phenyl groups and p is 0, 1, or 2, and in which the terminal groups have the formula HR2SiOl/2. It is preferred that each R represents a methyl group.

Preferably compound C is chosen from polysiloxanes terminated with silicon bonded hydrogen atoms which have from 0.0001 mol/g to 2 mol/g hydrogen atoms based on the weight of the polymer.

Compound C is preferably a diorganohydrogensiloxy- terminated polydiorganosiloxane, wherein, preferably the organic substituents are alkyl or phenyl groups having no more than 8 carbon atoms.

The polysiloxanes having silicon bonded hydrogen used as compounds B and C preferably have viscosities on the order of from about 1 mm2/s to about 1000 mm2/s.

Compound A can be chosen from polysiloxanes having sufficient silicon bonded unsaturated groups for formation of the polymer network.

For example, compound A can be chosen from polysiloxanes having siloxane units according to the general formula RmR' SiO (3-m/2) in which each R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms such as alkyls (e.g., methyl, ethyl, propyl or butyl) or phenyl groups, m is 0, 1 or 2 and

R' represents an aliphatically unsaturated group such as vinyl, allyl, hexenyl and cyclohexenyl or a group R¹¹CH=CHR'", where R" represents a divalent aliphatic chain linked to the silicon atom and R'" represents a hydrogen atom or an alkyl group. Preferably, R is methyl .

Compound A can also be chosen from polysiloxanes having silicon bonded unsaturated groups which are copolymers having, for instance, units RnSiO (4-n/2) in which R is as referred to above, and n is 0, 1, 2 or 3.

The polysiloxanes having silicon bonded unsaturated groups, used as compound A, can also comprise functional siloxane resins with unsaturated groups. The functional siloxane resin structure may comprise R3SiOl/2 units (M units) and SiO4/2 units (Q units) wherein each R is independently a linear, branched or cyclic hydrocarbon group having 1-20 carbon atoms. R can be unsubstituted or substituted with halogen atoms. Each R can be identical or different, as desired. The hydrocarbon group of R can be exemplified by alkyl groups such as methyl , ethyl , propyl , butyl , hexyl , octyl, vinyl, hexenyl , 3 , 3 , 3-trifluoropropyl , chloromethyl , and decyl , cycloaliphatic groups such as cyclohexyl, aryl groups such as phenyl, tolyl, and xylyl , chlorophenyl , and aralkyl groups such as benzyl, styryl and alpha-methylstyryl . The resin can also contain triorganosiloxy units (T units) , for example 0.5 to 1 triorganosiloxy group for every SiO4/2 unit, alternatively 0.6 to 0.9 triorganosiloxy group for every SiO4/2 unit. The functional siloxane resin structure may comprise RSiO3/2 units (also known as T units) in which the groups R, which can be different in different siloxane units, are selected from hydroxyl , hydrocarbon, substituted hydrocarbon, hydrocarbonoxy and substituted hydrocarbonoxy groups. The silicone resin optionally also comprises R2SiO2/2 units (D units) and/or R3SiOl/2 units (M units) , in which each R is defined as above. The hydrocarbon and hydrocarbonoxy groups each preferably contain 1 to 20, more preferably 1 to 8 , carbon atoms.

Preferably, the polysiloxanes having silicon bonded unsaturated groups, used as compound A, have from 0.00001mol/g as vinyl group based on the weight of the polymer to 2 mol/g as vinyl group based on the weight of the polymer and a viscosity on the order of about 3 mm2/s to about 600,000 mm2/s at 25° C. Mixtures of polysiloxanes having silicon-bonded unsaturated groups can also be used as compound A.

l.a Additional reactive compound

According to one embodiment, at least one of the compositions comprising the compounds A and/or B and/or C may also comprise an additional reactive compound comprising at least two unsaturated aliphatic groups, for instance:

- organic or mineral particles comprising at the surface at least two unsaturated aliphatic groups: examples that may be mentioned include silicas that have been surface-treated, for example with silicone compounds containing vinyl groups, for instance cyclotetramethyltetravinylsiloxane- treated silica,

- silazane compounds such as hexamethyldisilazane .

l.b Catalyst

The hydrosilylation reaction is advantageously performed in the presence of a catalyst (compound D) that may be present in one of the compositions comprising compound A and/or compound B and/or compound C or in a separate composition, the catalyst preferably being platinum-based or rhodium-based.

Examples that may be mentioned include platinum- or rhodium-based catalysts deposited on a support of silica gel or charcoal (coal) powder, platinum chloride, platinum salts and chloroplatinic acids.

Chloroplatinic acids in hexahydrate or anhydrous form, which are readily dispersible in organosilicone media, are preferably used.

Mention may also be made of platinum complexes such as those based on chloroplatinic acid hexahydrate and on divinyltetramethyldisiloxane .

The catalyst may be present in the composition (s) in a content ranging from 0.0001% to 20% by weight relative to the total weight of the composition comprising it.

When the compounds A, B and C and the catalyst D of the invention are mixed, they cure at room temperature (20 ± 5° C) within 10 minutes or, more preferably, within five minutes or less.

Higher temperature, such as skin temperature is beneficial as it can decrease the cure time.

In order to achieve satisfactory cure it is important that the ratio of silicon-bonded hydrogen atoms of the polysiloxanes to all groups reactive therewith in the composition (s) (e.g., the unsaturated groups) is appropriate to affect the desired cure. The curing time is dependent on various factors including the type and proportion of other component materials present in the formulation.

Working with low or intermediate viscosity materials (<10,000 mm2/s) , having a RHAIk > 1.5, preferably having a RHAIk > 2.0, more preferably having a RHAIk > 3.0, and a Pt level between lOppm and 150ppm are factors that allow for that short curing time.

According to a preferred embodiment, the RH_CE is lower than 0.5, and preferably equal or lower than 0.4, to avoid tacky films. According to another preferred embodiment, the RHAIk needs to be higher than 3 to ensure a more appropriate curing time for cosmetic applications.

Polymerization inhibitors, and more particularly catalyst inhibitors, may also be introduced into the compositions of the invention, in order to increase the stability of the composition over time or to retard the polymerization. Non- limiting examples that may be mentioned include cyclic polymethylvinylsiloxanes, in particular tetravinyl tetramethyl cyclotetrasiloxane, acetylenic alcohols, preferably volatile, such as methylisobutynol .

The presence of ionic salts in one and/or the other of the compositions may have an influence on the rate of polymerization of the compounds.

Examples of a combination of such compounds A, B and C reacting via hydrosilylation that may be mentioned include the following components:

Vinyl -terminated polydimethylsiloxane; Dimethyl, methylhydrogen siloxane,- and Dimethylhydrogenterminated polydimethylsiloxane .

Advantageously, compounds A, B and C are chosen from silicone compounds capable of reacting via hydrosilylation; in particular, compound A is chosen from polyorganosiloxanes comprising units of formula RmR'SiO (3-m/2) or RnSiO (4 -n/2) described above and compound B is chosen from organosiloxanes comprising alkylhydrogenosiloxane units of formula RnSiO (4 -n/2) described above and compound C is chosen from diorganohydrogensiloxy-terminated polydiorganosiloxanes, wherein the organic substituents are alkyl or phenyl groups having no more than 8 carbon atoms. According to a specific embodiment, compound A is a polydimethylsiloxane with vinyl end groups, compound B is a methylhydrogenosiloxane, and compound C is a dimethylhydrogenterminated polydimethylsiloxane.

According to a particular embodiment, compound A contains at least one polar group.

According to one embodiment, the hydrosilylation reaction between compounds A, B and C is accelerated by supplying heat, for example by raising the temperature of the system to between 25⁰C and 18O⁰C. The system will especially react on the skin.

Compound A may have a weight-average molecular mass (Mw) ranging from 150 to 1 000 000, preferably from 200 to 800 000 and more preferably from 200 to 250 000.

Compound B may have a weight-average molecular mass (Mw) ranging from 200 to 1 000 000, preferably 300 to 800 000 and more preferably from 500 to 250 000.

The ratio between compounds A, B and C may be varied so as to modify the rate of reaction and thus the rate of formation of the film or so as to adapt the properties of the formed film (for example its adhesive properties) according to the desired use.

According to one embodiment, at least one of the compositions may comprise silica, especially synthetic silica surface-treated with a hydrophobic agent (preferably a silicon agent) , in particular fumed silica subjected to a hydrophobic surface treatment, such as the silicas described below as fillers and/or gelling agents.

Finally, the present invention also relates to a process for the making up and/or cosmetic treatment of keratinous materials comprising the step of applying on said keratinous material, via at least one composition, the compounds :

(A) a polydiorganosiloxane having at least two silicon-bonded hydrogen atoms per molecule, (B) a polydiorganosiloxane compound having at least 3 silicon-bonded alkenyl groups per molecule,

(C) a diorganoalkenylsiloxy-terminated polydiorganosiloxane,

(D) a hydrosilylation catalyst for the hydrosilylation reaction of SiH groups with Si-Alkenyl groups, and Wherein,

(2) 0 < RAIkCE < 0.7 wherein RAIkCE is the ratio of the number of SiAlkenyl moles in C with respect to the number of SiAlkenyl moles in B and C, and further wherein the compounds A, B, C and D are applied in such a way that at least part of said hydrosilylation reaction occurs at least in part on the keratinous material to be treated and/or made up, and further wherein the compounds are applied on the keratinous materials in a coat having a thickness lower than 200 μm..

11/ Additives

The compositions according to the invention may also contain ingredients commonly used in cosmetics, such as solvents, dyestuffs, fillers, oils, waxes, pasty fatty substances, thickeners, gelling agents, film-forming polymers, surfactants, fibres, or mixtures thereof .

The proportion of additives in the composition may vary widely depending on the intended site of application and the use of the composition. For example, the compositions may contain from 0.01 % to 95 % by weight of such additives.

The final composition can be in the form of a gel or an elastomer and it can have pores (e.g., foams) or it can be pore-free.

If it is desired to prolong the cure time, one may include in the composition (s) one of the known catalyst inhibitors such as cyclic polymethylvinylsiloxane compounds or an acetylenic alcohol e.g. methyl butynol but these are not generally preferred in a composition according to the invention.

If foaming of the composition is desired, it may be induced by, for example, including a polysiloxane having silicon-bonded hydroxyl groups which reacts with the polysiloxane having silicon-bonded hydrogen atoms as more fully described, for example, in U.S. 4, 026, 845. Alternatively aliphatic alcohol (for example a primary aliphatic or araliphatic alcohol such as a lower aliphatic monofunctional alcohol having up to 12 carbon atoms (e.g. ethanol, npropanol, or benzyl alcohol), a silanol or a volatile blowing material can be included in the formulation as more fully described, for example, in U.S. 4,550,125.

Preferred foamable compositions include compounds having silicon-bonded or carbon bonded hydroxyl groups which foam and cure in presence of a platinum catalyst according to the patent EP 0 865 787. For example the composition (s) can comprise a liquid fatty or aqueous phase to adjust the viscosity of the composition and the comfort of the film after curing. The liquid fatty or aqueous phase which may be employed includes volatile and non volatile fluids such as silicone volatiles, silicone fluids, hydrocarbons, alcohols, ketones, esters and any other liquid material. Examples of liquid fatty or aqueous phase include hexamethyldisiloxane, octamethyltrisiloxane, and other linear siloxanes, cyclic siloxanes such as octamethylcyclotetrasiloxane,decamethylcyclopentasiloxa ne and dodecamethylcyclohexasiloxane . Examples also includes isododecane, isohexadecane, ethylacetate, ethyl alcohol, isopropyl alcohol, ester palmitate, propylene glycol, C12-15 alkyl benzoate, Caprylic/capric triglyceride, Coco-caprylate/caprate, Diisopropyl adipate, Diisostearyl fumarate, Diisostearyl malate, Isocetyl stearate, Isopropyl isostearate, Isopropyl laurate, Isopropyl myristate, Isopropyl palmitate, Isopropyl stearate, Isostearyl benzoate, Myristyl ether acetate w/ propylene glycol, Myristyl lactate, Octyldodecyl stearoyal stearate,

Octylpalmitate, Octylstearate, Tridecyl neopentanoate, Triisocetyl citrate, Lauryl alcohol, Oleyl alcohol, Glyceryl trioctanate, Polyglyceryl-3 diisostearate, Mineral oil, Dipropylene glycol, Glycol ether, Glycerin, Castor oil, Lanolin oil, Sunflower oil, Isododecane, Cll-12 isoparaffin, Polydecene .

The aqueous phase may consist essentially of water, it may also comprise a mixture of water and/or of water- miscible solvent (miscibility in water of greater than 50% by weight at 25⁰C) , for instance lower monoalcohols containing from 1 to 5 carbon atoms, such as ethanol or isopropanol, glycols containing from 2 to 8 carbon atoms, such as propylene glycol, ethylene glycol, 1,3- butylene glycol or dipropylene glycol, C3-C4 ketones and C2-C4 aldehydes, and mixtures thereof.

The aqueous phase (water and optionally the water- miscible solvent) may be present in a content ranging from 5% to 95% by weight, preferably from 10% to 85% by weight and better still from 2% to 80% by weight relative to the total weight of the composition.

In a preferred embodiment, the liquid fatty or aqueous phase is a liquid fatty phase.

For the purposes of the present patent application, the term "liquid fatty phase" means a fatty phase that is liquid at room temperature (25⁰C) and atmospheric pressure (760 mmHg) , composed of one or more mutually compatible non-aqueous fatty substances that are liquid at room temperature, also known as organic solvents or oils .

The oil may be chosen from volatile oils and/or non- volatile oils, and mixtures thereof.

The oil may be present in a content ranging from 1% to 90% by weight and preferably from 5% to 50% by weight relative to the total weight of the composition.

For the purposes of the invention, the term "volatile oil" means an oil that is capable of evaporating on contact with the skin or the keratin materials in less than one hour, at room temperature and atmospheric pressure. The volatile organic solvent (s) and volatile oils of the invention are volatile organic solvents and cosmetic oils that are liquid at room temperature, with 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 ranging from 1.3 Pa to 13 000 Pa (0.01 to

100 mmHg) , and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg).

The term "non-volatile oil" means an oil that remains on the skin or the keratin materials at room temperature and atmospheric pressure for at least several hours and that especially has a vapour pressure of less than 10^"3 mmHg (0.13 Pa).

These oils may be hydrocarbon-based oils, silicone oils or fluoro oils, or mixtures thereof.

The term "hydrocarbon-based oil" means an oil mainly containing hydrogen and carbon atoms and optionally oxygen, nitrogen, sulfur or phosphorus atoms. The volatile hydrocarbon-based oils may be chosen from hydrocarbon-based oils containing from 8 to 16 carbon atoms, and especially branched C8-C16 alkanes, for instance C8-C16 isoalkanes of petroleum origin (also known as isoparaffins) , for instance isododecane (also known as 2 , 2 , 4 , 4 , 6-pentamethylheptane) , isodecane and isohexadecane, for example the oils sold under the trade names Isopar or Permethyl, branched C8-C16 esters and isohexyl neopentanoate, and mixtures thereof. Other volatile hydrocarbon-based oils, for instance petroleum distillates, especially those sold under the name Shell SoIt by the company Shell, may also be used. The volatile solvent is preferably chosen from volatile hydrocarbon-based oils containing from 8 to 16 carbon atoms, and mixtures thereof.

Volatile oils that may also be used include volatile silicones, for instance volatile linear or cyclic silicone oils, especially those with a viscosity < 8 centistokes (8 x 10^~6 m²/s) and especially containing from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oils that may be used in the invention, mention may be made especially of octamethylcyclotetrasiloxane, decamethylcyclo- pentasiloxane, dodecamethylcyclohexasiloxane, hepta- methylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof .

Mention may also be made of the linear volatile alkyltrisiloxane oils of general formula (I) :

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

Among the oils of general formula (I) that may be mentioned are: 3 -butyl -1 ,1,1,3,5,5, 5-heptamethyltrisiloxane,

3-propyl-l, 1,1,3,5,5, 5-heptamethyltrisiloxane, and 3 -ethyl -1 ,1,1,3,5,5, 5-heptamethyltrisiloxane, corresponding to the oils of formula (I) for which R is, respectively, a butyl group, a propyl group or an ethyl group. Volatile fluorinated solvents such as nonafluoromethoxybutane or perfluoromethylcyclopentane may also be used.

The oil of formula (I) for which R is an ethyl group is especially sold under the name Baysilone TP 3886 and the oil for which R is a butyl group is especially sold under the name Baysilone TP 3887 by the company Bayer Silicones .

Preferably, the compositions used in the process according to the invention each have a volatile oil content of less than or equal to 50% by weight, preferably less than or equal to 30% and better still less than or equal to 10% by weight relative to the total weight of each first and second composition. More preferably, the composition (s) are free of volatile oil.

According to one advantageous embodiment, at least one of the first and second compositions used in the process according to the invention comprises at least one non-volatile oil, chosen in particular from nonvolatile hydrocarbon-based oils and/or silicone oils and/or fluoro oils.

Non-volatile hydrocarbon-based oils that may especially be mentioned include: hydrocarbon-based oils of plant origin, such as triesters of fatty acids and of glycerol, the fatty acids of which may have varied chain lengths from C4 to C24, these chains possibly being linear or branched, and saturated or unsaturated; these oils are especially wheatgerm oil, sunflower oil, grapeseed oil, sesame seed oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppyseed oil, pumpkin oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passionflower oil or musk rose oil; or caprylic/capric acid triglycerides, for instance those sold by the company Stearineries

Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel; synthetic ethers containing from 10 to 40 carbon atoms ;

- apolar hydrocarbon-based oils, for instance squalene, linear or branched hydrocarbons such as liquid paraffin, liquid petroleum jelly and naphthalene oil, hydrogenated or partially hydrogenated polyisobutene, isoeicosane, squalane, decene/butene copolymers and polybutene/polyisobutene copolymers, especially Indopol L- 14, and polydecenes such as Puresyn 10, and mixtures thereof;

- synthetic esters, for instance oils of formula RiCOOR₂ in which Ri represents a linear or branched fatty acid residue containing from 1 to 40 carbon atoms and R₂ represents a hydrocarbon-based chain, which is especially branched, containing from 1 to 40 carbon atoms, on condition that Ri + R₂ > 10, for instance Purcellin oil (cetostearyl octanoate) , isopropyl myristate, isopropyl palmitate, Ci₂ to Ci₅ alkyl benzoates, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, alcohol or polyalcohol octanoates, decanoates or ricinoleates, for instance propylene glycol dioctanoate,- hydroxylated esters, for instance isostearyl lactate or diisostearyl malate,- and pentaerythritol esters,- - fatty alcohols that are liquid at room temperature with a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance octyldodecanol , isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol or 2-undecylpenta- decanol ;

- higher fatty acids such as oleic acid, linoleic acid or linolenic acid;

- carbonates; - acetates;

- citrates;

- and mixtures thereof .

The non-volatile silicone oils may be: - non-volatile polydimethylsiloxanes (PDMS) ,

- polydimethylsiloxanes comprising alkyl or alkoxy groups, which are pendent and/or at the end of a silicone chain, these groups each containing from 3 to 40 carbon atoms, - phenylsilicones, for instance phenyl trimethi- cones, phenyl dimethicones, phenyltrimethylsiloxy- diphenylsiloxanes, diphenyl dimethicones, diphenyl- methyldiphenyltrisiloxanes and 2-phenylethyl trimethyl- siloxysilicates ; - optionally fluorinated polyalkylmethylsiloxanes, for instance polymethyltrifluoropropyldimethyl- siloxanes, polyalkylmethylsiloxanes substituted with functional groups such as hydroxyl , thiol and/or amine groups;

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

- and mixtures thereof .

According to one embodiment, the liquid fatty phase comprises an ester oil. This ester oil may be chosen from the esters of monocarboxylic acids with monoalcohols and polyalcohols .

Advantageously, the said ester corresponds to formula (IV) below:

where Ri represents a linear or branched alkyl radical of 1 to 40 carbon atoms and preferably of 7 to 19 carbon atoms, optionally comprising 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 better still of 3 to 20 carbon atoms, optionally comprising one or more ethylenic double bonds, and optionally substituted.

The term "optionally substituted" means that Ri and/or R₂ can bear one or more substituents chosen, for example, from groups comprising one or more hetero atoms chosen from 0, N and S, such as amino, amine, alkoxy and hydroxy1.

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

Ri may represent the residue of a linear or, preferably, branched fatty acid, preferably a higher fatty acid, containing from 1 to 40 and even better from 7 to 19 carbon atoms, and R₂ may represent a linear or, preferably, branched hydrocarbon-based chain containing from 1 to 40, preferably from 3 to 30 and even better from 3 to 20 carbon atoms. Once again, preferably the number of carbon atoms of Ri + R₂ > 9. Examples of groups Ri are those derived from fatty acids chosen from the group consisting of acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, oleic acid, linolenic acid, linoleic acid, oleostearic acid, arachidonic acid and erucic acid, and mixtures thereof .

Examples of esters include purcellin oil (cetostearyl octanoate) , isononyl isononanoate, isopropyl myristate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2-octyldodecyl erucate, isostearyl isostearate, and heptanoates, octanoates, decanoates or ricinoleates of alcohols or polyalcohols, for example of fatty alcohols .

Advantageously, the esters are chosen from the compounds of formula (IV) above, in which Ri represents an unsubstituted linear or branched alkyl group of 1 to 40 carbon atoms and preferably of 7 to 19 carbon atoms, optionally comprising one or more ethylenic double bonds, and R₂ represents an unsubstituted linear or branched alkyl group of 1 to 40 carbon atoms, preferably of 3 to 30 carbon atoms and even better of 3 to 20 carbon atoms, optionally comprising one or more ethylenic double bonds .

Preferably, Ri is an unsubstituted branched alkyl group of 4 to 14 carbon atoms and preferably of 8 to 10 carbon atoms, and R₂ is an unsubstituted branched alkyl group of 5 to 15 carbon atoms and preferably of 9 to 11 carbon atoms. Preferably, in formula (I), Ri-CO- and R₂ have the same number of carbon atoms and are derived from the same radical, preferably an unsubstituted branched alkyl, for example isononyl, i.e. the ester oil molecule is advantageously symmetrical .

The ester oil will preferably be chosen from the following compounds: isononyl isononanoate, cetostearyl octanoate, - isopropyl myristate,

2-ethylhexyl palmitate,

2-octyldodecyl stearate,

2-octyldodecyl erucate, isostearyl isostearate.

Advantageously, the non-volatile oil is chosen from the ester oils of formula (IV) above and phenyl silicones, and mixtures thereof .

The non-volatile oil may be present in a content ranging from 0.1% to 80% by weight, preferably from 1% to 60% by weight, better still from 5% to 50% by weight and even better still from 14% to 40% by weight relative to the total weight of each composition or relative to the total weight of the composition when A, B and C are present in the same composition.

When the first and second compositions are intended to be applied to the lips, a "viscous" oil may be used in particular, i.e. an oil whose viscosity at 25⁰C is advantageously greater than or equal to 200 cSt, especially greater than or equal to 500 cSt or even greater than or equal to 1000 cSt . The viscous oil advantageously has a molecular mass of greater than or equal to 600 g/mol, for example greater than or equal to 700, or even 800, or even 900 g/mol .

The dynamic viscosity at 25⁰C of the viscous oil may be measured with a Mettler RM 180 rotary viscometer, taking into account the density of the oil in order to make the conversion into cSt .

The Mettler RM 180 machine (Rheomat) may be equipped with different spindles depending on the order of magnitude of the viscosity that it is desired to measure. For a viscosity of between 0.18 and 4.02 Pa. s, the machine is equipped with a No . 3 spindle. For a viscosity of between 1 and 24 Pa. s, the machine is equipped with a No . 4 spindle, and for a viscosity of between 8 and 122 Pa. s, the machine is equipped with a No. 5 spindle. The viscosity is read on the machine in deviation units (DU) . Reference is then made to charts provided with the measuring machine to obtain the corresponding value in poises, and then to convert it into stokes. The spin speed of the spindle is 200 rpm.

Once the spindle is in rotation, at a constant set spin speed (in the present case 200 rpm) , the viscosity value of the oil may vary over time. Measurements are taken at regular time intervals until they become constant. The viscosity value that has become constant over time is the value retained as being the dynamic viscosity value of the viscous oil.

This oil may be chosen from the silicone oils or apolar hydrocarbon-based oils with a viscosity of greater than or equal to 200 cSt mentioned above.

The additive can also be a fatty substance that is solid at room temperature, chosen especially from waxes and pasty fatty substances, and mixtures thereof. These fatty substances may be of animal, plant, mineral or synthetic origin.

Thus, at least one of the first, second compositions according to the invention may comprise a wax or a mixture of waxes .

The wax under consideration in the context of the present invention is in general a lipophilic compound, which is solid at room temperature (25⁰C) , with a reversible solid/liquid change of state, having a melting point of greater than or equal to 3O⁰C that may be up to 12O⁰C.

By bringing the wax to the liquid state (melting) , it is possible to make it miscible with the oils and to form a microscopically homogeneous mixture, but on returning the temperature of the mixture to room temperature, recrystallization of the wax in the oils of the mixture is obtained.

In particular, the waxes that are suitable for the invention may have a melting point of greater than about 45⁰C and in particular greater than 55⁰C.

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

The measuring protocol is as follows:

A 15 mg sample of product placed in a crucible is subjected to a first temperature rise ranging from O⁰C to 12O⁰C, at a heating rate of 10°C/minute, it is then cooled from 12O⁰C to O⁰C at a cooling rate of

10°C/minute and is finally subjected to a second temperature rise ranging from O⁰C to 12O⁰C at a heating rate 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 as a function of the temperature. The melting point of the compound is the temperature value corresponding to the top of the peak of the curve representing the variation in the difference in power absorbed as a function of the temperature .

The waxes that may be used in the first and second compositions according to the invention are chosen from waxes that are solid and rigid at room temperature, of animal, plant, mineral or synthetic origin, and mixtures thereof .

The wax may also have a hardness ranging from 0.05 MPa to 30 MPa and preferably ranging from 6 MPa to 15 MPa. The hardness is determined by measuring the compression force, measured at 2O⁰C using the texturometer sold under the name TA-TX2i by the company Rheo, equipped with a stainless-steel cylinder 2 mm in diameter travelling at a measuring speed of 0.1 mm/s, and penetrating the wax to a penetration depth of 0.3 mm. The measuring protocol is as follows: The wax is melted at a temperature equal to the melting point of the wax +2O⁰C. The molten wax is poured into a container 30 mm in diameter and 20 mm deep. The wax is recrystallized at room temperature (25⁰C) for 24 hours and is then kept at 2O⁰C for at least 1 hour before performing the hardness measurement. The hardness value is the maximum compression force measured divided by the surface area of the texturometer cylinder in contact with the wax.

Hydrocarbon-based waxes, for instance beeswax, lanolin wax or Chinese insect wax,- rice wax, carnauba wax, candelilla wax, ouricury wax, esparto grass wax, cork fibre wax, sugarcane wax, Japan wax and sumach wax; montan wax, microcrystalline waxes, paraffins and ozokerite; polyethylene waxes, the waxes obtained by Fisher-Tropsch synthesis and waxy copolymers, and also esters thereof, may especially be used.

Mention may also be made of waxes obtained by catalytic hydrogenation of animal or plant oils containing linear or branched C₈-C₃₂ fatty chains.

Among these waxes that may especially be mentioned are hydrogenated jojoba oil, isomerized jojoba oil such as the trans-isomerized partially hydrogenated jojoba oil manufactured or sold by the company Desert Whale under the commercial reference Iso-Jojoba-50 ^" , hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil, hydrogenated lanolin oil and bis (1,1,1 - trimethylolpropane) tetrastearate sold under the name Hest 2T-4S by the company Heterene, bis (1,1,1- trimethylolpropane) tetrabehenate sold under the name Hest 2T-4B by the company Heterene.

Mention may also be made of silicone waxes, for instance alkyl or alkoxy dimethicones containing from 16 to 45 carbon atoms, and fluoro waxes.

The wax obtained by hydrogenation of olive oil esterified with stearyl alcohol, sold under the name Phytowax Olive 18 L57 or else the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol sold under the names Phytowax ricin 16L64 and 22L73 by the company Sophim may also be used. Such waxes are described in Patent Application FR-A-2 792 190.

According to one particular embodiment, the first and second compositions according to the invention may comprise at least one "tacky" wax, i.e. a wax with a tack of greater than or equal to 0.7 N.s and a hardness of less than or equal to 3.5 MPa.

The tacky wax used may especially have a tack ranging from 0.7 N.s to 30 N.s, in particular greater than or equal to 1 N.s, especially ranging from 1 N.s to 20 N.s, in particular greater than or equal to 2 N.s, especially ranging from 2 N.s to 10 N.s and in particular ranging from 2 N.s to 5 N.s.

The tack of the wax is determined by measuring the change in force (compression force or stretching force) as a function of time, at 2O⁰C, using the texturometer sold under the name TA-TX2i^® by the company Rheo, equipped with a conical acrylic polymer spindle forming an angle of 45°.

The measuring protocol is as follows:

The wax is melted at a temperature equal to the melting point of the wax + 1O⁰C. The molten wax is poured into a container 25 mm in diameter and 20 mm deep. The wax is recrystallized at room temperature (25⁰C) for 24 hours such that the surface of the wax is flat and smooth, and the wax is then stored for at least 1 hour at 2O⁰C before measuring the tack. The texturometer spindle is displaced at a speed of

0.5 mm/s then penetrates the wax to a penetration depth of 2 mm. When the spindle has penetrated the wax to a depth of 2 mm, the spindle is held still 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 (compression force) decreases greatly until it becomes zero, and then, during the withdrawal of the spindle, the force (stretching force) becomes negative and then rises again to the value 0. The tack corresponds to the integral of the curve of the force as a function of time for the part of the curve corresponding to negative values of the force (stretching force) . The tack value is expressed in N.s.

The tacky wax that may be used generally has a hardness of less than or equal to 3.5 MPa, in particular ranging from 0.01 MPa to 3.5 MPa, especially ranging from 0.05 MPa to 3 MPa or even ranging from 0.1 MPa to 2.5 MPa.

The hardness is measured according to the protocol described previously.

A tacky wax that may be used is a C_2O-C₄₀ alkyl

(hydroxystearyloxy) stearate (the alkyl group containing from 20 to 40 carbon atoms) , alone or as a mixture, in particular a C₂₀-C₄₀ alkyl 12- (12 ' -hydroxystearyloxy) - stearate .

Such a wax is especially sold under the names Kester Wax K 82 P^® and Kester Wax K 80 P^® by the company Koster Keunen. The waxes mentioned above generally have a starting melting point of less than 45⁰C.

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

Wax microdispersions are stable dispersions of colloidal wax particles, and are described especially in "Microemulsions Theory and Practice", L. M. Prince Ed., Academic Press (1977) pages 21-32.

In particular, these wax microdispersions may be obtained by melting the wax in the presence of a surfactant, and optionally of a portion of water, followed by gradual addition of hot water with stirring. The intermediate formation of an emulsion of the water-in-oil type is observed, followed by a phase inversion, with final production of a microemulsion of the oil-in-water type. On cooling, a stable microdispersion of solid wax colloidal particles is obtained.

The wax microdispersions may also be obtained by stirring the mixture of wax, surfactant and water using stirring means such as ultrasound, high-pressure homogenizers or turbomixers .

The particles of the wax microdispersion preferably have mean sizes of less than 1 μm (especially ranging from 0.02 μm to 0.99 μm) and preferably less than 0.5 μm (especially ranging from 0.06 μm to 0.5 μm) . These particles consist essentially of a wax or a mixture of waxes. However, they may comprise a small proportion of oily and/or pasty fatty additives, a surfactant and/or a common liposoluble additive/active agent .

The term "pasty fatty substance" means a lipophilic fatty compound comprising at a temperature of 23⁰C a liquid fraction and a solid fraction.

The said pasty compound preferably has a hardness at 2O⁰C ranging from 0.001 to 0.5 MPa and preferably from 0.002 to 0.4 MPa.

The hardness is measured according to a method of penetration of a probe in a sample of compound and in particular using a texture analyser (for example the TA-XT2i machine from Rheo) equipped with a stainless- steel spindle 2 mm in diameter. The hardness measurement is performed at 2O⁰C at the centre of five samples. The spindle is introduced into each sample at a pre- speed of 1 mm/s and then at a measuring speed of 0.1 mm/s, the penetration depth being 0.3 mm. The hardness value revealed is that of the maximum peak.

The liquid fraction of the pasty compound measured at 23⁰C preferably represents 9% to 97% by weight of the compound. This liquid fraction at 23⁰C preferably represents between 15% and 85% and more preferably between 40% and 85% by weight. The liquid fraction by weight of the pasty compound at 23⁰C is equal to the ratio of the heat of fusion consumed at 23⁰C to the heat of fusion of the pasty compound. The heat of fusion of the pasty compound is the heat consumed by the compound to change 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 heat of fusion of the pasty compound is equal to the area under the curve of the thermogram obtained using a differential scanning calorimeter (DSC) , such as the calorimeter sold under the name MDSC 2920 by the company TA Instrument, with a temperature rise of 5 or 1O⁰C per minute, according to standard ISO 11357- 3:1999. The heat of fusion of the pasty compound is the amount of energy required to make the compound change from the solid state to the liquid state. It is expressed in J/g.

The heat of fusion consumed at 23⁰C is the amount of energy absorbed by the sample to change from the solid state to the state that it has at 23⁰C, consisting of a liquid fraction and a solid fraction.

The liquid fraction of the pasty compound, measured at 32⁰C, preferably represents from 30% to 100% by weight of the compound, preferably from 80% to 100% and more preferably from 90% to 100% by weight 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 32⁰C is equal to the ratio of the heat of fusion consumed at 32⁰C to the heat of fusion of the pasty compound. The heat of fusion consumed at 32⁰C is calculated in the same manner as the heat of fusion consumed at 23⁰C.

The pasty substances are generally hydrocarbon-based compounds, for instance lanolins and derivatives thereof, or alternatively PDMSs.

The nature and amount of the solid substances depend on the desired mechanical properties and textures. As a guide, the waxes may represent from 0.1% to 70% by weight, better still from 1% to 40% and even better still from 5% to 30% by weight relative to the total weight of the composition.

The compositions used in the process according to the invention may comprise at least one dyestuff chosen from pigments, nacres, dyes and materials with an effect, and mixtures thereof.

These dyestuffs may be present in a content ranging from 0.01% to 50% by weight and preferably from 0.01% to 30% by weight relative to the weight of each first and second composition or relative to the total weight of the composition when A, B and C are present in the same composition.

The pigments that are useful in the present invention may be in the form of powder or of pigmentary paste.

The term "dyes" should be understood as meaning compounds, generally organic, which are soluble in at least one oil or in an aqueous-alcoholic phase. The term "pigments" should be understood as meaning white or coloured, mineral or organic particles, which are insoluble in an aqueous medium, and which are intended to colour and/or opacify the resulting film.

The term "nacres" or nacreous pigments should be understood as meaning coloured particles of any form, which may or may not be iridescent, especially produced by certain molluscs in their shell or else synthesized, and which have a colour effect via optical interference .

The pigment may be an organic pigment . The term "organic pigment" means any pigment that satisfies the definition in Ullmann's encyclopaedia in the chapter on organic pigments. The organic pigment may especially be chosen from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanin, metal complex, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds .

The organic pigment (s) may be chosen, for example, from carmine, carbon black, aniline black, melanin, azo yellow, quinacridone, phthalocyanin blue, sorghum red, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 73000, 74100 and 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000 and 47005, the green pigments codified in the Color Index under the references CI 61565, 61570 and 74260, the orange pigments codified in the Color Index under the references CI 11725, 15510, 45370 and 71105, the red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420,

12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915 and 75470, and the pigments obtained by oxidative polymerization of indole or phenolic derivatives as described in patent FR 2 679 771.

These pigments may also be in the form of composite pigments as described in patent EP 1 184 426. These composite pigments may be composed especially of particles comprising an inorganic nucleus at least partially coated with an organic pigment and at least one binder to fix the organic pigments to the nucleus.

Examples that may also be mentioned include pigmentary pastes of organic pigments such as the products sold by the company Hoechst under the names :

- Jaune Cosmenyl IOG: Pigment Yellow 3 (CI 11710) ;

- Jaune Cosmenyl G: Pigment Yellow 1 (CI 11680) ; - Orange Cosmenyl GR: Pigment Orange 43 (CI 71105) ;

- Rouge Cosmenyl R": Pigment Red 4 (CI 12085);

- Carmine Cosmenyl FB: Pigment Red 5 (CI 12490);

- Violet Cosmenyl RL: Pigment Violet 23 (CI 51319) ;

- Bleu Cosmenyl A2R: Pigment Blue 15.1 (CI 74160); - Vert Cosmenyl GG: Pigment Green 7 (CI 74260) ;

- Noir Cosmenyl R: Pigment Black 7 (CI 77266) .

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

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

Among the organic dyes, mention may be made of cochineal carmine. Mention may also be made of the products known under the following names: D&C Red 21

(CI 45 380) , D&C Orange 5 (CI 45 370) , D&C Red 27 (CI

45 410) , D&C Orange 10 (CI 45 425) , D&C Red 3 (CI

45 430) , D&C Red 4 (CI 15 510) , D&C Red 33 (CI 17 200) ,

D&C Yellow 5 (CI 19 140) , D&C Yellow 6 (CI 15 985) , D&C Green (CI 61 570), D&C Yellow 1 O (CI 77 002), D&C

Green 3 (CI 42 053), D&C Blue 1 (CI 42 090).

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

The pigment may also be a pigment with special effects. The term "pigments with special effects" means pigments that generally create a non-uniform coloured appearance (characterized by a certain shade, a certain vivacity and a certain lightness) that changes as a function of the conditions of observation (light, temperature, observation angles, etc.). They thus contrast with white or coloured pigments that afford a standard uniform opaque, semi-transparent or transparent shade.

Two types of pigment with special effects exist: those with a low refractive index, such as fluorescent, photochromic or thermochromic pigments, and those with a high refractive index, such as nacres or flakes.

Pigments with special effects that may be mentioned include nacreous pigments such as white nacreous pigments such as mica coated with titanium or with bismuth oxychloride, coloured nacreous pigments such as titanium mica with iron oxides, titanium mica especially with ferric blue or with chromium oxide, titanium mica with an organic pigment of the abovementioned type, and also nacreous pigments based on bismuth oxychloride .

Mention may also be made of pigments with an interference effect that are not fixed onto a substrate, for instance liquid crystals (Helicones HC from Wacker) , holographic interference flakes

(Geometric Pigments or Spectra f/x from Spectratek) .

Pigments with special effects also comprise fluorescent pigments, whether these are substances that are fluorescent in daylight or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, sold, for example, by the company Quantum Dots Corporation.

Quantum dots are luminescent semiconductive nanoparticles capable of emitting, under light excitation, irradiation with a wavelength of between 400 nm and 700 nm. These nanoparticles are known from the literature. They may be manufactured in particular according to the processes described, for example, in US 6 225 198 or US 5 990 479, in the publications cited therein, and also in the following publications: Dabboussi B.O. et al . "(CdSe)ZnS core- shell quantum dots: synthesis and characterization of a size series of highly luminescent nanocrystallites" Journal of Physical Chemistry B, vol. 101, 1997, pp. 9463-9475 and Peng, Xiaogang et al . "Epitaxial growth of highly luminescent CdSe/CdS core/shell nanocrystals with photostability and electronic accessibility", Journal of the American Chemical Society, vol. 119, No. 30, pp. 7019 - 7029 .

Pigments with special effects also comprise fluorescent pigments, whether these are substances that are fluorescent in daylight or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments and thermochromic pigments.

The pigment may be a mineral pigment . The term "mineral pigment" means any pigment that satisfies the definition in Ullmann's encyclopaedia in the chapter on inorganic pigments. Among the mineral pigments that are useful in the present invention, mention may be made of zirconium oxide or cerium oxide, and also iron oxide or chromium oxide, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium dioxide. The following mineral pigments may also be used: Ta₂O₅, Ti₃O₅, Ti₂O₃, TiO, ZrO₂ as a mixture with TiO₂, ZrO₂, Nb₂O₅, CeO₂, ZnS.

The pigment may also be a nacreous pigment such as white nacreous pigments, for example mica coated with titanium or with bismuth oxychloride, coloured nacreous pigments such as mica coated with titanium and with iron oxides, mica coated with titanium and especially with ferric blue or chromium oxide, mica coated with titanium and with an organic pigment as defined above, and also nacreous pigments based on bismuth oxychloride. Examples that may be mentioned include the Cellini pigments sold by Engelhard (Mica-TiO₂-lake) , Prestige sold by Eckart (Mica-TiO₂) or Colorona sold by Merck (MiCa-TiO₂-Fe₂O₃) .

In addition to nacres on a mica support, multilayer pigments based on synthetic substrates such as alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicates, and aluminium, may be envisaged.

The size of the pigment that is useful in the context of the present invention is generally between 10 nm and 200 μm, preferably between 20 nm and 80 μm and more preferentially between 30 nm and 50 μm.

The pigments may be dispersed in the product by means of a dispersant.

The dispersant serves to protect the dispersed particles against agglomeration or flocculation. This dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof, bearing one or more functionalities with strong affinity for the surface of the particles to be dispersed. In particular, they can physically or chemically attach to the surface of the pigments. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, 12-hydroxystearic acid esters and C₈ to C₂o fatty acid esters of polyols such as glycerol or diglycerol are used, such as poly (12-hydroxystearic acid) stearate with a molecular weight of about 750 g/mol, such as the product sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel, or polyhydroxystearic acid such as the product sold under the reference Arlacel PlOO by the company Uniqema, and mixtures thereof.

As other dispersants that may be used in the composition of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids, for instance Solsperse 17 000 sold by the company Avecia, and polydimethylsiloxane/oxypropylene mixtures such as those sold by the company Dow Corning under the references DC2-5185 and DC2-5225 C.

The polydihydroxystearic acid and the 12-hydroxystearic acid esters are preferably intended for a hydrocarbon- based or fluorinated medium, whereas the mixtures of oxyethylene/oxypropylene dimethylsiloxane are preferably intended for a silicone medium.

The additive can also be a filler to adjust the rheology behavior or the physical properties or to compatibilize the various components of the formulation.

The fillers may be mineral or organic and of any form, platelet- shaped, spherical or oblong, irrespective of the crystallographic form (for example lamellar, cubic, hexagonal, orthorhombic, etc.) . Mention may be made of siloxane resin, rosin type resins, acrylic polymer resins, polysaccharides, carbomer, alginate, zinc oxide, ground, precipitated, and colloidal calcium carbonates which can be untreated or treated with stearate or stearic acid, talc, mica, silica, reinforcing silicas such as fumed silicas, precipitated silicas, and hydrophobed silicas (silica surface- treated with a hydrophobic agent) , crushed quartz, ground quartz, alumina, aluminium hydroxide, diatomaceous earth, kaolin, polyamide powder, for instance Nylon® (Orgasol® from Atochem) , poly- [beta] - alanine powder and polyethylene powder, tetrafluoroethylene polymer powders (Teflon) , lauroyllysine, starch, boron nitride, expanded hollow polymer microspheres such as those made of polyvinylidene chloride/acrylonitrile, for instance Expancel [deg . ] (Nobel Industrie), acrylic acid copolymers (Polytrap® from Dow Corning) and silicone resin microbeads (for example Tospearls® from Toshiba) , elastomeric polyorgano- siloxane particles, precipitated calcium carbonate, magnesium carbonate optionally treated with stearic acid or stearate, magnesium hydrocarbonate, hydroxyapatite, hollow silica microspheres (Silica Beads® from Maprecos) , glass or ceramic microcapsules, and metal soaps derived from organic carboxylic acids containing from 8 to 22 carbon atoms and preferably from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate or magnesium myristate.

The filler can be used to adjust the rheology behavior or the physical properties or to compatibilize the various components of the formulation. For example, the filler can be silica to provide the following benefits when used in the following ranges: 0.1 wt . % to 5 wt . % compatibilizer and drying agent / 5 wt . % to 15 wt . % rheological modifier and texture enhancer / 15 wt . % to 30 wt .% mechanical strength enhancer.

The additive can also be a gelling agent. The gelling agents used in the compositions according to the invention may be organic or mineral, and polymeric or molecular, hydrophilic or lipophilic gelling agents.

Mineral lipophilic gelling agents that may be mentioned include optionally modified clays, for instance hectorites modified with a Ci₀ to C₂₂ fatty acid ammonium chloride, for instance hectorite modified with distearyldimethylammonium chloride, for instance the product sold under the name "Bentone 38V " by the company Elementis.

Mention may also be made of fumed silica optionally subjected to a hydrophobic surface treatment, the particle size of which is less than 1 μm. Specifically, it is possible to chemically modify the surface of the silica, by chemical reaction generating a reduction in the number of silanol groups present at the surface of the silica. It is especially possible to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained. The hydrophobic groups may be: trimethylsiloxyl groups, which are obtained especially by treating fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are known as "silica silylate" according to the CTFA (6th edition, 1995) . They are sold, for example, under the references Aerosil R812^®, R8200 by the company Degussa, Wacker HDX H2000 by Wacker and Cab-O-Sil TS-530⁰ by the company Cabot ;

- dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained especially by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane . Silicas thus treated are known as "silica dimethyl silylate" according to the CTFA (6th edition, 1995) . They are sold, for example, under the references Aerosil R972^" and Aerosil R974^" by the company Degussa, and Cab-O-Sil TS-610^® and Cab-O-Sil TS-72O⁰ by the company Cabot.

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

It is also possible to use non-polymeric, molecular organic gelling agents, also known as organogelling agents, associated with a liquid fatty phase (which may be the liquid fatty phase of the composition according to the invention) , which are compounds whose molecules are capable of establishing between themselves physical interactions leading to self- aggregation of the molecules with formation of a supramolecular 3D network that is responsible for the gelation of the liquid fatty phase.

The supramolecular network may result from the formation of a network of fibrils (caused by the stacking or aggregation of organogelling molecules) , which immobilizes the molecules of the liquid fatty phase.

The ability to form this network of fibrils, and thus to gel, depends on the nature (or chemical class) of the organogelling agent, on the nature of the substituents borne by its molecules for a given chemical class, and on the nature of the liquid fatty phase .

The physical interactions are of diverse nature but exclude co-crystallization. These physical interactions are in particular interactions of self-complementary hydrogen interaction type, π interactions between unsaturated rings, dipolar interactions, coordination bonds with organometallic derivatives, and combinations thereof. In general, each molecule of an organogelling agent can establish several types of physical interaction with a neighbouring molecule. Thus, advantageously, the molecules of the organogelling agents according to the invention comprise at least one group capable of establishing hydrogen bonds and better still at least two groups, at least one aromatic ring and better still at least two aromatic rings, at least one or more ethylenically unsaturated bonds and/or at least one or more asymmetric carbons. Preferably, the groups capable of forming hydrogen bonds are chosen from hydroxyl , carbonyl, amine, carboxylic acid, amide, urea and benzyl groups, and combinations thereof.

The organogelling agent (s) according to the invention is (are) soluble in the liquid fatty phase after heating to obtain a transparent uniform liquid phase. They may be solid or liquid at room temperature and atmospheric pressure.

The molecular organogelling agent (s) that may be used in the composition according to the invention is (are) especially those described in the document "Specialist Surfactants" edited by D. Robb, 1997, pp. 209-263, Chapter 8 by P . Terech, European patent applications EP-A-I 068 854 and EP-A-I 086 945, or alternatively in patent application WO-A-02/47031.

Mention may be made especially, among these organogelling agents, of amides of carboxylic acids, in particular of tricarboxylic acids, for instance cyclohexanetricarboxamides (see European patent application EP-A-I 068 854) , diamides with hydrocarbon- based chains each containing from 1 to 22 carbon atoms, for example from 6 to 18 carbon atoms, the said chains being unsubstituted or substituted with at least one substituent chosen from ester, urea and fluoro groups

(see patent application EP-A-I 086 945) and especially diamides resulting from the reaction of diamino- cyclohexane, in particular diaminocyclohexane in trans form, and of an acid chloride, for instance N, N' -bis- (dodecanoyl) -1 , 2 -diaminocyclohexane, N-acylamino acid amides, for instance the diamides resulting from the action of an N-acylamino acid with amines containing from 1 to 22 carbon atoms, for instance those described in document WO-93/23008 and especially N- acylglutamic acid amides in which the acyl group represents a C₈ to C₂₂ alkyl chain, such as N-lauroyl- L-glutamic acid dibutylamide, manufactured or sold by the company Aj inomoto under the name GP-I, and mixtures thereof .

The polymeric organic lipophilic gelling agents are, for example, partially or totally crosslinked elastomeric organopolysiloxanes of three-dimensional structure, for instance those sold under the names KSG6⁰, KSG16⁰ and KSG18^® from Shin-Etsu, Trefil E-505C^® or Trefil E-5O6C⁰ from Dow Corning, Gransil SR-CYC^®, SR DMF 10^®, SR-DC556⁰, SR 5CYC gel^®, SR DMF 10 gel^® and SR DC 556 gel" from Grant Industries and SF 1204^® and JK 113 from General Electric; ethylcellulose, for instance the product sold under the name Ethocel by Dow Chemical; polycondensates of polyamide type resulting from condensation between (α) at least one acid chosen from dicarboxylic acids containing at least 32 carbon atoms, such as fatty acid dimers, and (β) an alkylenediamine and in particular ethylenediamine, in which the polyamide polymer comprises at least one carboxylic acid end group esterified or amidated with at least one saturated and linear monoalcohol or one saturated and linear monoamine containing from 12 to 30 carbon atoms, and in particular ethylenediamine/stearyl dilinoleate copolymers such as the product sold under the name Uniclear 100 VG^" by the company Arizona Chemical; silicone polyamides of the polyorganosiloxane type, for instance 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, for instance those sold under the reference Dow Corning 2-8179 Gellant by the company Dow Corning ; galactomannans comprising from one to six and in particular from two to four hydroxyl groups per saccharide, substituted with a saturated or unsaturated alkyl chain, for instance guar gum alkylated with Ci to C₆, and in particular Ci to C₃, alkyl chains, and mixtures thereof; block copolymers of "diblock" or "triblock" type, of the polystyrene/polyisoprene or polystyrene/polybutadiene type, such as the products sold under the name Luvitol HSB by the company BASF, of the polystyrene/copoly (ethylene-propylene) type, such as the products sold under the name Kraton by the company Shell Chemical Co., or of the polystyrene/copoly (ethylene-butylene) type . It is also possible to use silicone 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 may belong to the following two families : polyorganosiloxanes comprising at least two groups capable of establishing hydrogen interactions, these two groups being located in the polymer chain, and/or polyorganosiloxanes comprising at least two groups capable of establishing hydrogen interactions, these two groups being located on grafts or branches.

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

The lipophilic gelling agents may be present in the compositions according to the invention in a content ranging from 0.05% to 40% by weight, preferably from

0.5% to 20% and better still from 1% to 15% by weight relative to the total weight of the composition.

Hydrophilic or water-soluble gelling agents that may be mentioned include:

- homopolymers or copolymers of acrylic or methacrylic acid or the salts and esters thereof, and in particular the products sold under the names Versicol F or Versicol " by the company Allied Colloid, Ultrahold 8 by the company Ciba-Geigy, and the polyacrylic acids of Synthalen K type,-

- copolymers of acrylic acid and of acrylamide sold in the form of the sodium salt thereof under the names Reten by the company Hercules, sodium polymethacrylate sold under the name Darvan No . 7 by the company Vanderbilt, and the sodium salts of polyhydroxycarboxylic acids sold under the name Hydagen F by the company Henkel; - polyacrylic acid/alkyl acrylate copolymers of the Pemulen type;

- AMPS (polyacrylamidomethylpropanesulfonic acid partially neutralized with ammonia and highly crosslinked) sold by the company Clariant; - AMPS/acrylamide copolymers of the Sepigel or Simulgel type, sold by the company SEPPIC, and

- AMPS/polyoxyethylenated alkyl methacrylate copolymers (crosslinked or non-crosslinked) ; and mixtures thereof .

As other examples of water-soluble gelling polymers, mention may be made of:

- proteins, for instance proteins of plant origin, such as wheat or soybean proteins,- proteins of animal origin such as keratins, for example keratin hydrolysates and sulfonic keratins;

- anionic, cationic, amphoteric or nonionic chitin or chitosan polymers; non-liposoluble cellulose polymers such as hydroxyethylcellulose, hydroxypropylcellulose, methyl - cellulose, ethylhydroxyethylcellulose and carboxy- methylcellulose, and also quaternized cellulose derivatives ; vinyl polymers, for instance polyvinyl - pyrrolidones, copolymers of methyl vinyl ether and of malic anhydride, the copolymer of vinyl acetate and of crotonic acid, copolymers of vinylpyrrolidone and of vinyl acetate; copolymers of vinylpyrrolidone and of caprolactam; polyvinyl alcohol; - associative polyurethanes such as the Ci₆-OEi₂₀-Ci₆ polymer from the company Servo Delden (sold under the name Ser Ad FXIlOO, which is a molecule containing urethane functions and having a weight-average molecular weight of 1300) , OE being an oxyethylene unit, Rheolate 205 containing urea functions, sold by the company Rheox, or Rheolate 208 or 204 (these polymers being sold in pure form) or DW 1206B from Rohm & Haas, containing a C₂o alkyl chain and a urethane bond, sold at a solids content of 20% in water. It is also possible to use solutions or dispersions of these associative polyurethanes, especially in water or in aqueous-alcoholic medium. Examples of such polymers that may be mentioned include Ser Ad FXlOlO, 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 product DW 1206F and DW 1206J, and also Acrysol RM 184 or Acrysol 44 from the company Rohm & Haas, or Borchigel LW 44 from the company Borchers,- - optionally modified polymers of natural origin, such as :

- gum arabics, guar gum, xanthan derivatives and karaya gum;

- alginates and carrageenans,- - glycoaminoglycans, and hyaluronic acid and its derivatives ;

- shellac resin, sandarac gum, dammar resins, elemi gums and copal resins,-

- deoxyribonucleic acid; - mucopolysaccharides such as hyaluronic acid and chondroitin sulfates, and mixtures thereof.

The hydrophilic gelling agents may be present in the composition according to the invention in a content ranging from 0.05% to 20% by weight, preferably from 0.5% to 10% and better still from 0.8% to 5% by weight relative to the total weight of the composition.

The additive may also be a film- forming polymer. According to the present invention, the term "film- forming polymer" means a polymer capable, by itself or in the presence of an auxiliary film- forming agent, of forming a continuous film that adheres to a support and especially to keratin materials.

The film- forming polymer may be present in a solids content (or active material content) ranging from 0.1% to 30% by weight, preferably from 0.5% to 20% by weight and better still from 1% to 15% by weight relative to the total weight of the composition.

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

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

The film-forming polymers of free-radical type may be, in particular, vinyl polymers or copolymers, in particular acrylic polymers.

The vinyl film- forming polymers may result from the polymerization of ethylenically unsaturated monomers containing at least one acidic group and/or esters of these acidic monomers and/or amides of these acidic monomers .

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

The esters of acidic monomers are advantageously chosen from (meth) acrylic acid esters (also known as (meth) acrylates) , especially (meth) acrylates of an alkyl, in particular of a Ci-C₃O and preferably Ci-C₂O alkyl, (meth) acrylates of an aryl , in particular of a C₆-Ci₀ aryl, and (meth) acrylates of a hydroxyalkyl , in particular of a C₂-C₆ hydroxyalkyl.

Among the alkyl (meth) acrylates that may be mentioned are methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate and cyclohexyl methacrylate.

Among the hydroxyalkyl (meth) acrylates that may be mentioned are hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate .

Among the aryl (meth) acrylates that may be mentioned are benzyl acrylate and phenyl acrylate.

The (meth) acrylic acid esters that are particularly preferred are the alkyl (meth) acrylates .

According to the present invention, the alkyl group of the esters may be either fluorinated or perfluorinated, i.e. some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.

Examples of amides of the acid monomers that may be mentioned are (meth) acrylamides, and especially N- alkyl (meth) acrylamides, in particular of a C₂-Ci₂ alkyl. Among the N-alkyl (meth) acrylamides that may be mentioned are N-ethylacrylamide, N-t-butylacrylamide, N-t-octylacrylamide and N-undecylacrylamide .

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

Examples of vinyl esters that may be mentioned are vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butylbenzoate .

Styrene monomers that may be mentioned are styrene and α-methylstyrene .

Among the film- forming polycondensates that may be mentioned are polyurethanes, polyesters, polyester- amides, polyamides, epoxyester resins and polyureas .

The polyurethanes may be chosen from anionic, cationic, nonionic and amphoteric polyurethanes, polyurethane- acrylics, polyurethane-polyvinylpyrrolidones, poly- ester-polyurethanes, polyether-polyurethanes, polyureas and polyurea/polyurethanes, and mixtures thereof.

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

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

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

The polyesteramides may be obtained in a manner analogous to that of the polyesters, by polycon- densation of diacids with diamines or amino alcohols. Diamines that may be used are ethylenediamine, hexamethylenediamine and meta- or para-phenylenedi- amine . An amino alcohol that may be used is monoethanolamine .

The polyester may also comprise at least one monomer bearing at least one group -SO₃M, with M representing a hydrogen atom, an ammonium ion NH₄ ⁺ or a metal ion such as, for example, an Na⁺, Li⁺, K⁺, Mg²⁺, Ca²⁺, Cu²⁺, Fe²⁺ or Fe³⁺ ion. A difunctional aromatic monomer comprising such a group -SO₃M may be used in particular.

The aromatic nucleus of the difunctional aromatic monomer also bearing a group -SO₃M as described above may be chosen, for example, from benzene, naphthalene, anthracene, biphenyl, oxybiphenyl, sulfonylbiphenyl and methylenebiphenyl nuclei. As examples of difunctional aromatic monomers also bearing a group -SO₃M, mention may be made of: sulfoisophthalic acid, sulfotereph- thalic acid, sulfophthalic acid, 4-sulfonaphthalene- 2, 7-dicarboxylic acid. The copolymers preferably used are those based on isophthalate/sulfoisophthalate, and more particularly copolymers obtained by condensation of diethylene glycol, cyclohexanedimethanol , isophthalic acid and sulfoisophthalic acid.

The polymers of natural origin, optionally modified, may be chosen from shellac resin, sandarac gum, dammar resins, elemi gums, copal resins and cellulose polymers, and mixtures thereof.

According to a first embodiment of the invention, the film- forming polymer may be a water-soluble polymer and may be present in an aqueous phase of the first and/or second composition; the polymer is thus solubilized in the aqueous phase of the composition.

According to another variant, the film- forming polymer may be a polymer dissolved in a liquid fatty phase comprising organic solvents or oils such as those described above (the film-forming polymer is thus said to be a liposoluble polymer) . The liquid fatty phase preferably comprises a volatile oil, optionally mixed with a non-volatile oil, the oils possibly being chosen from those mentioned above.

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

These copolymers may be crosslinked with the aid of crosslinking agents, which may be either of the vinyl type or of the allylic or methallylic type, such as tetraallyloxyethane, divinylbenzene, divinyl octane- dioate, divinyl dodecanedioate and divinyl octadecane- dioate .

Examples of these copolymers that may be mentioned are the following copolymers: vinyl acetate/allyl stearate, vinyl acetate/vinyl laurate, vinyl acetate/vinyl stearate, vinyl acetate/octadecene, vinyl acetate/ octadecyl vinyl ether, vinyl propionate/allyl laurate, vinyl propionate/vinyl laurate, vinyl stearate/ 1-octadecene, vinyl acetate/1-dodecene, vinyl stearate/ ethyl vinyl ether, vinyl propionate/cetyl vinyl ether, vinyl stearate/allyl acetate, vinyl 2 , 2-dimethyloctan- oate/vinyl laurate, allyl 2 , 2-dimethylpentanoate/vinyl laurate, vinyl dimethylpropionate/vinyl stearate, allyl dimethylpropionate/vinyl stearate, vinyl propionate/ vinyl stearate, crosslinked with 0.2% divinylbenzene, vinyl dimethylpropionate/vinyl laurate, crosslinked with 0.2% divinylbenzene, vinyl acetate/octadecyl vinyl ether, crosslinked with 0.2% tetraallyloxyethane, vinyl acetate/allyl stearate, crosslinked with 0.2% divinylbenzene, vinyl acetate/1-octadecene, crosslinked with 0.2% divinylbenzene, and allyl propionate/allyl stearate, crosslinked with 0.2% divinylbenzene.

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

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

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

Mention may also be made of liposoluble homopolymers, and in particular those resulting from the homopolymerization of vinyl esters containing from 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, the alkyl radicals containing from 2 to 24 carbon atoms .

Examples of liposoluble homopolymers that may especially be mentioned include: polyvinyl laurate and polylauryl (meth) acrylates, these poly (meth) acrylates possibly being crosslinked using ethylene glycol dimethacrylate or tetraethylene glycol dimethacrylate.

According to one advantageous embodiment, the first and/or second composition of the process according to the invention comprises at least one polyvinyl laurate film- forming polymer.

As liposoluble film- forming polymers which may be used in the invention, mention may also be made of polyalkylenes and in particular copolymers of C₂-C₂O alkenes, such as polybutene, alkylcelluloses with a linear or branched, saturated or unsaturated Ci-C₈ alkyl radical, for instance ethylcellulose and propylcellulose, copolymers of vinylpyrrolidone (VP) and in particular copolymers of vinylpyrrolidone and of C₂ to C₄O and better still C₃ to C₂₀ alkene . As examples of VP copolymers which may be used in the invention, mention may be made of the copolymers of VP/vinyl acetate, VP/ethyl methacrylate, butylated polyvinylpyrrolidone (PVP) , VP/ethyl methacrylate/methacrylic acid, VP/eicosene, VP/hexadecene, VP/triacontene, VP/styrene or VP/acrylic acid/lauryl methacrylate.

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

Examples of commercially available polymethylsilsesqui- oxane resins that may be mentioned include those sold: by the company Wacker under the reference Resin MK, such as Belsil PMS MK; by the company Shin-Etsu under the reference KR-220L. Siloxysilicate resins that may be mentioned include trimethyl siloxysilicate (TMS) resins such as those sold under the reference SR 1000 by the company General Electric or under the reference TMS 803 by the company Wacker. Mention may also be made of the trimethyl siloxysilicate resins sold in a solvent such as cyclomethicone, sold under the name KF- 7312J by the company Shin-Etsu, and DC 749 and DC 593 by the company Dow Corning .

Mention may also be made of silicone resin copolymers such as those mentioned above with polydimethyl- siloxanes, for instance the pressure-sensitive adhesive copolymers sold by the company Dow Corning under the reference Bio-PSA and described in document US 5 162 410, or the silicone copolymers derived from the reaction of a silicone resin, such as those described above, and of a diorganosiloxane, as described in document WO 2004/073 626.

According to one embodiment of the invention, the film- forming polymer is a film- forming linear block ethylenic polymer, which preferably comprises at least a first block and at least a second block with different glass transition temperatures (Tg) , the said first and second blocks being linked together via an intermediate block comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block.

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

Such polymers are described, for example, in document EP 1 411 069 or WO 04/028 488. The film- forming polymer may also be present in the composition in the form of particles dispersed in an aqueous phase or in a non-aqueous solvent phase, which is generally known as a latex or pseudolatex. The techniques for preparing these dispersions are well known to those skilled in the art.

Aqueous dispersions of film- forming polymers that may be used include the acrylic dispersions sold under the names Neocryl XK-90⁰, Neocryl A-1070⁰, Neocryl A-1090⁰, 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 SJ⁰ by the company Daito Kasey Kogyo,- Syntran 5760 by the company Interpolymer, Allianz OPT by the company Rohm & Haas, aqueous dispersions of acrylic or styrene/acrylic polymers sold under the brand name Joncryl^" by the company Johnson Polymer, or the aqueous dispersions of polyurethane sold under the names Neorez R- 981 ^" and Neorez R- 974^" by the company Avecia-Neoresins, Avalure UR-405 , Avalure UR-410 , Avalure UR-425⁰, Avalure UR-450⁰, Sancure 875^®, Sancure 861^®, Sancure 878^® and Sancure 2060^® by the company Goodrich, Impranil 85^" by the company Bayer and Aquamere H-1511⁰ by the company Hydromer; the sulfopolyesters sold under the brand name Eastman AQ^" by the company Eastman Chemical Products, and vinyl dispersions, for instance Mexomer PAM^" from the company Chimex, and mixtures thereof.

Examples of non-aqueous film- forming polymer dispersions that may also be mentioned include acrylic dispersions in isododecane, for instance Mexomer PAP^® from the company Chimex, and dispersions of particles of a grafted ethylenic polymer, preferably an acrylic polymer, in a liquid fatty phase, the ethylenic polymer advantageously being dispersed in the absence of additional stabilizer at the surface of the particles as described especially in document WO 04/055 081.

The composition according to the invention may comprise a plasticizer that promotes the formation of a film with the film-forming polymer. Such a plasticizer may be chosen from any compound known to those skilled in the art as being capable of fulfilling the desired function.

The compositions according to the invention may contain emulsifying surfactants, which are especially present in a proportion ranging from 0.1% to 30% by weight, better still from 1% to 15% and even better still from 2% to 10% relative to the total weight of the composition. These surfactants may be chosen from anionic, nonionic, amphoteric and zwitterionic surfactants. Reference may be made to the document "Encyclopedia of Chemical Technology, Kirk-Othmer" , Volume 22, pp. 333-432, 3rd Edition, 1979, Wiley, for the definition of the properties and functions (emulsifying) of surfactants, in particular pp. 347-377 of this reference, for the anionic and nonionic surfactants .

The surfactants preferentially used in the first and second compositions according to the invention are chosen from: a) nonionic surfactants with an HLB of greater than or equal to 8 at 25⁰C, used alone or as a mixture,- mention may be made especially of: - oxyethylenated and/or oxypropylenated ethers (which may comprise from 1 to 150 oxyethylene and/or oxypropylene groups) of glycerol;

- oxyethylenated and/or oxypropylenated ethers (which may comprise from 1 to 150 oxyethylene and/or oxypropylene groups) of fatty alcohols (especially of C₈-C₂4 and preferably Ci₂-Ci₈ alcohol) , such as oxyethylenated cetearyl alcohol ether containing 30 oxyethylene groups (CTFA name Ceteareth-30) and the oxyethylenated ether of the mixture of Ci₂-Ci₅ fatty alcohols comprising 7 oxyethylene groups (CTFA name C12-15 Pareth-7 sold under the name Neodol 25-7^® by Shell Chemicals) ;

- fatty acid esters (especially of a C₈-C₂₄ and preferably Ci₆-C₂₂ acid) of polyethylene glycol (which may comprise from 1 to 150 ethylene glycol units) , such as PEG-50 stearate and PEG-40 monostearate sold under the name Myrj 52P by the company ICI Uniqema,-

- fatty acid esters (especially of a C₈-C₂₄ and preferably Ci₆-C₂₂ acid) of oxyethylenated and/or oxypropylenated glyceryl ethers (which may comprise from 1 to 150 oxyethylene and/or oxypropylene groups) , for instance PEG-200 glyceryl monostearate sold under the name Simulsol 220 TM by the company SEPPIC; glyceryl stearate polyethoxylated with 30 ethylene oxide groups, for instance the product Tagat S sold by the company Goldschmidt, glyceryl oleate polyethoxylated with 30 ethylene oxide groups, for instance the product Tagat 0 sold by the company Goldschmidt, glyceryl cocoate polyethoxylated with 30 ethylene oxide groups, for instance the product Varionic LI 13 sold by the company Sherex, glyceryl isostearate polyethoxylated with 30 ethylene oxide groups, for instance the product Tagat L sold by the company Goldschmidt, and glyceryl laurate polyethoxylated with 30 ethylene oxide groups, for instance the product Tagat I from the company Goldschmidt ;

- fatty acid esters (especially of a C₈-C₂₄ and preferably Ci₆-C₂₂ acid) of oxyethylenated and/or oxypropylenated sorbitol ethers (which may comprise from 1 to 150 oxyethylene and/or oxypropylene groups) , for instance polysorbate 60 sold under the name Tween 60 by the company Uniqema,- - dimethicone copolyol, such as the product sold under the name Q2-5220 by the company Dow Corning;

- dimethicone copolyol benzoate (Finsolv SLB 101 and 201 by the company Finetex) ;

- copolymers of propylene oxide and of ethylene oxide, also known as EO/PO polycondensates, for instance the polyethylene glycol/polypropylene glycol/polyethylene glycol triblock polycondensates sold under the name Synperonic, for instance Synperonic PE/L44 and Synperonic PE/F127, by the company ICI, and mixtures thereof;

- and mixtures thereof . b) nonionic surfactants with an HLB of less than 8 at 25⁰C, optionally combined with one or more nonionic surfactants with an HLB of greater than 8 at 25⁰C, as mentioned above, such as:

- saccharide esters and ethers, such as sucrose stearate, sucrose cocoate and sorbitan stearate, and mixtures thereof, for instance Arlatone 2121 sold by the company ICI; - fatty acid esters (especially of a C₈-C₂₄ and preferably Ci₆-C₂₂ acid) of polyols, especially of glycerol or of sorbitol, such as glyceryl stearate, glyceryl stearate such as the product sold under the name Tegin M by the company Goldschmidt, glyceryl laurate such as the product sold under the name Imwitor 312 by the company Hϋls, polyglyceryl-2 stearate, sorbitan tristearate or glyceryl ricinoleate,-

- the mixture of cyclomethicone/dimethicone copolyol sold under the name Q2-3225C by the company Dow Corning . c) anionic surfactants such as:

- Ci₆-C₃O fatty acid salts, especially those derived from amines, for instance triethanolamine stearate;

- polyoxyethylenated fatty acid salts, especially those derived from amines or alkali metal salts, and mixtures thereof;

- phosphoric esters and salts thereof, such as DEA oleth-10 phosphate (Crodafos N ION from the company Croda) and cetyl phosphate (Amphisol K from the company DSM Nutritional Products) ;

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

- alkyl ether sulfates, such as sodium lauryl ether sulfate;

- isethionates,-

- acylglutamates such as Disodium hydrogenated tallow glutamate (Amisoft HS-21 R sold by the company Ajinomoto), and mixtures thereof.

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

Surfactants that allow an oil-in-water or wax-in-water emulsion to be obtained are preferably used.

The additive may also be chosen among fibres. The term "fibre" should be understood as meaning an object of length L and diameter D such that L is very much greater than D, D being the diameter of the circle in which the cross section of the fibre is inscribed. In particular, the ratio L/D (or shape factor) is chosen in the range from 3.5 to 2500, preferably from 5 to 500 and better still from 5 to 150.

They may especially be fibres used in the manufacture of textiles, and especially silk fibre, cotton fibre, wool fibre, flax fibre, cellulose fibre extracted in particular from wood, from plants or from algae, rayon fibre, polyamide (Nylon ) fibre, viscose fibre, acetate fibre, especially rayon acetate fibre, poly(p- phenyleneterephthalamide) (or aramid) fibre, especially Kevlar^® fibre, acrylic polymer fibre, especially polymethyl methacrylate fibre or poly (2-hydroxyethyl methacrylate) fibre, polyolefin fibre and especially polyethylene or polypropylene fibre, glass fibre, silica fibre, carbon fibre, especially of carbon in graphite form, polytetrafluoroethylene (such as Teflon^®) fibre, insoluble collagen fibre, polyester fibre, polyvinyl chloride fibre or polyvinylidene chloride fibre, polyvinyl alcohol fibre, polyacrylo- nitrile fibre, chitosan fibre, polyurethane fibre, polyethylene phthalate fibre, and fibres formed from a mixture of polymers such as those mentioned above, for instance polyamide/polyester fibres.

The compositions according to the invention may comprise any cosmetic active agent, such as active agents chosen from antioxidants, preserving agents, fragrances, bactericidal or antiperspirant active agents, neutralizers, emollients, moisturizers, vitamins and screening agents, in particular sunscreens. Needless to say, a person skilled in the art will take care to select this or these optional additional compound (s) , and/or the amount thereof, such that the advantageous properties of the corresponding composition according to the invention are not, or are not substantially, adversely affected by the envisaged addition, especially so as not to interfere with the reaction between compounds A, B and C.

The first and second, and where appropriate third, compositions of the process according to the invention may be, independently, in the form of a suspension, a dispersion, a solution, a gel, an emulsion, especially an oil-in-water (0/W) emulsion, a wax-in-water or water-in-oil (W/0) emulsion or a multiple emulsion

(W/O/W or polyol/O/W or 0/W/O) or in the form of a cream, a paste, a mousse, a vesicular dispersion, especially of ionic or nonionic lipids, a two-phase or multiphase lotion, a powder or a paste, especially a soft paste.

The process according to the invention may be advantageously used for making up the skin, the lips, the eyelashes and/or the nails depending on the nature of the ingredients used. In particular, the compositions in the process according to the invention may be, independently, in the form of a solid foundation, a lipstick wand or paste, a concealer product, an eye contour product, an eyeliner, a mascara, an eyeshadow, a body makeup product or a skin colouring product.

According to one embodiment, the first and second, and where appropriate third, compositions are lipstick compositions .

According to another embodiment, the first and second, and where appropriate third, compositions are compositions for coating the eyelashes or the eyebrows and more particularly mascaras.

According to another embodiment, the first and second, and where appropriate third, compositions are compositions for coating bodily or facial skin, more particularly compositions for making up bodily or facial skin, for instance foundations or body makeup compositions .

A person skilled in the art may select the appropriate galenical form, and also the method for preparing it, on the basis of his general knowledge, taking into account firstly the nature of the constituents used, especially their solubility in the support, and secondly the intended use of the composition.

The invention is illustrated in greater detail by the examples described below. Unless otherwise mentioned, the amounts indicated are expressed as mass percentages.

Examples

Examples that follow illustrate the methods of the invention.

Unless indicated, all parts are by weight and all viscosities are at 25⁰C.

The formulation components used to illustrate the invention are:

TiO2 : 44 Wt. %

Red 7 : 8 Wt. %

Blue 1

3 Wt. %

Pigments Lake : blend Yellow 6 41 Wt. % Lake :

Black

Iron 4 Wt. %

Oxide :

NA = not applicable

The formulations used to illustrate the invention are lips make-up products:

Procedure to prepare the evaluation samples of the formulations Fl, F2 , F3 , and F4 :

1) Weigh (a)

2) Disperse the pigments in (a) using three-roll-mill

3) Weigh (b) and add to the blend 2) and mix at 800 rpm

4) Weigh (c) and add to the blend 3) and mix at 800 rpm

5) Add the catalyst (d) to the blend 4) and mix at 800 rpm

6) Coat with a blade the blend 5) onto a drawdown card (Form WP-I, The Leneta Co., Mahwah NJ07430, USA) to obtain a thickness of 100 microns

7) Let cure at room temperature (23⁰C +/-2⁰C)

The formulation with no chain extender (F4, RHCE=O) leads to a film that is considered not tacky but with an insufficient adhesion level . Formulation with the highest chain level of chain extender (F3, RHCE=O.68) leads to a film with a high adhesion level but which is too tacky.

Formulations Fl (RHCE=O.40) & F2 (RHCE=O.19) have been shown as being the best compromise between adhesion and tack.

The formulations Fl, F2 , F3 , and F4 present acceptable curing time for cosmetic applications. The RHAIk for these formulations is 2.74. The RHAIk needs to be higher than 3 to ensure a more appropriate curing time for cosmetic applications. F5 (RHAIk = 5.72) is an example of formulation with highly appropriate curing time for cosmetic applications .

Formulation

F5 component

(a) 88.51 Wt .%

(b) 2.38 Wt .%

(O 6.93 Wt .%

(d) 1.19 Wt .%

Pigments

0.99 Wt .% blend

RHAIk 5. 72

RHCE 0. 40

Other example with a different vinyl -terminated polydimethylsiloxane :

(a) = Vinyl -terminated polydimethylsiloxane with 2000 mm²/s and 8.5 * 10^"5 mol/g of vinyl

Application process:

The application process consists in applying the compositions on the lips, and in spreading out the compositions on the lips using a finger or any appropriate tool, until the compositions become thin and homogenous coating layers. The thicknesses should be lower than 200 μm, preferably lower than 150 μm, and more preferably lower than 100 μm. Then let the compositions cure, until they form non tacky films. Due to the thinness of the coatings, the films present satisfying feelings of comfort when applied on the lips .

Claims

1. Process for the making up and/or cosmetic treatment of keratinous materials comprising the step of applying on said keratinous material, via at least one composition, the compounds:

(A) a polydiorganosiloxane having at least two silicon-bonded alkenyl groups per molecule, (B) a hydrosilicon compound having at least 3 silicon-bonded hydrogen atoms per molecule,

(C) a diorganohydrogensiloxy-terminated polydiorganosiloxane,

(2) 0 < RHCE < 0.7 wherein RHCE is the ratio of the number of SiH moles in C with respect to the number of SiH moles in B and C, and further wherein the compounds A, B, C and D are applied in such a way that said hydrosilylation reaction occurs at least in part on the keratinous material to be treated and/or made up, and further wherein the compounds are applied on the keratinous materials in a coat having a thickness lower than 200 μm..

2. Process according to claim 1, wherein RHAIk > 2, preferably > 2.5, preferably > 3.

3. Process according to claim 1 or 2, wherein the compounds A, B, C and D are applied via at least a first and a second compositions to be mixed either extemporaneously prior to application on the keratinous materials or upon application on said keratinous materials, the compounds A, B, C and D being contained in either one of said first and second compositions so that no hydrosilylation reaction occurs prior to said mixing of the first and second compositions.

4. Process according to claim 3 wherein the first composition comprises the compounds A and D, and the second composition comprises the compounds B and C.

5. Process according to claim 3 or 4 wherein the first composition comprises the compounds A and D, and the second composition comprises the compounds A, B and C.

6. Process according to one of Claims 1 to 5, characterized in that compound A is chosen from polysiloxanes comprising siloxane units of formula

in which each R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms such as alkyls or phenyl groups, m is 0, 1 or 2 and

R' represents an aliphatically unsaturated group such as vinyl, allyl, hexenyl and cyclohexenyl or a group R¹¹CH=CHR'", where R" represents a divalent aliphatic chain linked to the silicon atom and R'" represents a hydrogen atom or an alkyl group .

7. Process according to Claim 6, characterized in that R represents a methyl radical.

8. Process according to one of Claims 1 to 7, characterized in that the compound A is chosen from polyorganosiloxanes comprising units of formula

n (4~n)

T (ID in which R is a monovalent hydrocarbon group having 1 to 20 carbon atoms such as alkyls or phenyl groups, and n is O, 1, 2 or 3.

9. Process according to one of Claims 1 to 8, characterized in that compound B is chosen from organosiloxanes comprising at least one alkylhydrogenosiloxane unit of the following formula:

in which: each R represents a monovalent hydrocarbon group containing from 1 to 20 carbon atoms or a phenyl group, and p is equal to 0 , 1 or 2.

10. Process according to Claim 9, in which the compound B is such that R represents a methyl group.

11. Process according to one of Claims 1 to 10, in which the compound C is a diorganohydrogensiloxy-terminated polydiorganosiloxane, wherein the organic substituents are alkyl or phenyl groups having no more than 8 carbon atoms.

12. Process according to Claim 11, in which the compound C is a dimethylhydrogensiloxy- terminated polydimethylsiloxane .

13. Process according to one of Claims 1 to 12, characterized in that the compound D is a platinum-based catalyst.

14. Process according to the preceding claim, characterized in that the catalyst represents from 0.0001% to 20% by weight relative to the total weight of the composition comprising it.

15. Process for the making up and/or cosmetic treatment of keratinous materials comprising the step of applying on said keratinous material, via at least one composition, the compounds:

(C) a diorganoalkenylsiloxy-terminated polydiorganosiloxane,