WO2013092378A1

WO2013092378A1 - Application device comprising a pigment dyeing composition based on specific acrylic polymer and on silicone copolymer, and method for dyeing keratinous fibres employing it

Info

Publication number: WO2013092378A1
Application number: PCT/EP2012/075413
Authority: WO
Inventors: Karen Teboul
Original assignee: L'oreal
Priority date: 2011-12-20
Filing date: 2012-12-13
Publication date: 2013-06-27
Also published as: FR2984090A1; FR2984090B1

Abstract

A subject-matter of the present invention is an application device for a composition for dyeing keratinous fibres comprising an aqueous dispersion of particles of hybrid hydrophobic film-forming acrylic polymer, a linear block silicone copolymer and a pigment, and also a dyeing method employing such a device. The composition makes it possible to obtain a coloured sheathing which is persistent towards shampooing operations and which leaves the treated fibres individualized, with an improved cosmetic feel. The device according to the invention makes it possible to deposit in a simple way the dyeing composition included in it, without the risk of the product running, in a rapid way and in an effective way without requiring the use of additional accessories, with homogeneous impregnation of the fibres, whatever their length. In addition, the composition applied makes it possible to obtain a coloured sheathing which is visible on all hair types and which is persistent, while retaining the physical qualities of the keratinous fibres and while leaving them completely individualized and easily styled.

Description

APPLICATION DEVICE COMPRISING A PIGMENT DYEING COMPOSITION BASED ON SPECIFIC ACRYLIC POLYMER AND ON SILICONE COPOLYMER, AND METHOD FOR DYEING KERATINOUS FIBRES EMPLOYING IT

A subject-matter of the present invention is an application device for a composition for dyeing keratinous fibres comprising an aqueous dispersion of particles of specific acrylic polymer, a linear block silicone copolymer and a pigment, and also a dyeing method employing such a device.

It is known, in the field of the dyeing of keratinous fibres, in particular human keratinous fibres, to dye keratinous fibres by different techniques, in particular starting from dye precursors for permanent colourings or also from direct dyes or pigments for non-permanent colourings.

The present invention is concerned more particularly with the field of non- permanent colouring produced starting from pigments (in other words, starting from colouring substances which are insoluble in the composition in which they are present).

One of the advantages of this type of colouring, in comparison with those deploying direct dyes or dye precursors, is that, in order to be visible, the colouring does not require the use of a stage of prior or simultaneous bleaching of the keratinous fibres, a bleaching stage, carried out with an oxidizing agent, such as hydrogen peroxide or also persalts. This bleaching stage results in not insignificant damage to the keratinous fibres, which detrimentally affects their cosmetic properties. The hair then has a tendency to become rough, more difficult to disentangle and more brittle.

In point of fact, in the case of colouring based on a composition comprising one or more pigments, visible colourings are obtained, also on dark hair since the surface pigment(s) masks (mask) the colour of the fibres, whether the colour is natural or artificial.

On the other hand, the disadvantage of methods of this type lies in the temporary nature of the colourings obtained.

The use of pigments to dye keratinous fibres is, for example, described in Patent Application FR 2 741 530, which recommends the use, for the temporary colouring of keratinous fibres, of a composition comprising at least one dispersion of particles of film-forming polymer comprising at least one acid functional group and at least one pigment dispersed in the continuous phase of the said dispersion.

The colourings obtained by this form of colouring exhibit, on the other hand, the disadvantage of having a low resistance to shampooing operations.

Furthermore, it is known to produce coloured sheathings of the hair using a composition comprising an electrophilic monomer of cyanoacrylate type and a pigment, in particular in the document EP 1 649 898. Such a composition makes it possible to obtain completely sheathed and non-greasy hair. However, the sheathing obtained is not completely satisfactory in the face of external agents, such as washing and perspiration. Furthermore, the sheathing obtained is sensitive to fatty substances, such as sebum.

It is also possible to colour the hair (coloured sheathing) using a pressure- sensitive adhesive silicone copolymer, in particular a copolymer based on silicone resin and on fluid silicone. Once deposited on the individual hair, these copolymers exhibit the advantage of contributing colour which is persistent. On the other hand, the hair treated is rather rough to the touch.

Other disadvantages are also met with, encountered during the use of dyeing compositions based on pigments, such as, for example, the need to employ several stages and associated accessories, such as a board, a brush, gloves or drying. In addition, the time taken for the application of the composition may be regarded as too great by the consumer or the hairdresser, in particular if the poorer performance, in particular in terms of persistence, than that of the permanent colourings or non- permanent colourings deploying direct dyes is taken into consideration.

Thus, the aim of the present invention is to provide a device which facilitates the application of a dyeing composition based on pigment(s); this composition in addition giving access to a coloured sheathing which is persistent towards shampooing operations and towards the various attacks which keratinous fibres may be subjected to, without damage to the latter; this sheathing being in addition homogeneous and smooth on the keratinous fibres, leaving the latter completely individualized.

This aim is achieved with the present invention, a subject-matter of which is thus a device (1 ) for the application of a composition for dyeing keratinous fibres, comprising:

i) an application means (2) which is capable of retaining an amount of the dyeing composition (P) in a container (20),

ii) a holding member (4) which is capable of interacting with the application means (2) in order, during a longitudinal displacement of the device (1 ) relative to a keratinous fibre or to a combination of keratinous fibres, such as a lock, to keep the fibre or fibres engaged with the application means (2), so as to make possible the coating thereof with the dyeing composition (P), iii) the said application means (2) comprising an applicator end piece (30) mounted on the container (20) and comprising an outlet orifice (31 ) equipped with an opening/closing element (32) which, in a first position, closes off the said outlet orifice and which, in a second position, at least partly releases the said outlet orifice, the change from the first position to the second position taking place in response to a force exerted on the opening/closing element (32) by the engaging of the fibre or fibres between the holding member and this opening/closing element (32), iv) the said dyeing composition (P) comprising at least one aqueous dispersion of particles of hybrid hydrophobic film-forming acrylic polymer, at least one linear block silicone copolymer and at least one pigment.

Another subject-matter of the invention is a method for dyeing keratinous fibres comprising the application, to the fibre or fibres, of a dyeing composition (P) included in a device as described above; the application optionally being followed by a drying of the fibres.

The term "at least one" is understood to mean "one or more".

The term "comprising a" is understood to mean "comprising at least one", unless otherwise specified.

It is possible, by the use of such a device, to deposit in a simple way the dyeing composition included in it, without the risk of the product running, whether in the context of a self-application or of a dyeing carried out by another person. The application is fast and efficient, without requiring the use of additional accessories, and the impregnation of the fibres is homogeneous, whatever their length.

Furthermore, the composition applied makes it possible to obtain a coloured sheathing, visible on fibres of all types in a way persistent towards shampooing operations, while preserving the physical qualities of the keratinous fibre. Such a sheathing is in particular resistant to the external attacks which the fibres may be subjected to, such as blow drying and perspiration. It makes it possible in particular to obtain a smooth and homogeneous deposited layer. Furthermore, it has been found, surprisingly, that the fibres remain completely individualized and can be styled without problems, and that the styling properties contributed to the fibre are persistent towards shampooing operations.

The term "individualized fibres" is understood to mean fibres which, after application of the composition and drying, are not stuck together (or are all separated from one another) and thus do not form clumps, the sheathing being formed around virtually each fibre. Device

The device according to the invention is particularly suited to making possible an application of a dyeing product to one or more fibres.

The application in the hair field can be carried out overall on a complete head of hair by operating successively on at least all the obvious locks of the said head of hair.

It is also possible to operate on only a few locks in order to obtain, once the treatment is complete, a non-homogeneous dyeing effect, thus emphasizing such and such a movement of the head of hair with shades which are lighter or darker in colour than the natural or overall shade of the head of hair.

It is also possible to operate on only isolated fibres, which makes it possible to have a very slight modification to the appearance of the head of hair. Preferably, the holding member can move with respect to the application means.

According to an alternative form, the holding member and the application means are connected by a connecting means and form a single piece.

According to another alternative form, the holding member and the application means form two separate pieces.

Advantageously, the container comprising the composition comprises an annular narrowing to help it to be grasped between two fingers.

In accordance with a specific embodiment, the applicator end piece comprises a surface capable of storing and releasing the dyeing composition.

Preferably, the surface of the holding member can be chosen to be greater than or equal to the surface of the applicator end piece.

Advantageously, the holding member comprises combing means.

Preferably, the change from the first position to the second position takes place in response to a force exerted axially on the opening/closing element.

Preferably, the application means and the holding member can be chosen to be symmetrical with respect to one another in relation to an axis cutting the connecting means.

Reference may be made to the figures, which, however, are presented only by way of indication and without any implied limitation of the device.

In the figures:

Figure 1 : shows an exploded perspective view of a device according to the invention for the application to locks of a hair product,

Figure 2: shows an exploded perspective view of another device according to the invention for the application to locks of a hair product,

Figure 3: shows an exploded perspective view of the top part of the applicator,

Figure 4: shows a top view of the applicator in the released position (second position), Figure 5: shows a top view of the applicator in the closed-off position (first position), Figure 6: shows a perspective view of an opening/closing element in the released position (second position),

Figure 7: shows a perspective view of an opening/closing element in the closed-off position (first position),

Figure 8: shows a front view of the skirt of the applicator,

Figure 9: shows a top view of the skirt of the applicator,

Figure 10: shows a perspective view of a device according to the invention in one piece before use,

Figure 11 : shows a perspective view of a device according to the invention in two pieces before use,

Figure 12: shows a perspective view of a device according to the invention in one piece during use. The device represented in Figures 1 and 2 comprises an application means 2 comprising the composition according to the invention and a holding member 4. The application means 2 is known per se and is described in particular in US 5 961 665.

The application means 2 comprises a container 20 in the form of a small flexible or rigid bottle. Alternatively, a bottle made of thermoplastic material, for example of PET, can be used. The bottle has, for example, a capacity of 6 ml. The bottle comprises a side wall in the form of a cylinder of revolution, one end of which is closed by a base 23. The second end is formed by a portion having a narrowed diameter, which ends in a free edge 24a defining an opening 25.

An applicator end piece 30 is provided to be fitted onto the bottle and to be snap- fastened or screwed onto the opening 25 of the bottle. The end piece is provided in the form of a substantially cylindrical shell having a uniform circular diameter over a large part of its length. It could have any other form, for example a frustoconical form, becoming progressively smaller until it defines a circular portion. The end piece 30 has, for example, a diameter of approximately 15 mm. Axial ribs can be provided on the internal wall of the shell. They can comprise a radial indentation which, in the fitted position of the shell, will become housed in the opening 25 of the bottle, thereby allowing the shell to be snap-fastened onto the bottle. Alternatively, it is possible to provide for the internal wall of the shell to be supplied with a thread intended to interact with a thread provided on the neck of the bottle.

As can be seen in Figures 3 to 9, the end piece comprises a cylindrical skirt 34, which provides sealing between the opening 25 of the bottle and the outlet orifice 31 . The skirt extends substantially axially from the cylindrical or frustoconical portion of the shell, around the seat 33, as far as a free edge 340 which forms a sealing lip. In the fitted position of the applicator end piece 30, the lip 340 will be supported in sealed fashion on the upper edge 24a. Thus, the sealing skirt does not overlap the bottle laterally, so that the presence of the skirt does not affect the lateral space requirement of the shell. A radial shoulder 341 is provided on the internal wall of the skirt 34 for receiving in abutment the opening/closing element 32. This is a continuous circular bead. It is quite clear that a discontinuous bead formed for example of portions which are angularly spaced apart can be used for receiving in abutment the closing element.

The end piece is advantageously obtained by moulding a single piece of a preferably thermoplastic material, in particular of a polyethylene, of a polypropylene, of a polyethylene terephthalate, of a polyvinyl chloride or of a polyamide.

The opening/closing element 32 comprises a spring 321 which is formed by helical turns, the lower part of which is integrally incorporated in a mounting ring 323. The lower edge 323a of the mounting ring 323 is in abutment against the radial shoulder 341 of the skirt 34. The upper part of the spring is integrally incorporated in a body hollow in form which ends with a frustoconical region 320 intended to be supported on the seat 33, thus forming a valve. The frustoconical region is extended by a stud 322 having a circular cross section, the end 322a of which can be slightly rounded in order not to damage the surface to be treated, with which it comes into direct contact. The diameter of the stud is less than the diameter of the dispensing orifice in order that the stud can easily slide through the orifice 31 , allowing product for dispensing to pass through. In the rest position, the stud 322 protrudes out of the orifice, so that its end 322a can be brought into direct contact with a surface to be treated or into indirect contact via a membrane 37.

The opening/closing element 32 is likewise obtained by moulding a single piece of a preferably thermoplastic material, in particular of a polyethylene, of a polypropylene, of a polyethylene terephthalate, of a polyvinyl chloride or of a polyamide.

In the fitted position of the opening/closing element, the lower edge 323a of the mounting ring is in abutment against the radial shoulder and the spring 321 is slightly compressed, in order to keep the frustoconical region 320 supported in sealed fashion on the seat 33, so as to prevent any leakage of product through the orifice 31. When the stud is brought into contact with a surface to be treated, a force is exerted on the stud, the said force being transmitted to the spring so as to compress it. The stud is thus driven into the orifice 31 and the frustoconical portion disengages from the seat 33, as is represented in Figures 3 to 7.

The membrane 37 can be porous or non-porous, be carried on the end piece 30, for example have passed through at least one orifice for dispensing the product, and be externally at least partially covered with a flocked surface, the membrane defining, with the end piece 30, an internal space which can comprise product to be dispensed.

The membrane can be flexible and/or mounted on the end piece 30 so as to exhibit the possibility of deformation and/or movement in relation to the support and/or to the reservoir, leading to a reduction in volume of the internal space of at least 0.1 ml.

As indicated in Figures 10 and 1 1 , in order to use the device, the user takes hold of the bottle, inverts it and applies the end piece to the lock. It then suffices for him to prolong his hand movement in order to drive in the stud 322 and to disengage the frustoconical region 320 from the seat 33 in order at least partly to release the orifice 31 (Figure 3). For this, he places his thumb in contact with the holding member 4. The product exits by gravity through the orifice. Since the orifice has a small diameter, the product flows onto the lock in a very localized manner, which makes it possible to apply the product with great accuracy. Next, he moves the device while gripping the lock. As soon as the user moves the dispenser away from the lock or no longer exerts pressure with his thumb and as soon as the force exerted on the stud ceases, the spring returns to its rest position and the frustoconical portion returns to being supported on the seat. The product then stops flowing and air is drawn into the bottle before the valve is closed. According to a specific embodiment, the holding member 4 comprises a circular cover 41 having a diameter greater than that of the membrane 37. It also comprises a connecting strip 50 made of soft or flexible material chosen so as to elastically lengthen by the distance necessary for the positioning of the lock. This strip 50 can be formed of elastomer, in particular of thermoplastic elastomer, such as a polyethylene elastomer. The strip 50 can be moulded in a single piece with the cover 41 or be connected to the cover 41 by adhesive bonding or welding.

The connecting means 50 can be composed in particular of film hinges or of hinges of the type having an attached pin or of the type having an element carried by either of the said first or second parts, the said element being mounted in rotation inside a recess formed in the other of the said base or the said cover 41 .

The cover 41 can exhibit a shape chosen from the following list: circular or non- circular, in particular oblong, oval, elliptical or polygonal, in particular square, rectangular, kidney-shaped, crenellated or star-shaped, with one or more grooves.

The cover 41 and the membrane 50 can be made of different materials. At least one can be made of a thermoplastic material, in particular one of the materials chosen from the group consisting of: PE, PP, POM, PA, PET and PBT.

The cover 41 can comprise at least one of the following application elements: bundle of bristles, felt, flock coating, foam or else other application elements such as studs or teeth. These application elements are positioned on the surface of the cover 41 , coming into contact with the lock.

These application elements can be positioned in the form of one or more lines or can be distributed in a periodic pattern. The application element can, for example, be a comb or a brush.

The application elements can in particular be attached by adhesive bonding, stapling or overmoulding onto the part 41. The application elements can also comprise a flocked tip.

The holding member 4 can additionally comprise a grasping member which favours the grasping of the device with a predefined orientation. The grasping member can comprise at least one region for receiving a finger, in particular a plane or a cavity, which extends generally substantially parallel to an axis having a greater dimension of a cross section of the flexible part.

According to an alternative which is not represented, the geometric articulation axis is defined by a single film hinge, while the elastic return is ensured by two lateral connecting strips positioned on either side of the film hinge. The choice of such and such a configuration depends to a large extent on the cross section of the container.

When the connecting member 4 does not comprise a connecting means 50, the cover 41 can be welded, moulded or adhesively bonded to a ring or to a fingerstall, into which at least one finger can be inserted. In this case, the ring or the fingerstall is slipped onto the thumb of a hand of the user and the application means 2 is gripped between the other fingers of the same hand. The lock to be coated is positioned next to the membrane 37 of the application means 2. The thumb is bent back in order to pinch the lock between the membrane 37 and the cover 41 . Manual pressure is exerted along the axis of the container 20 and at right angles to the membrane 37. The user moves his hand away from the head while maintaining this pressure. He releases said pressure in order to stop the dyeing of the lock.

The application means 2 can comprise a foam end piece which can be replaced by an end piece of roll-on type (the roll-on can be a sphere or a cylinder or else can have an ovoid shape of the rugby ball type).

With the device according to the invention, the hand (for the hairdresser or a person) can be positioned in the manner most appropriate to the choice of the user, with or without the annular narrowing to favour the grasping of the application means 2.

This device is described in particular in French Patent Application FR 1 155 305, filed on 17.06.201 1 .

Dyeing composition

Aqueous dispersion of particles of hybrid hydrophobic film-forming acrylic polymer The term "polymer" is understood to mean, within the meaning of the invention, a compound corresponding to the repetition of one or more units (these units resulting from compounds known as monomers). This or these unit(s) is (are) repeated at least twice and preferably at least 3 times.

The term "film-forming polymer" is understood to mean a polymer which is capable of forming, by itself alone or in the presence of an additional film-forming agent, a macroscopically continuous film on a support, in particular on keratinous substances, and preferably a cohesive film.

The term "hydrophobic polymer" is understood to mean a polymer having a solubility in water at 25°C of less than 1 % by weight.

The dispersion can be a simple dispersion in the aqueous medium of the composition.

Mention may be made, as specific case of dispersions, of latexes.

The term "hybrid acrylic polymer" is understood to mean, within the meaning of the present invention, a polymer synthesized from at least one compound (i) chosen from monomers having at least one (meth)acrylic acid group and/or from esters of these acid monomers and/or from amides of these acid monomers and from at least one compound (ii) other than the compounds (i), i.e. which does not comprises (meth)acrylic acid group and/or esters of these acid monomers and/or amides of these acid monomers.. The (meth)acrylic acid esters (also known as (meth)acrylates) are advantageously chosen from alkyl (meth)acrylates, in particular C1-C30, preferably d- C₂o and better still C1-C10 alkyl (meth)acrylates, aryl (meth)acrylates, in particular C₆- C10 aryl (meth)acrylates, or hydroxyalkyl (meth)acrylates, in particular C₂-C₆ hydroxyalkyl (meth)acrylates.

Mention may be made, among alkyl (meth)acrylates, of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate or cyclohexyl methacrylate.

Mention may be made, among hydroxyalkyl (meth)acrylates, of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate.

Mention may be made, among aryl (meth)acrylates, of benzyl acrylate and phenyl acrylate.

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

According to the present invention, the alkyl group of the esters can be either fluorinated or perfluorinated, that is to say that some or all of the hydrogen atoms of the alkyl group are replaced with fluorine atoms.

Mention may be made, as amides of the acid monomers, for example, of (meth)acrylamides and in particular N-alkyl(meth)acrylamides, especially N-(C₂-Ci₂ alkyl)(meth)acrylamides. Mention may be made, among N-alkyl(meth)acrylamides, of N-ethylacrylamide, N-(t-butyl)acrylamide, N-(t-octyl)acrylamide and N- undecylacrylamide.

Mention will be made, as compounds (ii) other than the compounds (i), for example, of the styrene monomers.

In particular, the acrylic polymer can be a styrene/acrylate copolymer and especially a polymer chosen from the copolymers resulting from the polymerization of at least one styrene monomer and at least one C1-C20 and preferably C1-C10 alkyl acrylate monomer.

Mention may be made, as styrene monomer which can be used in the invention, of styrene or omethylstyrene and preferably styrene.

The C1-C10 alkyl acrylate monomer can be chosen from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate or 2-ethylhexyl acrylate.

Mention may be made, as acrylic polymer synthesized with styrene compound, of the styrene/acrylate(s) copolymers sold under the name Joncryl 77 by BASF, under the name Yodosol GH41 F by Akzo Nobel and under the name Syntran 5760 CG by Interpolymer. Mention may also be made, as compound (ii), of the compounds which interact by a process other than the radical polymerization of unsaturated compounds or the compounds resulting from such a process. Such a process can, for example, be a polycondensation. Mention may be made, as polycondensation, of the formation of polyurethanes, polyesters or polyamides. In addition to the acrylic monomer or monomers, the hybrid hydrophobic film-forming polymer of the invention will then comprise the compound resulting from the polycondensation process or the compounds which interact in the polycondensation process.

Mention may in particular be made, as hybrid hydrophobic film-forming acrylic copolymers of this type, of that sold under the reference Hybridur 875 Polymer Dispersion by Air Products and Chemicals.

Use may also be made, as hybrid hydrophobic film-forming acrylic copolymer, of the product sold under the reference Primal HG 1000 by Dow.

The hybrid hydrophobic film-forming acrylic polymer or polymers in aqueous dispersion can be present in a content, as polymeric active materials, ranging from 0.1 % to 30% by weight, more particularly from 0.5% to 20% by weight and preferably from 1 % to 15% by weight, with respect to the total weight of the composition.

Linear block silicone copolymer

The silicone copolymer used in the composition according to the invention is a linear block copolymer, that is to say a non-crosslinked copolymer, obtained by chain extension and not by crosslinking.

The term "block copolymer" (or "sequential copolymer") denotes a polymer comprising at least two distinct blocks (sequences). Each block of the polymer results from one type of monomer or from several types of different monomers. This means that each block can be composed of a homopolymer or of a copolymer, it being possible for this copolymer constituting the block to be in its turn random or alternating.

The silicone copolymer used in the composition according to the invention preferably comprises at least two distinct silicone blocks, each block of the polymer resulting from one type of silicone monomer or from several types of different silicone monomers, such as mentioned below.

It should also be noted that the copolymer is "linear"; in other words, the structure of the polymer is neither branched nor star-shaped nor grafted.

The linear block silicone copolymer is advantageously provided in the form of particles in dispersion in an aqueous medium.

The aqueous dispersion of block copolymer particles is a silicone-in-water (Sil/W) emulsion, the oily globules of which are composed of a silicone of high viscosity, so that these globules appear to form as "soft particles". The size of the linear block silicone copolymer particles can vary widely. Preferably, in the present patent application, the linear block silicone copolymer particles generally exhibit a number-average size of less than or equal to 2 microns and preferably of less than or equal to 1 micron.

The aqueous dispersions of linear block silicone copolymer particles used composition according to the invention can be chosen in particular from those described in the document EP-A-874 017, the teaching of which is incorporated here by reference. According to this document, it is possible in particular to obtain the silicone copolymers constituting these particles by a chain extension reaction, in the presence of a catalyst, starting from at least:

- (a) one polysiloxane (i) having at least one reactive group and preferably one or two reactive groups per molecule; and

- (b) one organosilicone compound (ii) which reacts with the polysiloxane (i) by a chain extension reaction.

In particular, the polysiloxane (i) is chosen from the compounds of formula (I):

in which R-i and R₂ represent, independently of one another, a hydrocarbon group having from 1 to 20 carbon atoms and preferably from 1 to 10 carbon atoms, such as methyl, ethyl, propyl or butyl, or an aryl group, such as phenyl, or a reactive group, and n is an integer greater than 1 , provided that there are on average between one and two reactive groups per polymer.

The term "reactive group" is understood to mean any group capable of reacting with the organosilicone compound (ii) to form a block copolymer. Mention may be made, as reactive groups, of hydrogen; aliphatically unsaturated groups, in particular vinyl, allyl or hexenyl groups; the hydroxyl group; alkoxy groups, such as methoxy, ethoxy or propoxy groups; alkoxyalkoxy groups; the acetoxy group; amino groups, and their mixtures. Preferably, more than 90% and better still more than 98% of reactive groups are at the chain end, that is to say that the R₂ radicals generally constitute more than 90% and even 98% of the reactive groups.

n can in particular be an integer ranging from 5 to 30, preferably from 10 to 30 and better still from 15 to 25.

The polysiloxanes of formula (I) are linear polymers, that is to say comprising few branchings and generally less than 2 mol% of siloxane units. Furthermore, the Ri and R₂ groups can optionally be substituted by amino groups, epoxy groups or sulfur- comprising, silicon-comprising or oxygen-comprising groups.

Preferably, at least 80% of the Ri groups are alkyl groups and better still methyl groups. Preferably, the reactive group R₂ at the chain end is an aliphatically unsaturated group and in particular a vinyl group.

Mention may in particular be made, as polysiloxanes (i), of dimethylvinylsiloxy- polydimethylsiloxane, a compound of formula (I) in which the Ri radicals are methyl radicals and the R₂ radicals at the chain end are vinyl radicals while the other two R₂ radicals are methyl radicals.

The organosilicone compound (ii) can be chosen from polysiloxanes of formula (I) or compounds acting as chain-extending agent. If it is a compound of formula (I), the polysiloxane (i) will comprise a first reactive group and the organosilicone compound (ii) will comprise a second reactive group which will react with the first. If it is a chain-extending agent, it can be a silane, a siloxane (disiloxane or trisiloxane) or a silazane. Preferably, the organosilicone compound (ii) is a liquid organohydropolysiloxane of formula (II):

where n is an integer greater than 1 and preferably greater than 10, for example ranging from 2 to 100, preferably from 10 to 30 and better still from 15 to 25. According to a specific embodiment of the invention, n is equal to 20.

The silicone block copolymers used according to the invention are advantageously devoid of oxyalkylene group(s), in particular devoid of oxyethylene and/or oxypropylene group(s).

The catalyst of the reaction between the polysiloxane and the organosilicone compound can be chosen from metals and in particular from platinum, rhodium, tin, titanium, copper and lead. It is preferably platinum or rhodium.

The dispersion of silicone copolymer particles used in the composition according to the invention can in particular be obtained, for example, by mixing (a) water, (b) at least one emulsifier, (c) the polysiloxane (i), (d) the organosilicone compound (ii) and (e) a catalyst. Preferably, one of the constituents (c), (d) or (e) is added last to the mixture, in order for the chain extension reaction to begin only in the dispersion.

Mention may be made, as emulsifiers capable of being used in the preparation process described above in order to obtain the aqueous dispersion of particles, of non- ionic or ionic (anionic, cationic or amphoteric) emulsifiers. They are preferably non- ionic emulsifiers which can be chosen from polyalkylene glycol ethers of fatty alcohols comprising from 8 to 30 carbon atoms and preferably from 10 to 22 carbon atoms; polyoxyalkylenated and in particular polyoxyethylenated sorbitan alkyl esters, where the alkyl radical comprises from 8 to 30 carbon atoms and preferably from 10 to 22 carbon atoms; polyoxyalkylenated and in particular polyoxyethylenated alkyl esters, where the alkyl radical comprises from 8 to 30 carbon atoms and preferably from 10 to 22 carbon atoms; polyethylene glycols; polypropylene glycols; diethylene glycols; and their mixtures. The amount of emulsifier(s) is generally from 1 to 30% by weight, with respect to the total weight of the reaction mixture.

The emulsifier used to obtain the aqueous dispersion of particles is preferably chosen from polyethylene glycol ethers of fatty alcohols and their mixtures and in particular polyethylene glycol ethers of alcohols comprising 12 or 13 carbon atoms and from 2 to 100 oxyethylene units and preferably from 3 to 50 oxyethylene units, and their mixtures. Mention may be made, for example, of C12-C13 Pareth-3, C12-C13 Pareth-23 and their mixtures.

According to a specific embodiment of the invention, the dispersion of silicone copolymer particles is obtained from dimethylvinylsiloxy-polydimethylsiloxane (or divinyldimethicone), as compound (i), and from the compound of formula (II) with preferably n=20, as compound (ii), preferably in the presence of a catalyst of platinum type, and the dispersion of particles is preferably obtained in the presence of C12-C13 Pareth-3 and C12-C13 Pareth-23, as emulsifiers.

Use may in particular be made, as dispersion of silicone copolymer particles, of the product sold under the name HMW 2220 by Dow Corning (CTFA name: divinyldimethicone/dimethicone copolymer/Ci₂-Ci₃ Pareth-3/Ci₂-Ci₃ Pareth-23), which is a 60% aqueous dispersion of divinyldimethicone/dimethicone copolymer comprising Ci₂-Ci₃ Pareth-3 and Ci₂-Ci₃ Pareth-23, the said dispersion comprising approximately 60% by weight of copolymer, 2.8% by weight of Ci₂-Ci₃ Pareth-23, 2% by weight of Ci₂-Ci₃ Pareth-3 and 0.31 % by weight of preservatives, the remainder to 100% being water.

The linear block silicone copolymer or copolymers can be present, for example, in an amount, as polymeric active materials, ranging from 0.1 % to 30% by weight, better still from 0.5% to 20% by weight and even better still from 1 % to 15% by weight, with respect to the total weight of the composition.

According to one embodiment, the hybrid hydrophobic film-forming acrylic polymer or polymers and the linear block silicone copolymer or copolymers are present in a hybrid hydrophobic film-forming acrylic polymer(s) to linear block silicone copolymer(s) ratio by weight (as polymeric active materials) ranging from 0.2 to 10, better still from 0.5 to 5 and even better still from 1 to 3.

When the hybrid hydrophobic film-forming acrylic polymer has a glass transition temperature which is too high for the desired use, a plasticizer can be combined therewith so as to lower this temperature of the mixture used. The plasticizer can be chosen from the plasticizers normally used in the field of application and in particular from compounds which can be solvents for the polymer.

Preferably, the plasticizer has a molecular weight of less than or equal to 5000 g/mol, preferably of less than or equal to 2000 g/mol, preferably of less than or equal to 1000 g/mol and more preferably of less than or equal to 900 g/mol. The plasticizer advantageously has a molecular weight of greater than or equal to 100 g/mol.

Thus, the composition can additionally comprise at least one plasticizing agent. In particular, mention may be made, alone or as a mixture, of the usual plasticizers, such as:

- glycols and their derivatives, such as diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether or diethylene glycol hexyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether or ethylene glycol hexyl ether,

- polyethylene glycols, polypropylene glycols, polyethylene glycol/polypropylene glycol copolymers and their mixtures, in particular polypropylene glycols of high molecular weight, for example having a molecular weight ranging from 500 to 15 000, such as, for example,

- glycol esters,

- propylene glycol derivatives and in particular propylene glycol phenyl ether, propylene glycol diacetate, dipropylene glycol ethyl ether, tripropylene glycol methyl ether, diethylene glycol methyl ether or dipropylene glycol butyl ether. Such compounds are sold by Dow Chemical under the names Dowanol PPH and Dowanol DPnB.

- acid esters, in particular carboxylic acid esters, such as citrates, phthalates, adipates, carbonates, tartrates, phosphates or sebacates,

- esters resulting from the reaction of a monocarboxylic acid of formula R11COOH with a diol of formula HOR12OH with R-n and R12, which are identical or different, representing a saturated or unsaturated and linear, branched or cyclic hydrocarbon chain preferably comprising from 3 to 15 carbon atoms and optionally comprising one or more heteroatoms, such as N, O or S, in particular the monoester resulting from the reaction of isobutyric acid and octanediol, such as 2,2,4-trimethyl- 1 ,3-pentanediol, such as that sold under the reference Texanol Ester Alcohol by Eastman Chemical,

- oxyethylenated derivatives, such as oxyethylenated oils, in particular vegetable oils, such as castor oil,

- their mixtures.

More particularly, the plasticizer can be chosen from esters of at least one carboxylic acid comprising from 1 to 7 carbon atoms and of a polyol comprising at least 4 hydroxyl groups.

The polyol can be a cyclized or non-cyclized monosaccharide - polyhydroxyaldehyde (aldose) or polyhydroxyketone (ketose). The polyol is preferably a cyclized monosaccharide in the hemiacetal form.

The polyol can be a mono- or polysaccharide comprising from 1 to 10 monosaccharide units, preferably from 1 to 4 monosaccharide units and more preferably one or two monosaccharide units. The polyol can be chosen from erythritol, xylitol, sorbitol, glucose, sucrose, lactose or maltose.

The polyol is preferably a disaccharide. Mention may be made, among disaccharides, of sucrose (also known as a-D-glucopyranosyl-(1 -2)^-D- fructofuranose), lactose (also known as β-D-galactopyranosyl-(1 -4)-β-D- glucopyranose) and maltose (also known as a-D-glucopyranosyl-(1 -4)^-D- glucopyranose), and preferably of sucrose.

The ester can be composed of a polyol esterified by at least two different monocarboxylic acids or by at least three different monocarboxylic acids.

The ester can be a copolymer of two esters, in particular a copolymer i) of a sucrose substituted by benzoyl groups and ii) of a sucrose substituted by acetyl and/or isobutyryl groups.

The carboxylic acid is preferably a monocarboxylic acid comprising from 1 to 7 carbon atoms and preferably from 1 to 5 carbon atoms, for example chosen from acetic acid, n-propanoic acid, isopropanoic acid, n-butanoic acid, isobutanoic acid, tert- butanoic acid, n-pentanoic acid and benzoic acid.

The ester can be obtained from at least two different monocarboxylic acids. According to one embodiment, the acid is a linear or branched acid which is unsubstituted.

The acid is preferably chosen from acetic acid, isobutyric acid, benzoic acid and their mixtures.

According to a preferred embodiment, the ester is sucrose diacetate hexa(2- methylpropanoate), such as that sold under the name Sustane SAIB Food Grade Kosher by Eastman Chemical.

According to another embodiment, the plasticizer can be chosen from esters of an aliphatic or aromatic polycarboxylic acid and of an aliphatic or aromatic alcohol comprising from 1 to 10 carbon atoms.

The aliphatic or aromatic alcohol comprises from 1 to 10 carbon atoms, preferably from 1 to 8 carbon atoms, for example from 1 to 6 carbon atoms. It can be chosen from F OH alcohols, such that F represents methyl, ethyl, propyl, isopropyl, butyl, hexyl, ethylhexyl, decyl, isodecyl, benzyl or benzyl substituted by an alkyl comprising from 1 to 3 carbon atoms, and their mixtures.

The aliphatic or aromatic polycarboxylic acid preferably comprises from 3 to 12 carbon atoms, preferably from 3 to 10 carbon atoms, preferably from 3 to 8 carbon atoms, for example 6 or 8 carbon atoms.

The aliphatic or aromatic polycarboxylic acid is advantageously chosen from dicarboxylic acids and tricarboxylic acids.

Mention may be made, among aliphatic dicarboxylic acids, of those of formula HOOC-(CH₂)_n-COOH, in which n is an integer ranging from 1 to 10, preferably ranging from 2 to 8, for example equal to 2, 4, 6 or 8. Preference is given to dicarboxylic acids chosen from succinic acid, adipic acid and sebacic acid.

Mention may be made, among aromatic dicarboxylic acids, of phthalic acid.

Mention may be made, among tricarboxylic acids, of triacids which correspond to the formula

in which R represents an -H, -OH or -OCOR' group in which R' represents an alkyl group having from 1 to 6 carbon atoms. Preferably, R represents an -OCOCH₃ group.

The tricarboxylic acid is chosen in particular from acetylcitric acid, butyroylcitric acid or citric acid.

Use may be made, among tricarboxylic acid esters, of esters derived from citric acid (or citrates), such as tributyl acetylcitrate, triethyl acetylcitrate, triethylhexyl acetylcitrate, trihexyl acetylcitrate, trihexyl butyroylcitrate, triisodecyl citrate, triisopropyl citrate, tributyl citrate and tri(2-ethylhexyl) citrate. Mention may be made, as commercial references for plasticizers mentioned above, of the Citroflex range sold by Vertellus, with in particular Citroflex A4 and Citroflex C2.

Mention may be made, among adipic acid esters, of dibutyl adipate and di(2- ethylhexyl) adipate.

Mention may be made, among sebacic acid esters, of dibutyl sebacate, di(2- ethylhexyl) sebacate, diethyl sebacate and diisopropyl sebacate.

Mention may be made, among succinic acid esters, of di(2-ethylhexyl) succinate and diethyl succinate.

Mention may be made, among phthalic acid esters, of benzyl butyl phthalate, dibutyl phthalate, diethylhexyl phthalate, diethyl phthalate and dimethyl phthalate.

Advantageously, the plasticizer or plasticizers can be present in the composition in a content such that the ratio by weight of the hybrid hydrophobic film-forming acrylic polymer or polymers to the plasticizer or plasticizers varies from 0.5 to 100, preferably from 1 to 50 and preferably from 1 to 10.

Pigments

The composition comprises pigments.

Such a composition makes it possible to obtain persistent and coloured sheathings, without damaging the keratinous fibres.

The term "pigment" is understood to mean white or coloured particles of any shape which are insoluble in the composition in which they are present. The pigments which can be used are chosen in particular from organic and/or inorganic pigments known in the art, in particular those which are described in Kirk- Othmer's Encyclopedia of Chemical Technology and in Ullmann's Encyclopedia of Industrial Chemistry.

They can be natural, of natural origin, or not.

These pigments can be provided in the pigment powder or paste form. They can be coated or uncoated.

The pigments can be chosen, for example, from inorganic pigments, organic pigments, lakes, special effect pigments, such as pearlescent agents or glitter, and their mixtures.

The pigment can be an inorganic pigment. The term "inorganic pigment" is understood to mean any pigment which corresponds to the definition of Ullmann's Encyclopedia in the "Inorganic Pigment" chapter. Mention may be made, among inorganic pigments of use in the present invention, of ocres, such as red ocre (clay (in particular kaolinite) and iron hydroxide (for example haematite)), brown ocre (clay (in particular kaolinite) and limonite) or yellow ocre (clay (in particular kaolinite) and goethite); titanium dioxide, optionally surface-treated; zirconium or cerium oxides; zinc, (black, yellow or red) iron or chromium oxides; manganese violet, ultramarine blue, chromium hydrate and ferric blue; or metal powders, such as aluminium powder or copper powder.

Mention may also be made of alkaline earth metal carbonates (such as calcium carbonate or magnesium carbonate), silicon dioxide, quartz and any other compound used as inert filler in cosmetic compositions, provided that these compounds contribute colour or whiteness to the composition under the conditions under which they are employed.

The pigment can be an organic pigment. The term "organic pigment" is understood to mean any pigment which corresponds to the definition of Ullmann's Encyclopedia in the "Organic Pigment" chapter.

The organic pigment can in particular be chosen from nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, fluoran or phthalocyanine compounds, compounds of metal complex type, or isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane or quinophthalone compounds.

Use may also be made of any inorganic or organic compound which is insoluble in the composition and is conventional in the field of cosmetics, provided that these compounds contribute colour or whiteness to the composition under the conditions under which they are employed, for example guanine, which, according to the refractive index of the composition, is a pigment.

In particular, the white or coloured organic pigments can be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, 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 1 1680, 1 1710, 15985, 19140, 20040, 21 100, 21 108, 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 1 1725, 15510, 45370 and 71 105, 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, or the pigments obtained by oxidative polymerization of indole or phenol derivatives, as are described in Patent FR 2 679 771.

Mention may also be made, by way of example, of pigment pastes formed of organic pigment, such as the products sold by Hoechst under the names:

- Cosmenyl Yellow 10G: Pigment Yellow 3 (CI 1 1710);

- Cosmenyl Yellow G: Pigment Yellow 1 (CI 1 1680);

- Cosmenyl Orange GR: Pigment Orange 43 (CI 71 105);

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

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

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

- Cosmenyl Blue A2R: Pigment Blue 15.1 (CI 74160);

- Cosmenyl Green GG: Pigment Green 7 (CI 74260);

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

The pigments in accordance with the invention can also be in the form of composite pigments, as are described in Patent EP 1 184 426. These composite pigments can be composed in particular of particles comprising an inorganic core, at least one binder, which provides for the attachment of the organic pigments to the core, and at least one organic pigment which at least partially covers the core.

The organic pigment can also be a lake. The term "lake" is understood to mean dyes adsorbed onto insoluble particles, the combination thus obtained remaining insoluble during use.

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

Mention may be made, among the dyes, of carminic acid. Mention may also be made of the dyes 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 10 (CI 47 005), D&C Green 3 (CI 42 053) or D&C Blue 1 (CI 42 090).

Mention may be made, by way of examples of lakes, of the product known under the following name: D&C Red 7 (CI 15 850:1 ). The pigment can also be a special effect pigment. The term "special effect pigments" is understood to mean pigments which generally create a coloured appearance (characterized by a certain shade, a certain vividness and a certain lightness) which is not uniform and which changes as a function of the conditions of observation (light, temperature, angles of observation, and the like). They thereby contrast with coloured pigments, which provide a conventional opaque, semi- transparent or transparent uniform colour.

There exist several types of special effect pigments: those with a low refractive index, such as fluorescent, photochromic or thermochromic pigments, and those with a greater refractive index, such as pearlescent agents, interferential pigments or glitter.

Mention may be made, as examples of special effect pigments, of pearlescent pigments, such as mica covered with titanium dioxide or with bismuth oxychloride, coloured pearlescent pigments, such as mica covered with titanium dioxide and with iron oxides, mica covered with iron oxide, mica covered with titanium dioxide and in particular with ferric blue or chromium oxide or mica covered with titanium dioxide and with an organic pigment as defined above, and pearlescent pigments based on bismuth oxychloride. Mention may be made, as pearlescent pigments, of the following pearlescent agents: Cellini sold by Engelhard (mica-Ti0₂-lake), Prestige sold by Eckart (mica-Ti0₂), Prestige Bronze sold by Eckart (mica-Fe₂0₃) or Colorona sold by Merck

Mention may also be made of pearlescent agents of gold colour sold in particular by Engelhard under the names of Brilliant Gold 212G (Timica), Gold 222C (Cloisonne), Sparkle Gold (Timica), Gold 4504 (Chromalite) and Monarch Gold 233X (Cloisonne); bronze pearlescent agents sold in particular by Merck under the names Bronze Fine (17384) (Colorona) and Bronze (17353) (Colorona) and by Engelhard under the name

Super Bronze (Cloisonne); orange pearlescent agents sold in particular by Engelhard under the names Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by Merck under the names Passion Orange (Colorona) and Matte Orange (17449) (Microna); brown-coloured pearlescent agents sold in particular by Engelhard under the names Nu-Antique Copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); pearlescent agents with a copper glint sold in particular by Engelhard under the name Copper 340A (Timica); pearlescent agents with a red glint sold in particular by Merck under the name Sienna Fine (17386) (Colorona); pearlescent agents with a yellow glint sold in particular by Engelhard under the name Yellow (4502) (Chromalite); red- coloured pearlescent agents with a gold glint sold in particular by Engelhard under the name Sunstone G012 (Gemtone); pink pearlescent agents sold in particular by Engelhard under the name Tan Opale G005 (Gemtone); black pearlescent agents with a gold glint sold in particular by Engelhard under the name Nu-Antique Bronze 240 AB (Timica); blue pearlescent agents sold in particular by Merck under the name Matte Blue (17433) (Microna); white pearlescent agents with a silvery glint sold in particular by Merck under the name Xirona Silver; golden green pinkish orangey pearlescent agents sold in particular by Merck under the name Indian Summer (Xirona); and their mixtures.

Mention may also be made, still as examples of pearlescent agents, of particles comprising a borosilicate substrate coated with titanium oxide.

Particles having a glass substrate coated with titanium oxide are sold in particular under the name Metashine MC1080RY by Toyal.

Finally, mention may also be made, as examples of pearlescent agents, of polyethylene terephthalate glitter, in particular that sold by Meadowbrook Inventions under the name Silver 1 P 0.004X0.004 (silver glitter).

It is also possible to envisage multilayer pigments based on synthetic substrates, such as alumina, silica, calcium sodium borosilicate, calcium aluminium borosilicate and aluminium.

The special effect pigments can also be chosen from reflective particles, that is to say in particular particles having a size, a structure, in particular a thickness of the layer or layers of which it is composed and their physical and chemical nature, and a surface condition which allow them to reflect incident light. This reflection may, if appropriate, have an intensity sufficient to create, at the surface of the composition or mixture, when the latter is applied to the substrate to be made up, highlight points visible to the naked eye, that is to say more luminous points which contrast with their surroundings by appearing to sparkle.

The reflective particles can be selected so as not to detrimentally affect, to a significant extent, the colouring effect generated by the colouring agents which are combined with them and more particularly so as to optimize this effect in terms of colour rendition. They can more particularly have a yellow, pink, red, bronze, orangey, brown, gold and/or coppery colour or glint.

These particles can exhibit varied forms and can in particular be in the platelet or globular form, especially the spherical form.

The reflective particles, whatever their form, may or may not exhibit a multilayer structure and, in the case of a multilayer structure, may exhibit, for example, at least one layer of uniform thickness, in particular of a reflective material.

When the reflective particles do not exhibit a multilayer structure, they can be composed, for example, of metal oxides, in particular of titanium or iron oxides obtained synthetically.

When the reflective particles exhibit a multilayer structure, they can, for example, comprise a natural or synthetic substrate, in particular a synthetic substrate, at least partially coated with at least one layer of a reflective material, in particular of at least one metal or metal material. The substrate can be made of one or more organic and/or inorganic materials. More particularly, it can be chosen from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, in particular aluminosilicates and borosilicates, synthetic mica and their mixtures, this list not being limiting.

The reflective material can comprise a layer of metal or of a metal material.

Reflective particles are described in particular in the documents

JP-A-09188830, JP-A-10158450, JP-A-10158541 , JP-A-07258460 and JP-A- 05017710.

Mention may also be made, still by way of example of reflective particles comprising an inorganic substrate coated with a layer of metal, of the particles comprising a borosilicate substrate coated with silver.

Particles comprising a glass substrate coated with silver, in the form of platelets, are sold under the name Microglass Metashine REFSX 2025 PS by Toyal. Particles comprising a glass substrate coated with nickel/chromium/molybdenum alloy are sold under the names Crystal Star GF 550 and GF 2525 by this same company.

Use may also be made of particles comprising a metal substrate, such as silver, aluminium, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze or titanium, the said substrate being coated with at least one layer of at least one metal oxide, such as titanium oxide, aluminium oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and their mixtures.

Mention may be made, as examples, of aluminium powder, bronze powder or copper powder coated with Si0₂ sold under the name Visionaire by Eckart.

Mention may also be made of pigments with an interference effect which are not attached to a substrate, such as liquid crystals (Helicones HC from Wacker), interference holographic glitter (Geometric Pigments or Spectra f/x from Spectratek). Special effect pigments also comprise fluorescent pigments, whether substances which are fluorescent in daylight or which produce ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, for example sold by Quantum Dots Corporation.

Quantum dots are luminescent semiconductor nanoparticles capable of emitting, under light excitation, radiation exhibiting a wavelength of between 400 nm and 700 nm. These nanoparticles are known from the literature. In particular, they can be synthesized according to the processes described, for example, in US 6 225 198 or US 5 990 479, in the publications which are cited therein and 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. 1 19, No. 30, pp. 7019-7029. The variety of the pigments which can be used in the present invention makes it possible to obtain a rich palette of colours as well as specific optical effects, such as interference, metallic effects.

The size of the pigment used in the cosmetic composition according to the present invention is generally between 10 nm and 200 μηη, preferably between 20 nm and 80 μηη and more preferably between 30 nm and 50 μηη.

The pigments can be dispersed in the product by virtue of a dispersing agent.

The dispersing agent serves to protect the dispersed particles from the agglomeration or flocculation thereof. This dispersing agent can be a surfactant, an oligomer, a polymer or a mixture of several of them carrying one or more functionalities having a strong affinity for the surface of the particles to be dispersed. In particular, they can become attached physically or chemically to the surface of the pigments. These dispersants additionally exhibit at least one functional group compatible with or soluble in the continuous medium. Use is made in particular of esters of 12- hydroxystearic acid and of C₈ to C₂₀ fatty acid and of polyol, such as glycerol or diglycerol, such as the stearate of poly(12-hydroxystearic acid) with a molecular weight of approximately 750 g/mol, such as that sold under the name of Solsperse 21 000 by Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name), sold under the reference Dehymyls PGPH by Henkel, or polyhydroxystearic acid, such as that sold under the reference Arlacel P100 by Uniqema, and their mixtures.

Mention may be made, as other dispersant which can be used in the compositions of the invention, of the quaternary ammonium derivatives of polycondensed fatty acids, such as Solsperse 17 000, sold by Avecia, or polydimethylsiloxane/oxypropylene mixtures, such as those sold by Dow Corning under the references DC2-5185 and DC2-5225 C.

The pigments used in the cosmetic composition according to the invention can be surface-treated with an organic agent.

Thus, the pigments surface-treated beforehand of use in the context of the invention are pigments which have been completely or partially subjected to a surface treatment of chemical, electronic, electrochemical, mechanochemical or mechanical nature with an organic agent, such as those which are described in particular in Cosmetics and Toiletries, February 1990, vol. 105, pp. 53-64, before being dispersed in the composition in accordance with the invention. These organic agents can, for example, be chosen from waxes, for example carnauba wax and beeswax; fatty acids, fatty alcohols and their derivatives, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol, lauric acid and their derivatives; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminium salts of fatty acids, for example aluminium stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic polymers, for example polymethyl methacrylates; polymers and copolymers comprising acrylate units; alkanolamines; silicone compounds, for example silicones or polydimethylsiloxanes; fluorinated organic compounds, for example perfluoroalkyl ethers; or fluorosilicone compounds.

The surface-treated pigments of use in the cosmetic composition according to the invention may also have been treated with a mixture of these compounds and/or have undergone several surface treatments.

The surface-treated pigments of use in the context of the present invention can be prepared according to surface treatment techniques well known to a person skilled in the art or found as such commercially.

Preferably, the surface-treated pigments are covered with an organic layer.

The organic agent with which the pigments are treated can be deposited on the pigments by evaporation of solvent, chemical reaction between the molecules of the surface agent or creation of a covalent bond between the surface agent and the pigments.

The surface treatment can thus be carried out, for example, by chemical reaction of a surface agent with the surface of the pigments and creation of a covalent bond between the surface agent and the pigments or fillers. This method is described in particular in Patent US 4 578 266.

Preferably, use will be made of an organic agent covalently bonded to the pigments.

The agent for the surface treatment can represent from 0.1 % to 50% by weight, preferably from 0.5% to 30% by weight and more preferentially still from 1 % to 10% by weight of the total weight of the surface-treated pigments.

Preferably, the surface treatments of the pigments are chosen from the following treatments:

- a PEG-silicone treatment, such as the AQ surface treatment sold by LCW;

- a methicone treatment, such as the SI surface treatment sold by LCW;

- a dimethicone treatment, such as the Covasil 3.05 surface treatment sold by

LCW;

- a dimethicone/trimethylsiloxysilicate treatment, such as the Covasil 4.05 surface treatment sold by LCW;

- a magnesium myristate treatment, such as the MM surface treatment sold by

LCW;

- an aluminium dimyristate treatment, such as the Ml surface treatment sold by Miyoshi;

- a perfluoropolymethylisopropyl ether treatment, such as the FHC surface treatment sold by LCW;

- an isostearyl sebacate treatment, such as the HS surface treatment sold by Miyoshi;

- a perfluoroalkyl phosphate treatment, such as the PF surface treatment sold by Daito; - an acrylate/dimethicone copolymer and perfluoroalkyl phosphate treatment, such as the FSA surface treatment sold by Daito;

- a polymethylhydrosiloxane/perfluoroalkyl phosphate treatment, such as the FS01 surface treatment sold by Daito;

- an acrylate/dimethicone copolymer treatment, such as the ASC surface treatment sold by Daito;

- an isopropyl titanium triisostearate treatment, such as the ITT surface treatment sold by Daito;

- an acrylate copolymer treatment, such as the APD surface treatment sold by Daito;

- a perfluoroalkyl phosphate/isopropyl titanium triisostearate treatment, such as the PF + ITT surface treatment sold by Daito.

Preferably, the pigment is chosen from inorganic pigments or inorganic/organic mixed pigments.

The amount of pigment(s) can vary from 0.01 % to 30% by weight, more particularly from 0.05% to 20% by weight and preferably from 0.1 % to 15% by weight, with respect to the total weight of the composition. The composition of the invention can comprise other coloured or colouring entities, such as direct dyes or dye precursors.

Thickening agent

According to a preferred embodiment, the composition according to the invention comprises at least one thickening agent chosen from polymeric or non-polymeric and inorganic or organic thickening agents and their mixtures.

The term "thickener" is understood to mean a compound which modifies the rheology of the medium in which it is incorporated.

According to a specific embodiment of the invention, the composition comprises at least one inorganic thickener.

Preferably, the thickener or thickeners is/are chosen from fumed silica, clays or their mixtures.

The fumed silicas can be obtained by high-temperature pyrolysis of a volatile silicon compound in an oxhydrogen flame, producing a finely divided silica. This process makes it possible in particular to obtain hydrophilic silicas which exhibit a large number of silanol groups at their surface. Such hydrophilic silicas are sold, for example, under the names Aerosil 130®, Aerosil 200®, Aerosil 255®, Aerosil 300® and Aerosil 380® by Degussa and Cab-O-Sil HS-5®, Cab-O-Sil EH-5®, Cab-O-Sil LM-130®, Cab-O-Sil MS-55® and Cab-O-Sil M-5® by Cabot. It is possible to chemically modify the surface of the said silica via a chemical reaction which brings about a reduction in the number of silanol groups. It is possible in particular to replace silanol groups with hydrophobic groups: a hydrophobic silica is then obtained.

The hydrophobic groups can be:

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

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

The fumed silica preferably exhibits a particle size which can be nanometric to micrometric, for example ranging from approximately 5 to 200 nm.

Clays are well known products which are described, for example, in the publication "Mineralogie des argiles" [Mineralogy of Clays], S. Caillere, S. Henin and M. Rautureau, 2nd Edition, 1982, Masson.

Clays are silicates including a cation which can be chosen from calcium, magnesium, aluminium, sodium, potassium or lithium cations, and their mixtures.

Mention may be made, as examples of such products, of clays of the family of the smectites, such as montmorillonites, hectorites, bentonites, beidellites or saponites, and also of the family of the vermiculites, stevensite or chlorites.

These clays can be of natural or synthetic origin. Use is preferably made of clays which are cosmetically compatible and acceptable with keratinous substances.

Mention may be made, as clay which can be used according to the invention, of synthetic hectorites (also known as laponites), such as the products sold by Laporte under the name Laponite XLG, Laponite RD and Laponite RDS (these products are sodium magnesium silicates and in particular lithium magnesium sodium silicates); bentonites, such as the product sold under the name Bentone HC by Rheox; magnesium aluminium silicates, in particular hydrated, such as the product sold by R.T. Vanderbilt Company under the name Veegum Ultra, or calcium silicates and in particular that in synthetic form sold by the company CELITE ET WALSH ASS under the name Micro-Cel C. The organophilic clay can be chosen from montmorillonite, bentonite, hectorite, attapulgite or sepiolite, and their mixtures. The clay is preferably a bentonite or a hectorite.

These clays can be modified with a chemical compound chosen from quaternary amines, tertiary amines, amine acetates, imidazolines, amine soaps, fatty sulfates, alkylarylsulfonates, amine oxides and their mixtures.

Mention may be made, as organophilic clays, of quaternium-18 bentonites, such as those sold under the names Bentone 3, Bentone 38 and Bentone 38V by Rheox, Tixogel VP by United Catalyst and Claytone 34, Claytone 40 and Claytone XL by Southern Clay; stearalkonium bentonites, such as those sold under the names Bentone 27 by Rheox, Tixogel LG by United Catalyst and Claytone AF and Claytone APA by Southern Clay; and quaternium-18/benzalkonium bentonites, such as those sold under the names Claytone HT and Claytone PS by Southern Clay.

The thickener can also be chosen from organic compounds.

Mention may be made, for example, of the following polymeric or non-polymeric products:

- C10-C30 fatty amides, such as lauric acid diethanolamide,

- the polyglyceryl (meth)acrylate polymers sold under the Hispagel or Lubragel names by Hispano Quimica or Guardian,

- polyvinylpyrrolidone,

- polyvinyl alcohol,

- crosslinked acrylamide polymers and copolymers, such as those sold under the names PAS 5161 or Bozepol C by Hoechst or Sepigel 305 by SEPPIC

the crosslinked methacryloyloxyethyltrimethylammonium chloride homopolymers sold under the name Salcare SC95 by Allied Colloid,

- associative polymers and in particular associative polyurethanes.

Such thickeners are described in particular in Application EP-A-1 400 234.

Preferably, the composition comprises at least one inorganic thickening agent which is preferably chosen from clays and more advantageously still from smectites.

The thickening agent is present in the composition in a total content ranging from 0.1 % by weight to 10% by weight, with respect to the weight of the composition.

The composition according to the invention comprises water, which can preferably be present in a content ranging from 20% by weight to 98% by weight, with respect to the weight of the composition.

The compositions can also comprise at least one agent commonly used in cosmetics, for example chosen from reducing agents, fatty substances, organic solvents or oils, softening agents, anti-foaming agents, moisturizing agents, UV screening agents, peptizing agents, solubilizing agents, fragrances, anionic, cationic, non-ionic or amphoteric surfactants, proteins, vitamins, propellants, oxyethylenated or non-oxyethylenated waxes, paraffins or C10-C30 fatty acids, such as stearic acid or lauric acid.

The above additives are generally present in an amount for each of them of between 0.01 % and 20% by weight, with respect to the weight of the composition.

Of course, a person skilled in the art will take care to choose this or these optional additive(s) so that the advantageous properties intrinsically attached to the formation of the sheathing in accordance with the invention are not, or not substantially, detrimentally affected.

The composition according to the invention can be provided in particular in the form of a suspension, a dispersion, a gel, an emulsion, in particular an oil-in-water (O/W), water-in-oil (W/O) or multiple (W/O/W or polyol/O/W or 0/W/O) emulsion, a cream, a foam, a stick, a dispersion of vesicles, in particular of ionic or non-ionic lipids, a two-phase or multiphase lotion, a spray or a paste. The composition can also be provided in the form of a lacquer.

A person skilled in the art can choose the appropriate formulation form, and also its method of preparation, on the basis of his general knowledge, taking into account first the nature of the constituents used, in particular their solubility in the support, and secondly the application envisaged for the composition.

Dyeing method

The composition described above can be employed on dry or wet keratinous fibres and also on any type of fibre, light or dark, natural or dyed, or permanent-waved, bleached or straightened.

According to a specific embodiment of the method of the invention, the fibres are washed before application of the composition described above.

The application to the fibres can be carried out by any conventional means, in particular using a comb, a brush, including a fine brush, or the fingers.

After the application of the composition, the fibres can be left to dry or dried, for example at a temperature of greater than or equal to 30°C. According to a specific embodiment, this temperature is greater than 40°C. According to a specific embodiment, this temperature is greater than 45°C and less than 220°C.

The drying, if it is employed, can be carried out immediately after the application or after a leave-in time which can range from 1 minute to 30 minutes.

Preferably, if the fibres are dried, they are dried, in addition to a supply of heat, with a flow of air. This flow of air during the drying makes it possible to improve the individualization of the sheathing. During the drying, a mechanical action can be exerted on the locks, such as combing, brushing or running the fingers through the hair. This operation can likewise be carried out once the fibres have dried, naturally or unnaturally.

The drying stage of the method of the invention can be carried out with a hood dryer, a hair dryer, a smoothing iron or a Climazone.

When the drying stage is carried out with a hood dryer or a hair dryer, the drying temperature is between 40°C and 1 10°C and preferably between 50°C and 90°C.

When the drying stage is carried out with a smoothing iron, the drying temperature is between 1 10°C and 220°C and preferably between 140°C and 200°C.

Once the drying is complete, a final rinsing or shampooing can optionally be carried out.

The invention will be illustrated more fully with the aid of the non-limiting examples that follow. Unless otherwise mentioned, the amounts indicated are expressed in grams.

EXAMPLES

Composition examples:

0.6 g of composition A is applied, with the applicator according to the invention, to 1 g of a lock of white hair.

After a few seconds, the lock of hair is dry, the hair is coloured and the colour is homogeneous and persistent towards several shampooing operations.

A dyed lock is obtained, the hairs of which are individualized and the colour of which is persistent towards shampooing.

by BASF under the name Joncryl 77 i.e. 10% as AM

Divinyldimethicone/dimethicone copolymer in aqueous 8.3 g

emulsion, sold by Dow Corning under the reference i.e. 5% as AM

HMW 2220 Non-Ionic Emulsion

Clay (Magnesium Aluminium Silicate), sold by Vanderbilt 2 g

under the name Veegum granules

Pearlescent agent formed of mica coated with brown iron 6 g

oxide, sold by Eckart under the name Prestige Soft

Bronze

Water q.s. 100 g

0.7 g of composition B is applied, with the applicator according to the invention, to a lock of hair weighing 1 g with a height of tone of 4.

0.6 g of composition C is applied, with the applicator according to the invention, to a lock of white hair weighing 1 g.

Claims

1 . Device (1 ) for the application of a composition for dyeing keratinous fibres, comprising:

ii) a holding member (4) which is capable of interacting with the application means (2) in order, during a longitudinal displacement of the device (1 ) relative to a lock of keratinous fibres, to keep the said lock engaged with the application means (2), so as to make possible the coating thereof with the dyeing composition (P),

iii) the said application means (2) comprising an applicator end piece (30) mounted on the container (20) and comprising an outlet orifice (31 ) equipped with an opening/closing element (32) which, in a first position, closes off the said outlet orifice and which, in a second position, at least partly releases the said outlet orifice, the change from the first position to the second position taking place in response to a force exerted on the opening/closing element (32) by the engaging of the said lock between the holding member and this opening/closing element (32),

iv) the said dyeing composition (P) comprising at least one aqueous dispersion of particles of hybrid film-forming acrylic polymer, at least one linear block silicone copolymer and at least one pigment.

2. Device according to the preceding claim, characterized in that the holding member (4) can move with respect to the application means (2).

3. Device according to either one of the preceding claims, characterized in that the holding member (4) and the application means (2) form two separate pieces or else are connected by a connecting means (50) and form a single piece.

4. Device according to any one of the preceding claims, characterized in that the applicator end piece (30) comprises a surface (37) capable of storing and releasing the dyeing composition (P).

5. Device according to any one of the preceding claims, in which the dyeing composition (P) comprises at least one linear block silicone copolymer provided in the form of particles in dispersion in an aqueous medium.

6. Device according to any one of the preceding claims, in which the dyeing composition (P) comprises at least one linear block silicone copolymer obtained by a chain extension reaction, in the presence of a catalyst, starting from at least:

(a) one polysiloxane (i) having at least one reactive group and preferably one or two reactive groups per molecule; and

(b) one organosilicone compound (ii) which reacts with the polysiloxane (i) by a chain extension reaction.

7. Device according to the preceding claim, characterized in that the organopolysiloxane (i) is chosen from the compounds of formula (I):

in which R-i and R₂ represent, independently of one another, a hydrocarbon group having from 1 to 20 carbon atoms or an aryl group or a reactive group, and n is an integer greater than 1 , provided that there are on average between one and two reactive groups per polymer.

8. Device according to the preceding claim, characterized in that the reactive group is chosen from hydrogen; aliphatically unsaturated groups; the hydroxyl group; alkoxy groups; alkoxyalkoxy groups; the acetoxy group; amino groups; and their mixtures.

9. Device according to either one of Claims 7 and 8, characterized in that R-i represents a methyl group and R₂ at the chain end represents a vinyl group.

10. Device according to any one of Claims 6 to 9, characterized in that the organosilicone compound (ii) is chosen from polysiloxanes of formula (I) or compounds acting as chain-extending agent such as a silane, a siloxane or a silazane.

1 1 . Device according to any one of Claims 5 to 9, characterized in that the compound (ii) is a liquid organohydropolysiloxane of formula (II):

where n is an integer greater than 1 and preferably greater than 10, preferably equal to 20.

12. Device according to any one of Claims 5 to 1 1 , characterized in that the dispersion is an aqueous dispersion of divinyldimethicone/dimethicone copolymer.

13. Device according to one of the preceding claims, in which the dyeing composition (P) exhibits a content of linear block silicone copolymer(s), expressed as polymeric active materials, ranging from 0.1 % to 30% by weight, more particularly from 0.5% to 20% by weight and preferably from 1 % to 15% by weight, with respect to the total weight of the composition.

14. Device according to any one of the preceding claims, in which the dyeing composition (P) comprises at least one hybrid film-forming acrylic polymer synthesized from at least one monomer having at least one (meth)acrylic acid group and/or from esters of these acid monomers and/or from amides of these acid monomers and from at least one styrene compound.

15. Device according to any one of the preceding claims, in which the dyeing composition (P) comprises at least one hybrid film-forming acrylic polymer chosen from styrene/acrylate copolymers, in particular a copolymer resulting from the polymerization of at least one styrene monomer and of at least one C1-C10 alkyl acrylate monomer, preferably chosen from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate or 2-ethylhexyl acrylate.

16. Device according to any one of the preceding claims, in which the hybrid hydrophobic film-forming acrylic polymer or polymers in aqueous dispersion is or are present in a content, as active materials, ranging from 0.1 % to 30% by weight, more particularly from 0.5% to 20% by weight and preferably from 1 % to 15% by weight, with respect to the total weight of the composition.

17. Device according to any one of the preceding claims, in which the hybrid hydrophobic film-forming acrylic polymer or polymers in aqueous dispersion and the linear block silicone copolymer or copolymers are present in a hybrid hydrophobic film- forming acrylic polymer(s) to linear block silicone copolymer(s) ratio by weight (as active materials) ranging from 0.2 to 10, advantageously from 0.5 to 5 and preferably from 1 to 3.

18. Device according to any one of the preceding claims, in which the amount of pigment(s) ranges from 0.01 % to 30% by weight, more particularly from 0.05% to 20% by weight and preferably from 0.1 % to 15% by weight, with respect to the total weight of the composition.

19. Device according to any one of the preceding claims, in which the composition additionally comprises at least one inorganic thickening agent preferably chosen from clays, preferably a smectite.

20. Method for dyeing keratinous fibres comprising the application, to the keratinous fibres, of a dyeing composition (P) included in a device according to any one of the preceding claims, optionally followed by a drying of the fibres.