APPLICATOR FOR APPLYING A PRODUCT TO THE EYEBROWS

- L'OREAL

The invention concerns an applicator (10) for applying a product (P) to the eyebrows, comprising: a rod (11) an application member (30) secured to one end of the rod, comprising: —a body (32) with a free end (36) and having an application face (33) with a portion (38) of which the width decreases towards the free end, —pins (34) projecting from the application face (33), at least some of said pins being connected to the portion (38) of decreasing width, with a series of at least three pins (34) in the direction of the width of the application face (33) and a series of at least three pins (34) in the direction of the length thereof.

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Description

The present invention relates to an applicator for applying a product to the eyebrows, a packaging and application device comprising such an applicator, and a method for cosmetic treatment of the eyebrows.

There is a need for making up hairs of the eyebrows, particularly in order to change their color, for example in such a way as to obtain a result in harmony with the color of the hair.

Various applicators for applying a product to the eyebrows have already been proposed.

The U.S. Pat. No. 8,051,860 thus discloses a device for applying a cosmetic coloring composition in the region of the eyebrows, comprising an endpiece impregnated with said composition. Such a device is used in the manner of a pad.

EP 1 649 777 A2 discloses a device for packaging a product and for applying it to the eyelashes or eyebrows, in particular mascara, said device comprising a comb with a relatively small number of teeth. Such a device is suitable very particularly for making up the eyelashes at the corner of the eye.

WO 2010/007588 A2 discloses an applicator comprising teeth that extend in different directions and that are connected to a body of generally cylindrical shape along the longitudinal axis of the application member. Although the application of product to the eyelashes is envisioned, such an applicator is nevertheless more particularly suitable for applying the product to the eyelashes.

There is a need to further improve the applicators for applying a product to the eyebrows, in particular in order to comb the latter and make them up with precision without staining the skin.

The invention aims to meet this need and it achieves this by virtue of an applicator comprising

    • a stem,
    • an application member which is fixed to one end of the stem and comprises:
    • a body having a free end and having an application face with a portion whose width decreases in the direction of the free end,
    • spikes projecting from the application face, at least some of them being connected to the portion of decreasing width, with, on the application face, a succession of at least three spikes in the direction of the width and a succession of at least three spikes in the direction of its length.

The term “length” designates the longitudinal direction of the application member, and the term “width” designates the perpendicular direction.

By virtue of the invention, the user has available an applicator which is very particularly suitable for precisely making up the eyebrow fringe. The user can use the applicator to color the eyebrows, without staining the skin. Preferably, this applicator is used with a container which is provided with a wiping element, as explained in detail below.

The stem of the applicator can be made relatively fine and does not greatly obstruct the view of the eyebrow fringe when the user is applying makeup.

A narrower shape at the end of the application member is compatible with an implantation of the spikes that is suitable for precise and effective making up of the fringe of the eyebrows, and the distal end of the application member can thus be used to manage the eyebrows, likewise the back of the application member, opposite the application face, which can be made without application element.

The applicator can comprise a succession of a maximum of four or five spikes, in the direction of the length of the application face and/or of three to five spikes in the direction of the width of the application face. The total number of spikes carried by the application member is thus relatively small and preferably between 8 and 15. A relatively low number of spikes is advantageous in that it facilitates the management of the eyebrows and the engagement of the hairs between the spikes. The application member is preferably used with a cosmetic composition that is more fluid than a mascara conventionally used for making up the eyelashes of the eyelid.

All the spikes are preferably implanted on the portion of decreasing width of the application face.

Preferably, the back of the application member, opposite the application face carrying the spikes, is smooth. This back can be used to manage the hairs while applying makeup, as indicated above.

The spikes can be arranged in rows, preferably at a constant spacing within one and the same row and, better still, a constant spacing between the spikes of all the rows.

Preferably, the number of spikes per row decreases in the direction away from a longitudinal median plane of the application member.

Preferably, the application member comprises a central row which comprises the greatest number of spikes, and the other rows comprise fewer spikes than this central row. The latter is preferably situated along a median plane of symmetry of the application member.

The spikes can be arranged in substantially concentric arcs of implantation around a point situated to the front of the application member.

The spikes can be arranged in rows that are aligned in the direction of the length of the application face.

The spikes can be arranged in rows parallel to the longitudinal axis of the application member. These rows may or may not be offset with respect to one another in the longitudinal direction of the application member, the offset between two adjacent rows being, for example, between ¼ and ¾ of the mean spacing between the spikes within one and the same row, said spacing being measured at the base of the spikes.

The spikes are preferably of a longitudinal axis parallel to a same direction, which is preferably not parallel and not perpendicular to a longitudinal axis of the application member.

The longitudinal axis of the spikes preferably forms, with the longitudinal axis of the application member, an angle that is not a right angle, such that the spikes are oriented obliquely with respect to the longitudinal axis of the stem, preferably by an angle α of between 30 and 80°. The spikes are thus preferably oriented toward the front of the applicator.

Preferably, no spike is of a longitudinal axis parallel to the longitudinal axis of the stem. Likewise preferably, no spike is of a longitudinal axis perpendicular to the longitudinal axis of the stem.

It is possible for the longitudinal axis of the application member to be coincident or not to be coincident with the longitudinal axis of the stem.

The application face can be slightly convex toward the outside, and the envelope surface defined by the free ends of the spikes can also be convex toward the outside, for example being parallel to the application face. Alternatively, and preferably, the free ends of the spikes all belong to one and the same plane, which is preferably not parallel to the longitudinal axis of the application member.

The body of the application member preferably has a general shape flattened in a flattening plane, which can be oriented generally perpendicularly with respect to a median plane for the application face. The greatest width of the body of the application member is preferably greater than the length of the largest of the spikes.

The greatest width wmax of the body of the application member can be greater than the diameter dtige of the stem of the applicator in its region adjacent to the application member.

When the application member is observed along its longitudinal axis, the axes of the spikes can be oriented substantially perpendicularly with respect to said flattening plane.

A flattened shape of the body of the application member is advantageous in that it tends to ovalize the wiping element to the passage of the application member and may lead to further wiping of the spikes, which reduces the quantity of product present at their end and reduces the risk of staining the skin by excessive application of product.

The application member may have a symmetrical shape with respect to a longitudinal median plane. At least one row of spikes can extend in this longitudinal median plane.

Preferably, the spikes are molded in one piece with the body of the application member and are preferably made of an elastomer material so as to impart flexibility to the application member.

In particular, the application member can have a sufficient flexibility such that the spikes and/or the body of the application member can deform during passage through the wiping element and/or during the application of the product to the eyebrows.

The application member preferably comprises an endpiece which is molded integrally with the body of the application member.

This endpiece serves for mounting the application member in the stem, the latter having a recess for this purpose.

The longitudinal axis of the endpiece can form an angle which is not zero with the longitudinal axis of the body of the application member. Preferably, the longitudinal axis of the body of the application member is coincident with the longitudinal axis of the endpiece.

It is particularly advantageous that the spikes are not flocked, since this reduces the quantity of product retained at the end and, hence, reduces the risk of applying product to the skin.

The spikes can be of the same length. However, the spikes are preferably of a variable length.

It is thus particularly advantageous that the application member comprises a spike of greater length situated near its distal end. This spike is preferably of a longitudinal axis situated in a median plane of symmetry of the application member.

Within a row of spikes, in particular a central row of spikes, preferably situated along a median plane of symmetry for the application member, the length of the spikes can thus increase toward the free end of the application member, preferably increasing by at least 20%, for example going from 2.4 mm to 3 mm, or in this case by 25%.

A longer spike, near the distal end of the application member, is advantageous in that it provides the user both with a spike that is well wiped and also with a reserve of product near this spike, said reserve being composed of the drop of product that tends to remain in the continuation of the application member after wiping, since it is not removed by the wiping element. Such a spike may help the user perform precise and careful making up of the eyebrows.

The application face to which the spikes are connected is preferably inclined with respect to the longitudinal axis of the application member.

The spikes can be connected non-rectilinearly to this application face, preferably leaning slightly forward when the application member is observed in cross section in a plane parallel to its longitudinal axis, for example in cross section in a median plane when the application member comprises a central row extending along this median plane.

The longest spike can be connected via its base to the application face at a position set back from the free end of the application member, by a distance which is for example substantially equal to the distance separating it from the following spike within the row.

In a very preferred embodiment, the application member comprises a central row of at least three spikes, preferably four spikes, of which the length increases, preferably linearly, toward the free end of the application member, and two lateral rows of at least two spikes each, preferably offset axially with respect to the central row by about half the spacing between two consecutive teeth, measured at their base, of the central row. In this preferred embodiment, all the spikes are present on a portion of the application face whose length decreases toward the free end of the application member. The spikes are connected to an inclined application face and are preferably of mutually parallel longitudinal axes, all preferably inclined toward the front.

A further subject of the invention, according to another of its aspects, is a packaging and application device, comprising an applicator according to the invention and a container containing the product to be applied.

This container is preferably provided with an element which serves for wiping the stem and the application member and through which the application member passes when the applicator is withdrawn from the container. It is particularly advantageous that the body of the application member is wider than the smallest internal diameter of the wiping element, since this makes it possible to wipe the spikes more vigorously, the tip thereof thus carrying less product, which fact reduces the risk of staining the skin and can allow makeup to be applied with care. The applicator can comprise a grip element designed to close the container when the latter is not in use. The stem of the applicator is connected to this grip element.

A further subject of the invention is a method for making up the eyebrows, in which method a cosmetic product is applied, with the aid of the applicator according to the invention, to the eyebrows. The product is advantageously taken from a container provided with a wiping element. The product is applied with the aid of the spikes and of the application face. The back of the application member can be used to move the hairs without seeking to apply product.

The invention may be better understood from reading the following detailed description of non-limiting implementation examples thereof and from examining the appended drawing, in which:

FIG. 1 shows a schematic front view of an example of a packaging and application device according to the invention,

FIG. 2 shows the application member in isolation, in a front view,

FIG. 3 is a side view along III in FIG. 2,

FIG. 4 is an axial view along IV in FIG. 2,

FIG. 5 is a view along V in FIG. 3, illustrating the implantation of the spikes on the application face,

FIG. 6 is a view, similar to FIG. 2, of a variant of the application member,

FIG. 7 is a side view along VII in FIG. 6,

FIG. 8 is an axial view along VIII in FIG. 6,

FIG. 9 is a view along IX in FIG. 7, illustrating the implantation of the spikes on the application face,

FIG. 10 is a view, similar to FIG. 2, of another variant of the application member,

FIG. 11 is a side view along XI in FIG. 10,

FIG. 12 is an axial view along XII in FIG. 10,

FIG. 13 is a view along XIII in FIG. 11, illustrating the implantation of the spikes on the application face,

FIG. 14 is a view, similar to FIG. 2, of a variant,

FIG. 15 is a side view along XV in FIG. 14,

FIG. 16 is an axial view along XVI in FIG. 14,

FIG. 17 is a view along XVII in FIG. 15, illustrating the implantation of the spikes on the application face,

FIG. 18 is a view, similar to FIG. 2, of a variant,

FIG. 19 is a view along IXX in FIG. 18,

FIG. 20 is a view along XX in FIG. 18,

FIG. 21 is a view along XXI in FIG. 19, illustrating the implantation of the spikes on the application face,

FIG. 22 is a view, similar to FIG. 2, of a variant,

FIG. 23 is a side view along XXIII in FIG. 22,

FIG. 24 is an axial view along XXIV in FIG. 22,

FIG. 25 is a view along XXV in FIG. 23,

FIG. 26 is a cross section along XXVI-XXVI in FIG. 24, and

FIGS. 27 to 51 show elevations, in particular front, rear and side views, of other examples of application members according to the invention.

The packaging and application device 1 shown in FIG. 1 comprises an applicator 10 according to the invention and a container 20 containing a product P to be applied to the eyebrows with the aid of the applicator 10.

The applicator 10 comprises a stem 11 which is connected to a grip element 12 designed to be fixed on the container 20 when the latter is not in use, so as to close the container sealingly.

At its distal end, opposite the grip element 12, the stem 11 carries an application member 30 according to the invention, comprising spikes 34.

The stem 11 can be rectilinear and have a circular cross section.

The application member 30 can extend along a longitudinal axis X, which can be coincident with that of the stem 11, as illustrated.

The applicator 10 can be fixed to the container 20 in various ways, for example by screwing the grip element 12 onto a neck 21 of the container 20. This neck 21 can at least partially accommodate an element 25 for wiping the stem 11 and the application member 30, it being possible for this wiping element 25 to be of any type known per se, in particular one with a flexible lip as illustrated, for example, in FIG. 45 of the publication WO 2010/007588 A2 or in FIGS. 25 to 28 of the application FR 2 900 036.

The smallest diameter of the wiping element 25 can be equal to the diameter of the stem 11, in its portion adjacent to the application member.

Although the use of a container provided with a wiping element is preferred because it makes it possible to leave little product at the end of the spikes 34, the product P can also be contained in a container designed to allow the application member 30 to be charged with product without passing through a wiping element. For example, the product can be contained in a container provided with a foam or with a wall permeable to the product, in contact with which the application member 30 can be charged with product. In another variant, the product is brought into contact with the application member by being removed by the latter directly from a pot containing the product or is applied to the application member 30 by withdrawal from a tube.

The stem 11 can have any shape; however, the stem 11 preferably has a circular cross section of which the diameter dtige is smaller than the greatest transverse dimension wmax of the application member 30. Thus, the latter deforms the wiping element 25 as it passes through.

The stem 11 can be hollow or solid and provided at its distal end with a recess into which an endpiece 31 of the application member 30, visible in FIG. 2, can be introduced. This endpiece 31 can be fixed in the recess of the stem 11 by any known means, for example by stapling, crimping, adhesive bonding, screwing, snap-fastening or welding.

In a variant not illustrated, the stem 11 is produced in one piece with the application member 30 by molding using one or more materials.

The container 20 can have a body made of thermoplastic material or glass, of any shape, and opaque or transparent.

Preferably, and generally, the product P is as described hereinbelow under the heading “Product”.

Preferably, the body 32 has a circular shoulder 37 in the area of the connection to the endpiece 31, and the diameter of this shoulder 37 at the base of the body 32 corresponds to the external diameter of the stem 11, such that the body 32 takes up a position externally in the continuation of the stem 11, without any appreciable discontinuity.

The body 32 of the application member defines an application face 33 which carries the spikes 34.

In the example in question, the application member 30 is made in one piece by the molding of a single thermoplastic material, preferably a single elastomeric material. The spikes 34 are not flocked. However, it is still within the scope of the present invention when the spikes 34 are made from a material different than that of the body 32, for example from a more flexible material or from a harder material.

The application face 33 has a portion 38 whose length decreases from the maximum wmax in the direction of a free end 36 of the application member 30.

The total length L of the application member 30 visible after the application member 30 has been mounted on the stem 11 is between 10 and 12 mm, for example.

In the example in question, the width of the visible portion of the application member 30, as observed in FIG. 2, decreases from the shoulder 37 and then increases in order to reach the maximum wmax, and it then decreases again along the portion 38.

The maximum width wmax of the body 32 of the application member 30 is, for example, between 4 mm and 8 mm, being for example equal to 6 mm.

The thickness of the portion 38 can likewise decrease, as can be seen in FIG. 3, in the direction of the free end 36.

The maximum thickness emax of the body 32 is, for example, between 3 and 3.6 mm, being for example 3.3 mm. The maximum thickness emax can be reached at the position where the width is also at its maximum, and this maximum thickness can be reached in a median plane of symmetry M for the application member 30.

It is advantageous that the body 32 of the application member 30 is wider than the internal diameter of the wiping element 25, since this makes it possible to dilate the wiping lip as the application member 30 passes through and thus to wipe the spikes 34 more vigorously, so as to leave less product near the free end thereof.

It is in particular preferred that the application member 30 has a transverse section flattened in a flattening plane F, which is generally perpendicular to the longitudinal axis of the spikes 34 after axial projection thereof on a plane perpendicular to the longitudinal axis of the body 32, as can be seen in FIG. 4.

In the example in question, the spikes 34 are of mutually parallel axes Y, all of them being oriented in a same direction, forming an angle α with the plane F in which the body 32 of the application member 30 is flattened.

This angle α is, for example, about 60°, being preferably between 30 and 80°. Thus, as can be seen in FIG. 3, the spikes 34 are oriented toward the front of the applicator.

The spikes 34 can have various shapes, including for example, as illustrated, a conical shape with a hemispherical tip.

The length l of the spikes 34 is, for example, between 2 and 4 mm, being for example equal to 3.5 mm in the example of FIGS. 2 to 15.

It will be seen in FIG. 5 that a row 34a of at least three spikes 34 arranged in succession in the longitudinal direction is connected to the portion 38 of the application face whose width decreases in the direction of the free end 36. The application face 33 likewise carries a succession 34b of at least three spikes in the direction of its width, that is to say in a direction perpendicular to the longitudinal median plane M in the example shown.

As can be seen in FIGS. 2 and 5 in particular, the application member 30 can comprise a central row 34a of spikes 34 arranged in the median plane M, this row of spikes comprising the greatest number of spikes, namely four in the example illustrated.

The spikes 34 can be arranged in various ways on the application face 33 and for example, as illustrated in FIG. 5, substantially concentrically along arcs of implantation C that are concave toward the free end 36.

In the example in FIG. 5, the application member 30 thus comprises three successions of spikes 34 each arranged in an arc of a circle C, the first succession comprising five spikes 34, and the two following ones comprising three spikes 34.

The free end 36 can have various shapes and, for example, can be curved toward the application side, as can be seen in particular in FIG. 3, in order to define a hemispherical point of which the diameter d at the base is between 0.4 and 0.5 mm, for example. The spacing t between the apex of the point and the nearest spike 34, measured along the longitudinal axis of the application member 30, is for example between 1 and 2 mm, being for example equal to 1.5 mm.

Within each longitudinally extending row of spikes 34, the spacing r between two consecutive spikes 34 can be between 0.80 mm and 1 mm, being for example equal to about 0.9 mm. This spacing r can be the same within one row and the same for all the longitudinal rows, as is illustrated in FIG. 5.

The distance between two consecutive spikes 34 along an arc C can be of the same order.

The size s in the vertical direction, when the application member 30 is observed in projection along the longitudinal axis of the body 32 as in FIG. 4, measured between the back 39 of the application member and the highest free end of the spikes 34, is for example between 6 and 7 mm, being for example equal to 6.5 mm.

The application face 33 is preferably convex, as illustrated in FIG. 4, such that the free ends of the spikes 34 of the central row 34a protrude beyond those of the other rows, when the application member 30 is observed along the longitudinal axis of the body 32.

To use the applicator 10 of FIGS. 1 to 5, the user withdraws it from the container 20 and applies the product P to the eyebrows with the aid of the spikes 34. During its withdrawal from the container 20, the application member 30 passes through the wiping element 25, and excess product is removed from the free ends of the spikes 34. After use, the user puts the applicator 10 back in the container 20, and the grip element 12 ensures leaktight closure of the latter.

The variant of the application member 30 illustrated in FIGS. 6 to 9 differs from that described with reference to FIGS. 2 to 5 mainly in terms of the implantation of the spikes 34 on the application face 33. In the example in FIGS. 2 to 5, the axial offset between the longitudinal rows of spikes 34 is relatively small, being associated with the implantation of the spikes along arcs of a circle C.

In the example in FIGS. 6 to 9, the axial offset between adjacent rows is more pronounced and is provided in such a way as to have a substantially staggered arrangement of the spikes in the lateral direction, as can be seen in particular in FIG. 9. In the example in FIGS. 6 to 9, the application member 30 comprises five rows of spikes parallel to the median plane M, namely a central row of five spikes, two intermediate lateral rows of three spikes 34 each, and two external lateral rows of two spikes each.

Most but not all of the spikes 34 are connected to the portion 38 whose width decreases toward the free end 36.

In the example in FIGS. 10 to 13, the body 32 of the application member 30 is narrower, for example with a width wmax of between 4 and 6 mm, for example equal to 5 mm, for a vertical size s for example equal to that of the examples in FIGS. 4 and 8.

The maximum thickness emax can also be equal to that of the examples in FIGS. 3 and 7.

In the example in FIGS. 10 to 13, it will be seen that the spikes 34 can be arranged with a maximum number of spikes 34 in the lateral direction equal to three, with, for example as illustrated, a central row 34a of four spikes 34 and two lateral rows of two spikes each.

In the example in FIGS. 14 to 17, the body 32 has the same shape as in the example in FIGS. 10 to 13, but the implantation of the spikes 34 is modified, with an axial offset between the adjacent longitudinal rows of spikes 34, so as to obtain, as illustrated in FIG. 17, a substantially staggered arrangement of the spikes 34 in the lateral direction.

In the example in FIGS. 14 to 17, the application member comprises a central row 34a of four spikes 34 and two lateral rows of only two spikes 34 each.

In the example in FIGS. 18 to 21, the spikes 34 are closer together in the longitudinal direction, for example with a spacing r, at their base, of between 0.5 and 0.6 mm.

The application member 30 comprises, for example, a central row 34a of five spikes 34 and two lateral rows of three spikes, with an axial offset between the rows, in such a way as to obtain a staggered arrangement.

The variant in FIGS. 22 to 26 is particularly preferred.

In this variant, the spike 34 situated closest to the free end 36 is longer than the spikes of the same row.

It will be seen in particular in FIG. 26 that the length of the spikes 34 increases toward the free end 36. This increase may be linear, as illustrated.

For example, the length of the spikes goes from lmin to lmax, with lmin=2.4 mm and lmax=3 mm.

The diameter m of a spike 34 at its base is for example between 0.5 and 0.6 mm.

In the example illustrated, the application member 30 comprises a central row 34a of four spikes 34 and two lateral rows 34c of two spikes 34 each, with a longitudinal offset between the spikes 34 of a row 34c and those of the row 34a having substantially the value of the spacing r between two spikes 34.

The spikes 34 of the lateral rows 34c can likewise have a height 1 that increases toward the free end 36.

When the application member is observed from the side, as illustrated in FIG. 23, the ends of the spikes 34 can all be situated in one and the same plane N, which may be non-parallel to the longitudinal axis of the application member 30 and non-parallel to the longitudinal axis of the stem 11 of the applicator.

Many modifications may be made to the invention, in particular to the shape given to the body 32.

In the examples in FIGS. 27 to 51, the application member 30 comprises a central row of four spikes and two lateral rows limited to a single spike, but the implantation of the spikes 34 could be other than this, for example identical to any one of the implantations that have been described with reference to FIGS. 1 to 26.

In the example in FIGS. 27 to 29, the back of the body 32 of the application member 30 has a central ridge, which extends in a median plane of symmetry.

In the example in FIGS. 30 to 32, the back of the body 32 has a twisted shape.

In the example in FIGS. 33 and 34, the back of the body 32 is concave toward the outside, when the application member 30 is observed from the side.

In the example in FIGS. 35 and 36, and in the one in FIGS. 37 and 38, the body 32 has a general triangular shape in side view.

In the example in FIGS. 39 and 40, the body 32 is openworked between the portion 38 of decreasing width and the endpiece 31 for fixing on the stem.

In the example in FIGS. 41 and 42, the body 32 has striations 60 between the portion 38 and the endpiece 31.

In the example in FIGS. 43 to 45, the free end 36 is substantially plane, seen from the front.

In the example in FIGS. 46 to 48, the application face 33 is delimited over part of its length by two opposite sides which are parallel to each other, before joining at the end in a rounded part, which delimits the portion 38 of decreasing width.

In the example in FIGS. 49 to 51, the back of the body 32 is completely rounded.

Product

The product can have any formulation suitable for making up the eyelashes or the eyebrows. Preferably, the product comprises an aqueous dispersion of particles of hydrophobic film-forming hybrid acrylic polymer, at least one linear block silicone copolymer, and at least one pigment.

Preferably, the composition likewise comprises at least one mineral thickener, preferably chosen from among clays, preferably a smectite.

By use of such a composition, it is possible to obtain, on the hairs, colored sheathings which provide a visible coloration on all types of hairs, in a manner resistant to washing, while at the same time preserving the physical qualities of the hairs. Such a sheathing is, in particular, resistant to the external attacking factors to which the hairs may be subjected, such as perspiration. It makes it possible in particular to obtain a smooth and uniform deposit with the aid of the applicator according to the invention.

The hairs remain individualized, which is to say that, after the composition has been applied and dries, the hairs are not stuck to each other and, therefore, do not form clusters of hairs, the sheath being formed around practically each hair.

After application of the composition to the hairs of the eyebrows, the color does not smudge when touched, does not transfer by contact and is resistant to water and to brushing with a small brush or a small comb.

Aqueous Dispersion of Particles of Hydrophobic Film-Forming Hybrid Acrylic Polymer

For the purposes of the invention, the term “polymer” means a compound corresponding to the repetition of one or more units (these units resulting from compounds known as monomers). This or these unit(s) are repeated at least twice and preferably at least three times.

The term “film-forming polymer” is understood to mean a polymer capable of forming, by itself alone or in the presence of an auxiliary 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 esters of these acid monomers and/or amides of these acid monomers and from at least one compound (ii) different from the compounds (i).

The esters of (meth)acrylic acid (also called the (meth)acrylates) are advantageously chosen from alkyl (meth)acrylates, in particular C1-C30, preferably C1-C20, better still C1-C10, alkyl (methacrylate), aryl (meth)acrylates, in particular C6-C10 aryl (meth)acrylate, hydroxyalkyl (meth)acrylates, in particular C2-C6 hydroxyalkyl (meth)acrylate.

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 a portion or all of the hydrogen atoms of the alkyl group are replaced by 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-C12 alkyl)(meth)acrylamides. Among the N-alkyl(meth)acrylamides that may be mentioned are N-ethylacrylamide, N-t-butylacrylamide, N-t-octylacrylamide and N-undecylacrylamide.

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

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

As styrene monomers that may be used in the invention, examples that may be mentioned include styrene and α-methylstyrene, 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 copolymers sold under the name Joncryl 77 by BASF, under the name Yodosol GH41F 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 via 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. Besides the acrylic monomer(s), the hybrid hydrophobic film-forming polymer of the invention will then contain the compound derived from the condensation process or the compounds that interact in the polycondensation process.

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

The hydrophobic film-forming hybrid acrylic polymer or polymers in aqueous dispersion can be 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.

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 different types of monomer. This means that each block can be composed of a homopolymer or a copolymer; this copolymer constituting the block can in turn be random or alternating.

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 oil globules of which consist of a silicone of high viscosity, such that these globules appear to form like “flexible 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 in the composition according to the invention can be chosen in particular from those described in the document EP-A-874 017. 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) a polysiloxane (i) having at least one reactive group and preferably one or two reactive groups per molecule; and
    • (b) an organosilicone compound (ii) which reacts with the polysiloxane (i) via a chain-extension reaction.

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

in which R1 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” means any group that is capable of reacting with the organosilicon compound (ii) to form a block copolymer. Mention may be made, as reactive groups, of hydrogen; aliphatically unsaturated groups, in particular vinyl, allyl or hexanyl 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 the 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 2 to 100, 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 branches and generally less than 2 mol % of siloxane units. Moreover, the R1 and R2 groups can optionally be substituted by amino groups, epoxy groups, groups comprising sulfur, silicon or oxygen.

Preferably, at least 80% of the R1 groups are alkyl groups and better still methyl groups.

Preferably, the reactive R2 group 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 dimethylvinylsiloxypolydimethylsiloxane, compound of formula (I) in which the R1 radicals are methyl radicals and the R2 radicals at the chain end are vinyl radicals, whereas the two other R2 radicals are methyl radicals.

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

in which 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 for the reaction between the polysiloxane and the organosilicon compound may be chosen from metals and especially from platinum, rhodium, tin, titanium, copper and lead. It is preferably platinum or rhodium.

The silicone copolymer particle dispersion used in the composition according to the invention may especially be obtained, for example, by mixing (a) water, (b) at least one emulsifier, (c) the polysiloxane (i), (d) the organosilicon 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 nonionic or ionic (anionic, cationic or amphoteric) emulsifiers. They are preferably nonionic emulsifiers which can be chosen from polyalkylene glycol ethers of a fatty alcohol 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 in order 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 dimethylvinylsiloxypolydimethylsiloxane (or divinyl dimethicone) 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: divinyl dimethicone/dimethicone copolymer/C12-C13 Pareth-3/C12-C13 Pareth-23), which is a 60% aqueous dispersion of divinyl dimethicone/dimethicone copolymer comprising C12-C13 Pareth-3 and C12-C13 Pareth-23, said dispersion comprising approximately 60% by weight of copolymer, 2.8% by weight of C12-C13 Pareth-23, 2% by weight of C12-C13 Pareth-3 and 031% by weight of preservatives, the remainder to 100% being water.

The linear block silicone copolymer(s) may be present in an amount of 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 relative to the total weight of the composition.

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

When the hydrophobic film-forming hybrid acrylic polymer has a glass transition temperature which is too high for the desired use, a plasticizer may 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 the compounds which may be solvents for the polymer.

Preferably, the plasticizer has a molecular mass of less than or equal to 5000 g/mol, preferably less than or equal to 2000 g/mol, preferentially less than or equal to 1000 g/mol and more preferentially 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 plasticizer. In particular, mention may be made, alone or as a mixture, of the normal 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 high molecular weight polypropylene glycols, 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 and diethylene glycol methyl ether, 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 R11 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;
    • mixtures thereof.

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 uncyclized monosaccharide—polyhydroxyaldehyde (aldose) or polyhydroxyketone (ketose). The polyol is preferably a monosaccharide cyclized in hemiacetal form.

The polyol can be a monosaccharide or a polysaccharide comprising from 1 to 10 monosaccharides, preferably from 1 to 4 monosaccharides and more preferably one or two monosaccharides. 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 the disaccharides, of sucrose (also known as α-D-glucopyranosyl-(1-2)-β-D-fructofuranose), lactose (also known as β-D-galactopyranosyl-(1-4)-β-D-glucopyranose) and maltose (also known as α-D-glucopyranosyl-(1-4)-β-D-glucopyranose), and preferably 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 an unsubstituted linear or branched acid.

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 and preferably from 1 to 8 carbon atoms, for example from 1 to 6 carbon atoms. It can be chosen from R1OH alcohols such that R1 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 and 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 the aliphatic dicarboxylic acids, of those of formula HOOC—(CH2)n—COOH, in which n is an integer ranging from 1 to 10 and preferably ranging from 2 to 8, for example equal to 2, 4, 6 or 8.

Dicarboxylic acids chosen from succinic acid, adipic acid and sebacic acid are preferred.

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

Mention may be made, among the tricarboxylic acids, of the 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 a —OCOCH3 group.

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

Among the tricarboxylic acid esters that may be used are esters derived from citric acid (or citrates) such as tributyl acetyl citrate, triethyl acetyl citrate, triethylhexyl acetyl citrate, trihexyl acetyl citrate, trihexyl butyroyl citrate, triisodecyl citrate, triisopropyl citrate, tributyl citrate and tris(2-ethylhexyl) citrate. Mention may be made, as commercial references of plasticizers mentioned above, of the Citroflex range sold by Vertellus, in particular Citroflex A4 and Citroflex C2.

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

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

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

Mention may be made, among the 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 weight ratio of the hydrophobic film-forming hybrid 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 colored and persistent sheathings without damaging the hairs.

The term “pigment” is understood to mean white or colored 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 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 pigment powder or paste form. They can be coated or uncoated.

The pigments may be chosen, for example, from mineral pigments, organic pigments, lakes, pigments with special effects, such as nacres or glitter flakes, and mixtures thereof.

The pigment can be a mineral pigment. The term “mineral pigment” means any pigment that satisfies the definition in Ullmann's encyclopedia in the chapter on inorganic pigments. Mention may be made, among mineral pigments of use in the present invention, of ochres, such as red ochre (clay (in particular kaolinite) and iron hydroxide (for example hematite)), brown ochre (clay (in particular kaolinite) and limonite) or yellow ochre (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 aluminum 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 color or whiteness to the composition under the conditions under which they are employed.

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

Use may also be made of any inorganic or organic compound which is insoluble in the composition and which is conventional in the cosmetics field, provided that these compounds contribute color 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 colored 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 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 phenol derivatives, as are described in the patent FR 2 679 771.

Mention may also be made, as 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 11710);
    • Cosmenyl Yellow G: Pigment Yellow 1 (CI 11680);
    • Cosmenyl Orange GR: Pigment Orange 43 (CI 71105);
    • 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 the patent EP 1 184 426. These composite pigments may be composed especially of particles comprising a mineral 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 mineral substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate, calcium aluminum borosilicate and aluminum.

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 1 O (CI 77 002), D&C Green 3 (CI 42 053) or D&C Blue 1 (CI 42 090).

Mention may be made, as 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 effects pigments” means pigments that generally create a colored appearance (characterized by a certain shade, a certain vivacity and a certain level of luminance) that is non-uniform and that changes as a function of the conditions of observation (light, temperature, angles of observation, etc.). They thus contrast with colored pigments that afford a standard uniform opaque, semi-transparent or transparent shade.

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 higher 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 or with bismuth oxychloride, colored pearlescent pigments, such as mica covered with titanium and with iron oxides, mica covered with iron oxide, mica covered with titanium and in particular with ferric blue or chromium oxide or mica covered with titanium 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-TiO2-lake), Prestige sold by Eckart (mica-TiO2), Prestige Bronze sold by Eckart (mica-Fe2O3) or Colorona sold by Merck (mica-TiO2—Fe2O3).

Mention may also be made of pearlescent agents of gold color sold in particular by Engelhard under the name 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 name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by Merck under the names Passion Orange (Colorona) and Matte Orange (17449) (Microna); brown-colored 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-colored 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, and 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 comprising 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 1P 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 aluminum borosilicate and aluminum.

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 coloring effect generated by the coloring agents which are combined with them and more particularly so as to optimize this effect in terms of color rendition. They can more particularly have a yellow, pink, red, bronze, orangey, brown, gold and/or coppery color 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, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze or titanium, said substrate being coated with at least one layer of at least one metal oxide, such as titanium oxide, aluminum oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and mixtures thereof.

Examples that may be mentioned include aluminum powder, bronze powder or copper powder coated with SiO2 sold under the name Visionaire by the company Eckart.

Mention may also be made of pigments with an interference effect not bound to a substrate, for instance liquid crystals (Helicones HC from Wacker), holographic interference flakes (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 U.S. Pat. No. 6,225,198 or U.S. Pat. No. 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. 119, No. 30, pp. 7019-7029.

The variety of pigments that may be used in the present invention makes it possible to obtain a wide range of colors, and also particular optical effects such as metallic effects or interference effects.

The size of the pigment used in the cosmetic composition according to 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 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, in particular, and of C8 to C20 fatty acid and of polyol, for instance glycerol or diglycerol, such as poly(12-hydroxystearic acid) stearate 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 may be surface-treated with an organic agent.

Thus, the pigments that have been surface-treated beforehand, which are useful in the context of the invention, are pigments that have totally or partially undergone a surface treatment of chemical, electronic, electrochemical, mechanochemical or mechanical nature, with an organic agent such as those described especially 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 aluminum salts of fatty acids, for example aluminum 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 solvent evaporation, 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 the patent U.S. Pat. No. 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 pigment.

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, for instance 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 aluminum dimyristate treatment, such as the MI 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) may range 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 relative to the total weight of the composition.

The composition of the invention can comprise other colored or coloring entities, such as direct dyes or dye precursors.

Thickener

According to a preferred embodiment, the composition according to the invention comprises at least one thickener chosen from polymeric or non-polymeric and inorganic or organic thickeners, 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 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 oxhydric 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 the company 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 the company Cabot.

It is possible to chemically modify the surface of 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 may 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 (6th edition, 1995). They are sold, for example, under the references Aerosil R812® by the company Degussa, and Cab-O-Sil TS-530® by the company Cabot;
    • dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained 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 (6th edition, 1995). They are sold, for example, under the references Aerosil R972® and Aerosil R974® by the company Degussa, and Cab-O-Sil TS-610® and Cab-O-Sil TS-720® by the company Cabot.

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

Clays are well-known products which are described, for example, in the publication Minéralogie des argiles [Mineralogy of Clays], S. Caillère, S. Hénin and M. Rautureau, 2nd Edition, 1982, Masson.

Clays are silicates including a cation which can be chosen from calcium, magnesium, aluminum, 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, stevensites or chlorites.

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

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 names 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 aluminum silicates, in particular hydrated, such as the product sold by Vanderbilt Company under the name Veegum Ultra, or calcium silicates and in particular that in synthetic form sold by the company under the name Micro-Cel C.

The organophilic clay can be chosen from montmorillonite, bentonite, hectorite, attapulgite or sepiolite, and mixtures thereof. The clay is preferably a bentonite or a hectorite.

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

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.

Examples that may be mentioned include the following polymeric or non-polymeric products:

    • C10-C30 fatty amides, such as lauric 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 by Allied Colloid, or alternatively
    • the crosslinked methacryloyloxyethyltrimethylammonium chloride homopolymers sold under the name Salcare SC95 by Allied Colloid,
    • associative polymers and especially associative polyurethanes.

Such thickeners are described especially in the application EP-A-1400234.

Preferably, the composition comprises at least one mineral thickener which is preferably chosen from clays and, even more advantageously, from smectites.

The thickener is present in the composition in a total content ranging from 0.1% 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% 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 may especially be in the form of a suspension, a dispersion, a gel, an emulsion, especially an oil-in-water (O/W) or water-in-oil (W/O) emulsion, or a multiple emulsion (W/O/W or polyol/O/W or O/W/O).

Those skilled in the art may select the appropriate galenical form, and also the method for preparing it, on the basis of their general knowledge, taking into account both the nature of the constituents used, in particular their solubility in the support, and the intended use of the composition.

Composition Examples

Composition A Styrene/acrylate copolymer in aqueous dispersion, sold 21.2 g by BASF under the name Joncryl 77 i.e. 10% of AM Divinyl dimethicone/dimethicone copolymer as an 2 g aqueous emulsion, sold by Dow Corning under the i.e. 1.2% of AM reference HMW 2220 Nonionic Emulsion Black 2 as an aqueous dispersion, from Daito Kasei 10 g, i.e. 2.5% of Kogyo under the name WD-CB2 AM Water q.s. for 100 g Composition B Styrene/acrylate copolymer in aqueous dispersion, 21.2 g sold by BASF under the name Joncryl 77 i.e. 10% of AM Divinyl dimethicone/dimethicone copolymer as an 2 g aqueous emulsion, sold by Dow Corning under the i.e. 1.2% of AM reference HMW 2220 Nonionic Emulsion Clay (magnesium aluminum silicate), sold by 2 g Vanderbilt under the name Veegum granules Nacre of mica coated with brown iron oxide, sold by 6 g Eckart under the name Prestige Soft Bronze Water q.s. for 100 g Composition C Styrene/acrylate copolymer in aqueous dispersion, 20 g, i.e. 9.43% sold by BASF under the name Joncryl 77 of AM Divinyl dimethicone/dimethicone copolymer as an 7.9 g, i.e. 4.76% aqueous emulsion, sold by Dow Corning under the of AM reference HMW 2220 Nonionic Emulsion Clay (magnesium aluminum silicate), sold by 1.8 g Vanderbilt under the name Veegum granules Black 2 as an aqueous dispersion, from Daito 9 g, i.e. 2.25% Kasei Kogyo under the name WD-CB2 of AM Water q.s. for 100 g

Of course, the invention is not limited to the exemplary embodiments illustrated. The application member may be produced with yet other arrangements of spikes. The product can have another formulation.

The expression “comprising a” is synonymous with “comprising at least one”.

Claims

1-14. (canceled)

15. An applicator for applying a product to the eyebrows, comprising

a stem,
an application member which is fixed to one end of the stem and comprises:
a body having a free end and having an application face with a portion whose width decreases in the direction of the free end,
spikes projecting from the application face, at least some of them being connected to the portion of decreasing width, with a succession of at least three spikes in the direction of the width of the application face and a succession of at least three spikes in the direction of its length.

16. The applicator as claimed in claim 15, comprising a succession of a maximum of four or five spikes in the direction of the length of the application face and/or of three to five spikes in the direction of the width of the application face.

17. The applicator as claimed in claim 15, the total number of spikes carried by the application member being between 8 and 15.

18. The applicator as claimed in claim 15, all the spikes being implanted on the portion of decreasing width of the application face.

19. The applicator as claimed in claim 15, the back of the application member, opposite the application face carrying the spikes, being smooth.

20. The applicator as claimed in any one of the preceding claims, the spikes being arranged in rows that are aligned in the direction of the length of the application face.

21. The applicator as claimed in claim 15, the spikes being arranged in rows that are parallel to the longitudinal axis of the application member, in particular in rows that are offset with respect to one another in the longitudinal direction of the application member, the offset between two adjacent rows preferably being between ¼ and ¾ of the mean spacing between the spikes within one row, said spacing (r) being measured at the base of the spikes.

22. The applicator as claimed in claim 15, the spikes being of a longitudinal axis parallel to a same direction, which is not parallel and not perpendicular to a longitudinal axis of the application member, the longitudinal axis of the spikes forming, with the longitudinal axis of the application member, an angle that is not a right angle, such that the spikes are oriented obliquely with respect to the longitudinal axis of the stem, by an angle of between 30 and 80°.

23. The applicator as claimed in claim 15, the body of the application member having a general shape flattened in a flattening plane, which is oriented generally perpendicularly with respect to a median plane for the application face.

24. The applicator as claimed in claim 15, the application member having a shape that is symmetrical with respect to a longitudinal median plane, at least one row of spikes extending in this longitudinal median plane.

25. The applicator as claimed in claim 15, the application face to which the spikes are connected being inclined with respect to the longitudinal axis of the application member.

26. The applicator as claimed in claim 25, the spikes not being connected rectilinearly to the application face but leaning forward when the application member is observed in cross section in a plane parallel to its longitudinal axis.

27. A packaging and application device comprising an applicator as defined in claim 15, and a container containing the product to be applied.

28. The device of claim 27, the product comprising an aqueous dispersion of particles of hydrophobic film-forming hybrid acrylic polymer and at least one linear block silicone copolymer, at least one pigment, and at least one mineral thickener, chosen from among clays, the container being provided with an element which serves for wiping the stem and the application member and through which the application member passes when the applicator is withdrawn from the container.

29. A method for making up the eyebrows, in which a cosmetic product is applied to the eyebrows with the aid of the applicator as claimed in claim 15, the product being taken from a container provided with a wiping element.

Patent History
Publication number: 20160150869
Type: Application
Filed: Jun 20, 2014
Publication Date: Jun 2, 2016
Applicant: L'OREAL (Paris)
Inventors: Eric CAULIER (Maignelay), Marcel SANCHEZ (Aulnay Sous Bois), Audrey THENIN (Meudon), Karen TEBOUL (Saint Mande), Cécile CADORE (Paris)
Application Number: 14/900,327
Classifications
International Classification: A45D 40/26 (20060101);