FR3140268A1 - COSMETIC PROCESS USING A PARTICLE WITH MICROPROTUBERANCE - Google Patents

Abstract

COSMETIC PROCESS USING A PARTICLE WITH MICROPROTUBERANCE The present invention relates to a cosmetic process for coloring the interior of a keratinous substance such as the skin or lips, comprising the steps: (1) application to the keratinous substance of a composition comprising (a) at least one particle having at least one micro-protuberance, comprising (a-1) at least one water-soluble or water-dispersible polymer, and (a-2) at least one coloring agent , (b) at least one oil, (c) at least one organic lipophilic gelling agent, and (d) at least one water-soluble particle, other than (a) particle having at least one micro-protrusion; and (2) applying water to the keratinous substance, to which the composition has been applied, to release the (a-2) coloring agent from the (a) particle having at least one micro-protuberance. The cosmetic process according to the present invention can provide a keratinous substance such as skin and lips with lasting and uniform color effects. Figure for the abstract: none

Description

COSMETIC PROCESS USING A PARTICLE WITH MICROPROTUBERANCE

The present invention relates to the use of a particle having at least one micro-protuberance in a specific composition for cosmetic treatments of a keratinous substance such as the skin and lips.

CONTEXT OF ART

Topical application of coloring agents such as dyes or pigments to the skin by application of a formulation comprising the coloring agents is well known. For example, the surface of the skin or lips is often colored or tinted with cosmetic products such as foundation and lipstick. These cosmetic makeup products are widely used to color or dye the skin, especially facial skin and lips.

However, coloring or dyeing with cosmetic makeup products is temporary and can be easily removed from the skin and lips by, for example, sebum, sweat and rain. Thus, users of cosmetic makeup products need to color their skin and/or lips on a daily basis. Therefore, there is a need to provide long-lasting coloring effects.

One of the possible options to achieve long-lasting coloring effects on the skin or lips is to deliver coloring agents inside the skin or lips. However, local application of a formulation containing coloring agents cannot allow sufficient penetration of the coloring agents into the skin or lips. A thin layer of stratum corneum of the skin or lips poses a major obstacle for substances to penetrate the skin or lips. Therefore, the most important point to deliver coloring agents inside the skin or lips is to pass through the stratum corneum.

Also, it is also important to evenly distribute the dyes inside the skin or lips. Document WO 2020/17441 discloses the use of a sheet of microneedles to color the inside of the skin. However, there is room to improve the uniform distribution of the coloring agent in the skin.

DISCLOSURE OF THE INVENTION

An objective of the present invention is to provide a cosmetic process which can provide a keratinous substance such as skin and lips with lasting and uniform coloring effects.

The above objective can be achieved by a cosmetic process of coloring the interior of a keratinous substance such as skin and lips, comprising the steps:

(1) application to the keratinous substance of a composition comprising

(a) at least one particle having at least one micro-protuberance, comprising

(a-1) at least one water-soluble or water-dispersible polymer, and

(a-2) at least one coloring agent,

(b) at least one oil,

(c) at least one organic lipophilic gelling agent, and

d) at least one water-soluble particle, other than (a) particle having at least one micro-protrusion;

And

(2) applying water to the keratinous substance, to which the composition has been applied, to release the (a-2) coloring agent from the (a) particle having at least one micro-protuberance.

The micro-protuberance of the (a) particle can take the shape of a cone or a pyramid.

The micro-protuberance of the (a) particle may have a height of 100 to 600 microns, preferably 200 to 500 microns, and more preferably 300 to 400 microns.

The base of the micro-protuberance of the (a) particle may have a width of 50 to 500 microns, preferably 100 to 300 microns, and more preferably 150 to 250 microns.

The ratio (height of the pyramid)/(width of the base of the pyramid) of the microneedle of the (a) particle may be 1 or more, preferably 1.3 or more, and more preferably 1.6 or more.

The (a-1) water-soluble or water-dispersible polymer may be chosen from hyaluronic acids, monosaccharides, disaccharides, oligosaccharides, polysaccharides, dextrins, dextrans, polyethylene glycols, polyalcohols. vinyls, poly(methylvinyl ether/maleic anhydride), polyvinylpyrrolidone, poly(methyl/vinyl ether/maleic acid) (PMVE/MA) and its esters, poly(methyl/vinyl ether/maleic anhydride) (PMVE/MAH) and their derivatives.

The (a-2) coloring agent can be chosen from dyes, preferably natural direct dyes, and more preferably coloring plant extracts.

The amount of the (a) particle with at least one protrusion in the composition used in the present invention can range from 1% to 25% by weight, preferably from 3% to 20% by weight and more preferably from 5%. at 15% by weight, relative to the total weight of the composition.

The quantity of (b) oil in the composition according to the present invention may be from 50% to 95% by weight, preferably from 60% to 90% by weight and, more preferably, from 70% to 85% by weight. , relative to the total weight of the composition.

The (c) organic lipophilic gelling agent can be chosen from styrene block copolymers, semi-crystalline polymers, glutamide-based compounds, polyamides and mixtures thereof, and preferably polyamides.

The quantity of (c) organic lipophilic gelling agent used in the present invention may be from 1% to 15% by weight, preferably from 2% to 10% by weight and, more preferably, from 3% to 5% by weight, relative to the total weight of the composition.

The (d) water-soluble particle may comprise a polysaccharide, monosaccharide, amino acid or salt thereof, sugar alcohol, ascorbic acid or salt thereof, or a mixture thereof.

The quantity of the (d) water-soluble particle used in the composition according to the present invention may be from 0.1% to 15% by weight, preferably from 0.5% to 10% by weight and, more preferably , from 1% to 5% by weight, relative to the total weight of the composition.

The cosmetic process according to the present invention may further comprise the step of pushing the (a) particle having at least one micro-protuberance in the keratinous substance, between step (1) and step (2).

The present invention also relates to a cosmetic composition allowing the coloring of the interior of a keratinous substance, such as the skin and the lips, comprising:

(a) at least one particle having at least one micro-protuberance, comprising

(a-1) at least one water-soluble or water-dispersible polymer, and

(a-2) at least one coloring agent;

(b) at least one oil;

(c) at least one organic lipophilic gelling agent; And

(d) at least one water-soluble particle, other than (a) particle having at least one micro-protrusion.

There shows a photograph of the surface of the skin before application of the anhydrous composition in Example 1.

There shows a photograph of the skin surface immediately after wiping off the anhydrous composition of Example 1 which was applied to the skin surface shown in the .

There shows a photograph of the skin surface immediately after the water cleanse that was applied to the skin surface shown on the .

There shows a photograph of the skin surface after the first wash with an aqueous solution of sodium laureth sulfate at 5% by weight of the skin surface shown on the .

There shows a photograph of the skin surface after the second wash with an aqueous solution of sodium laureth sulfate at 5% by weight of the skin surface shown on the .

There shows a photograph of the skin surface after removing the stratum corneum from the skin surface shown on the .

After careful research, the inventors discovered that it is possible to provide a cosmetic process that can provide a keratinous substance such as skin and lips with lasting and uniform coloring effects.

Thus, one aspect of the present invention is a cosmetic process for coloring the interior of a keratinous substance such as the skin and the lips, comprising the steps:

(1) application to the keratinous substance of a composition comprising

(a) at least one particle having at least one micro-protuberance, comprising

(a-1) at least one water-soluble or water-dispersible polymer, and

(a-2) at least one coloring agent,

(b) at least one oil,

(c) at least one organic lipophilic gelling agent, and

d) at least one water-soluble particle, other than (a) particle having at least one micro-protrusion;

And

(2) applying water to the keratinous substance, to which the composition has been applied, to release the (a-2) coloring agent from the (a) particle having at least one micro-protuberance.

The cosmetic process according to the present invention can provide a keratinous substance such as skin and lips with lasting and uniform color effects.

According to the present invention, the (a) particle having at least one micro-protrusion can penetrate into a keratinous substance, and can dissolve or collapse to release the (a-2) coloring agent in the keratinous substance, thereby providing the keratinous substance produces lasting and uniform color effects.

Specifically, the (a) particle having at least one micro-protrusion can penetrate a keratinous substance such as skin or lips, and can dissolve or collapse with water applied in step (2) to release the (a-2) coloring agent in the keratinous substance. The micro-protrusion can perforate a keratinous substance to form fine holes on and in the keratinous substance. Thus, the (a-2) coloring agent can penetrate into a keratinous substance so that it can enter into the keratinous substance. For example, the (a-2) coloring agent can enter the stratum corneum. Additionally, the coloring agent can pass through the stratum corneum to reach one of the lower layers of the epidermis, such as a granular layer, a spinous layer, and a basal layer. Therefore, the coloring agent can remain in the skin or lips for a long time. Therefore, the present invention can produce long-lasting coloring effects.

In addition, the (a-2) coloring agent which released from the (a) dissolved or collapsed particle can relatively easily diffuse into a keratinous substance, such as the stratum corneum or epidermis, to distribute uniformly in the keratinous substance , for example skin or lips, compared to using microneedles which can only penetrate up to specified points. Therefore, the present invention can provide uniform coloring effects.

As the micro-protrusion of the (a) particle is very small, it does not cause any pain. Therefore, the cosmetic process according to the present invention can provide cosmetic treatments, that is to say coloring treatments, without pain.

Furthermore, the cosmetic process according to the present invention can be carried out in a relatively short time.

Thus, the present invention is convenient for cosmetic or non-therapeutic treatments.

Hereinafter, the cosmetic process and the like according to the present invention will be described in detail.

[Cosmetic process]

The cosmetic process according to the present invention for coloring the interior of a keratinous substance such as the skin and the lips comprises the steps:

(1) application to the keratinous substance of a composition comprising

(a) at least one particle having at least one micro-protuberance, comprising

(a-1) at least one water-soluble or water-dispersible polymer, and

(a-2) at least one coloring agent,

(b) at least one oil,

(c) at least one organic lipophilic gelling agent, and

d) at least one water-soluble particle, other than (a) particle having at least one micro-protrusion;

And

(2) applying water to the keratinous substance, to which the composition has been applied, to release the (a-2) coloring agent from the (a) particle having at least one micro-protuberance.

Step (1) and/or (2) can be carried out using any applicator such as a brush.

It may be preferable that the composition comprising ingredients (a) to (d) is applied to the keratinous substance in combination with at least one porous sheet such as a woven or non-woven fabric, in order to obtain good contact of the composition with the keratinous substance and good coloring at the desired site of the keratinous substance.

A porous sheet can absorb and hold the composition comprising ingredients (a) to (d). Therefore, the application of a porous sheet may well facilitate the contact of the composition with the keratinous substance, which may contribute to good coloring of the keratinous substance.

The type of the above combination is not limited. Thus, a porous sheet can be applied to the keratinous substance after applying the composition to the keratinous substance. It is also possible to apply a porous sheet to the keratinous substance after applying the composition to the keratinous substance.

It is preferable that step (1) is carried out at a desired area on a keratinous substance. For example, it is preferable that the site of application of the composition comprising ingredients (a) to (d) can be suitably determined on the surface of a keratinous substance so that coloring can be carried out at the level of a desired area on the keratinous substance.

It is best to perform step (1) on a dry keratinous substance. In other words, it is preferable that the composition comprising ingredients (a) to (d) is applied to a dry keratinous substance, for example, non-wet skin.

The cosmetic process according to the present invention may further comprise the step of pushing the (a) particle having at least one micro-protuberance into a keratinous substance, after step (1). This step can be carried out, for example, by massaging with the fingers the keratinous substance to which the composition comprising ingredients (a) to (d) was applied in step (1).

It is preferable that the cosmetic process according to the present invention further comprises the step of maintaining or releasing the keratinous substance for a certain time, after step (1), and more preferably after the possible pushing step below. -above, if necessary, because the (a) particle having at least one micro-protuberance can effectively penetrate the keratinous substance.

The cosmetic process according to the present invention may further comprise the step of cleaning the keratinous substance after step (1), and if the above holding or exit step is present, after this step. During the cleaning step, an excessive amount of the composition comprising ingredients (a) to (d) may be removed from the surface of the keratinous substance. This step can be carried out, for example, by wiping with thin paper the keratinous substance to which the composition comprising ingredients (a) to (d) has been applied.

The cosmetic process according to the present invention may further comprise the step of pushing the (a-2) coloring agent into a keratinous substance, after step (2). This step can be carried out, for example, by massaging with the fingers the keratinous substance to which the water was applied in step (2).

It is preferable that the cosmetic process according to the present invention further comprises the step of maintaining or releasing the keratinous substance for a certain time, after step (2), and more preferably after the possible pushing step below. -above, if necessary, because the (a-2) coloring agent can effectively penetrate the keratinous substance.

The cosmetic process according to the present invention may further comprise the step of cleaning the keratinous substance after step (2), and if the above holding or exit step is present, after this step. During the cleaning step, an excessive amount of water may be removed from the surface of the keratinous substance. This step can be carried out, for example, by wiping with a thin paper the keratinous substance on which water has been applied.

The cosmetic process according to the present invention may be intended for cosmetic treatments of a keratinous substance such as the skin and the lips, preferably the skin, and more preferably the skin of the face.

The cosmetic process according to the present invention can be used to improve the aesthetic appearance of a keratinous substance, for example, by coloring the interior of the keratinous substance, preferably the interior of the surface layer of the keratinous substance, and more preferably the interior of the stratum corneum of the skin.

The cosmetic process according to the present invention can provide a keratinous substance with lasting and uniform color effects. Therefore, for example, makeup effects provided by the cosmetic process according to the present invention can be maintained for a long time, even in the face of, for example, sebum, perspiration and rain.

However, the cosmetic process according to the present invention does not correspond to skin tattooing, which is a semi-permanent coloring, because skin tattooing is accompanied by pain. Furthermore, the cosmetic process according to the present invention colors the surface layer of a keratinous substance such as skin and lips, and therefore, the color offered by the cosmetic process according to the present invention can only last, for example, a few weeks, which does not correspond to semi-permanent coloring.

Hereinafter, the composition and the like used for the cosmetic process according to the present invention will be explained in detail.

[Composition]

The composition to be used for the cosmetic process according to the present invention (hereinafter referred to as the composition according to the present invention) comprises:

(a) at least one particle having at least one micro-protuberance, comprising

(a-1) at least one water-soluble or water-dispersible polymer, and

(a-2) at least one coloring agent;

(b) at least one oil;

(c) at least one organic lipophilic gelling agent; And

(d) at least one water-soluble particle, other than (a) particle having at least one micro-protrusion.

Since the composition according to the present invention comprises the (b) oil and the (c) organic lipophilic gelling agent, the composition according to the present invention can be in the form of a gel, that is to say an oil gel .

The term "gel" here includes a thick liquid which may be a Newtonian fluid or a non-Newtonian fluid. Newtonian fluid refers to a fluid that does not change viscosity with a change in flow state. The gel also contains a rheofluidifying gel.

In a preferred embodiment, the composition according to the present invention is a gel having a non-Newtonian viscosity. In another preferred embodiment, the composition according to the present invention is a shear thinning gel. A non-Newtonian shear-thinning material changes from a gel to a liquid state in the presence of an applied shear stress and becomes a gel again in the absence of the applied shear stress. By definition, a shear thinning material is one in which, as an applied shear stress is increased, the viscosity of the material decreases in a non-linear manner.

The composition according to the present invention as a gel can be defined with its rheological characteristics. A gel composition having 10 ^-1 Pa or more linear viscoelastic regions of a profile of storage modulus (G') and loss modulus (G") and more than 4% strain of a point d 'intersection of a profile G' and G" may be preferable. Indeed, such a gel composition may exhibit a preferable shear thinning property such that the gel transforms into a fine viscous almost water-like state under gentle shear conditions, which allows (d)soluble particles in water to be dispersed homogeneously in the composition, and as soon as the shear is eliminated, the gel retains its original thick viscosity without too much increase in viscosity, i.e. without too much hysteresis. In addition, the composition of the gel can give a plump texture, which is preferred by consumers. Furthermore, this property can provide stability and long shelf life to the composition so that (c) water-soluble particles in the composition do not precipitate for a long period of time.

Regarding hysteresis, for the composition according to the present invention as a gel, a change in the final viscosity values under all shear conditions can be less than 10% compared to the initial viscosity values.

The "intersection point" of the amplitude sweep, also called the "tumble point", is a point where the conservation modulus (G') and the loss modulus (G) have the same value. This point is also called the transition point from a sol-gel state.

Preferably, the composition according to the present invention as a gel has 8% or more deformation of the intersection point, and more preferably 12% or more of the intersection point. In one embodiment, the point of intersection of the composition according to the present invention is 100% strain or less, and preferably 50% or less, and even more preferably 30% strain or less.

The linear viscoelastic region is a region where the G' or G" values are constant at low strain (%). A gel composition preferably has 0 Pa or more linear viscoelastic regions of G' and G" on a logarithmic scale. In one embodiment, the composition according to the present invention as a gel may have 10 ⁴ Pa or less of the linear viscoelastic region, preferably 10 ³ Pa or more of the linear viscoelastic region on a logarithmic scale. The linear viscoelastic region can be measured in the same way as the intersection point.

The modulus of the linear viscoelastic region and the point of intersection can be measured, for example, by plotting the G' and G" values of a gel sample versus strain (%) in an amplitude scan of the shear stress at a constant frequency In the present invention, the intersection point can be measured using a 40 mm cone plane rheometer and under the following conditions:

Adjust the spacing: 30 μm

Temperature: 25°C

Deformation (%): 0.01/1000%

Frequency: 1Hz

Furthermore, the composition according to the present invention as a gel can exhibit very low hysteresis. Hysteresis here means a difference between an initial viscosity and a final viscosity after the application of a shear force. For example, hysteresis can be measured by applying a cyclic shear force while measuring viscosity. Since the composition according to the present invention as a gel may exhibit very low hysteresis, the composition may possess a shape memory gel-like characteristic.

It is preferable that the composition according to the present invention is an anhydrous composition. The anhydrous composition may comprise a limited amount of water, preferably less than 5% by weight, preferably less than 3% by weight, and more preferably less than 1% by weight or less, relative to the total weight of the composition. . It is particularly preferable that the composition according to the present invention does not contain water.

{Particle with micro-protrusion}

The composition according to the present invention comprises (a) at least one particle having at least one micro-protrusion. Only one type of particle having at least one micro-protrusion can be used, but two or more different types of particles having at least one micro-protrusion can be used in combination.

The shape and size of the (a) particle having at least one micro-protrusion are not limited. It is preferable that the (a) particle having at least one micro-protuberance has a size ranging from 100 to 600 microns, preferably from 200 to 500 microns, and more preferably from 300 to 400 microns. “Size” refers to the greatest length of the (a) particle.

The number of micro-protrusions of the (a) particle is not limited. It is preferable that the (a) particle has one or two micro-protuberances, and more preferably one micro-protuberance.

The shape of the micro-protrusion of the (a) particle is not limited. It is preferable that the micro-protrusion is designed to penetrate or enter a keratinous substance, preferably the stratum corneum of the skin, particularly the skin of the face, as well as the lips. If necessary, the shape of the micro-protuberance can be adjusted so as to allow penetration of the epidermis and/or dermis of the skin, preferably of the epidermis, and more preferably of one of the layers of the skin. 'epidermis.

The micro-protrusion may have the same diameter at the tip as at the base or may be tapered in the direction from base to tip. The micro-protrusion may take the shape of a pyramid, cone, rod or pillar or a combination of these.

In one embodiment, the micro-protrusion may be in the form of a pyramid, such as a triangular pyramid, a square pyramid and a pentagonal pyramid. The pyramid may include a distal end such as a tip, and a base. It may be preferable for the micro-protrusion to be in the form of a triangular pyramid and a square pyramid. The shape of the base can be a triangle or a square.

In another embodiment, the micro-protuberance can be in the form of a cone. The cone may include a distal end such as a tip and a base. The base can be a circle or an oval. The tip of the cone may have an angle of 5 to 90 degrees, preferably 10 to 60 degrees, and more preferably 15 to 45 degrees.

Alternatively, the microneedle can also be in the shape of a cylinder, preferably with a tip which can be formed by cutting the cylinder diagonally. The section of the micro-protrusion may take any geometric shape, including circular, triangular, square, rectangular, polyhedral, regular or irregular, and the like. In one embodiment, a micro-protuberance may take the form of hollow microcapillaries. However, for the present invention, solid (not hollow) microneedles may be preferable.

It is preferable that the (a) particle having at least one micro-protuberance has at least one sharp edge. The sharp edge(s) may lead to a modification of the surface of a keratinous substance such as the structure of the stratum corneum.

It is preferable that the (a) particle itself forms a micro-protrusion. For example, the (a) particle itself may be in the shape of a pyramid, a cone, a pillar rod, or a combination of these. It is preferable that the (a) particle is in the form of a pyramid or a cone, and more preferably a cone.

The micro-protuberance may have a height of between 100 and 600 microns, preferably between 200 and 500 microns, and more preferably between 300 and 400 microns.

The base of the micro-protuberance may have a width of 50 to 500 microns, preferably 1000 to 300 microns, and more preferably 150 to 250 microns.

The ratio (height of the micro-protrusion)/(width of the base of the micro-protuberance) of the micro-protuberance may be 1 or more, preferably 1.3 or more, and more preferably 1.6 or more .

The quantity of the particle(s) having at least one micro-protrusion in the composition according to the present invention may be 1% by weight or more, preferably 3% by weight or more, and more preferably 5% by weight or more, relative to the total weight of the composition.

The quantity of the particle(s) having at least one micro-protrusion in the composition according to the present invention may be 25% by weight or less, preferably 20% by weight or less, and more preferably 15% by weight or less, relative to the total weight of the composition.

The quantity of the particle(s) presenting at least one micro-protuberance in the composition according to the present invention may be from 1% to 25% by weight, preferably from 3% to 20% by weight, and more preferably from 5% to 15% by weight, relative to the total weight of the composition.

The (a) particle having at least one micro-protuberance comprises:

(a-1) at least one water-soluble or water-dispersible polymer; And

(a-2) at least one coloring agent.

(Water soluble or water dispersible polymer)

The (a) particle having at least one micro-protrusion comprises (a-1) at least one water-soluble or water-dispersible polymer. Only one type of water-soluble or water-dispersible polymer may be used, but two or more different types of water-soluble or water-dispersible polymers may be used in combination.

Here, the terms “water soluble” and “water dispersible” mean soluble and dispersible, respectively, when in contact with water.

It is preferable that the (a-1) water-soluble or water-dispersible polymer is soluble or dispersible in a keratinous substance, and more preferably in the surface layer of the keratinous substance, such as the skin and the lips. . Thus, in one embodiment of the present invention, the (a-1) water-soluble or water-dispersible polymer is capable of being dissolved or dispersed after insertion into a keratinous substance such as the skin and the lips. Due to the solubility and dispersibility of the polymer, the (a) particle having at least one micro-protrusion can effectively release the (a-2) coloring agent into the (a) particle.

The (a-1) water-soluble or water-dispersible polymer can be chosen from hyaluronic acids (in particular hyaluronic acid of lower molecular weight), monosaccharides, disaccharides, oligosaccharides, polysaccharides ( including their derivatives such as cellulose and their derivatives, in particular hydroxymethylcellulose), dextrins, dextrans, polyethylene glycols, polyvinyl alcohols, poly(methylvinylether/maleic anhydride), polyvinylpyrrolidone, poly(methyl/ vinyl ether/maleic acid) (PMVE/MA) and its esters, poly(methyl/ether/maleic anhydride) (PMVE/MAH) and their compounds.

The (a-1) water-soluble or water-dispersible polymer may have a molecular weight of 10,000 to 400,000 Dalton, preferably 30,000 to 300,000 Dalton, and more preferably 50,000 to 200,000 Dalton.

The low molecular weight hyaluronic acid may have a molecular weight less than or equal to 100 kDa, preferably less than or equal to 70 kDa, and more preferably less than or equal to 50 kDa.

The polyvinylpyrrolidone may have a molecular weight of between 1 kDa and 300 kDa, preferably between 5 kDa and 200 kDa, and more preferably between 7 kDa and 100 kDa.

Poly(methyl/vinyl ether/maleic acid) (PMVE/MA) and its esters, and poly(methyl/vinyl ether/maleic anhydride) (PMVE/MAH) are known as Gantrez-type polymers.

The quantity (dry basis) of the (a-1) water-soluble or water-dispersible polymer(s) may be 50% by weight or more, preferably 60%. by weight or more and, more preferably, 70% by weight or more, relative to the total weight of the (a) particle. The quantity (dry basis) of the (a-1) water-soluble or water-dispersible polymer(s) in the (a) particle having at least one micro-protrusion can be 100% by weight or less, preferably 98% by weight or less, and more preferably 96% by weight or less, relative to the total weight of the (a) particle. Thus, the quantity (dry basis) of the (a-1) polymer(s) soluble in water or dispersible in water(s) in the (a) particle having at least one micro-protuberance can be comprised from 50% to 100% by weight, preferably from 60% to 98% by weight, and more preferably from 70% to 96% by weight, relative to the total weight of the (a) particle.

The (a) particle having at least one micro-protuberance may comprise at least one material which is inflatable, more preferably inflatable in water, and even more preferably inflatable in a keratinous substance such as skin and lips. The above material may be a polymer which is swellable, more preferably swellable in water and even more preferably swellable in the keratinous substance. Here, the term “water inflatable” means inflatable when in contact with water. The above swellable material or polymer can exhibit high swelling capacity such that it can swell at least more than 10 times in a 1 hour in vitro incubation in physiological saline or phosphate buffered saline, preferably at least 20 times in 1 hour incubation, more preferably at least 30 times in 1 hour incubation, even more preferably at least 40 times in 1 hour incubation, and preferably approximately 45 to 55 times in 1 hour incubation.

The above swellable material, preferably the above swellable polymer, can have high viscoelasticity so that it can form a gel after in vitro incubation in physiological saline or phosphate-buffered saline. The gel has a high elastic modulus G', a high viscosity modulus G'', a tangent (δ) (Tangent (δ) = G''/G') less than 1 and a high consistency G* (G *2=G'2 + G''2) even at low frequency (0.01 Hz) during a dynamic frequency sweep test with a rheometer.

In one embodiment, the above inflatable material, preferably the inflatable polymer, is not soluble in water or not dispersible in water.

In another embodiment, the above inflatable material, preferably the inflatable polymer, may be a hydrogel-forming polymer.

The above swellable polymer can be selected from high molecular weight hyaluronic acids, cross-linked hyaluronic acids, cross-linked polyethylene glycol, cross-linked poly lactic acid or poly glycolic acid or poly actic-co-glycolic acid or polydioxanone, poly (styrene)-poly-block (acrylic acid), cross-linked polyethylene glycol PMVE/MA, cross-linked polyvinylpyrrolidone, sodium starch glycolate; cellulose; natural and synthetic gums; alginates; cross-linked poly(methyl/vinyl ether/maleic acid) (PMVE/MA) sodium polyacrylate PEG and its esters, cross-linked poly(methyl/vinyl ether/maleic anhydride) PEG (PMVE/MAH) and its esters, and mixtures thereof .

The high molecular weight hyaluronic acid may have a molecular weight greater than 500 kDa, preferably greater than 1000 kDa, and more preferably greater than 2100 kDa, and preferably less than 10,000 kDa.

Unless otherwise stated, molecular weight herein means number average molecular weight.

Poly(methyl/vinyl ether/maleic acid) (PMVE/MA) and its esters, and poly(methyl/vinyl ether/maleic anhydride) (PMVE/MAH) are known as Gantrez-type polymers.

The quantity (dry basis) of the inflatable material(s) in the (a) particle having at least one micro-protuberance may be 1% by weight or more, preferably 5% by weight or more, and more preferably 10% by weight or more, relative to the total weight of the (a) particle. The quantity (dry basis) of the inflatable material(s) in the (a) particle having at least one micro-protrusion may be 30% by weight or less, preferably 25% by weight or less, and more preferably 20% by weight or less, relative to the total weight of the (a) particle. Thus, the quantity (dry basis) of the inflatable material(s) in the (a) particle having at least one micro-protuberance can be from 1% to 30% by weight, preferably from 5% to 25%. % by weight, and more preferably from 10% to 20% by weight, relative to the total weight of the (a) particle.

(Coloring agent)

the (a) particle having at least one micro-protuberance comprises (a-2) at least one coloring agent. Only one type of coloring agent may be used, but two or more different types of coloring agents may be used in combination.

As used herein, "coloring agent" includes all synthetic or natural, organic or inorganic pigments, dyes or lacquers, as well as all other coloring agents approved by the CTFA and FDA.

In one embodiment, the (a-2) coloring agent may be selected from dyes, pigments and mixtures thereof.

In the present invention, the (a-2) coloring agent may be water soluble or water dispersible, oil soluble or oil dispersible or with limited water solubility.

In one embodiment, the (a-2) coloring agent can be chosen from coloring pigments.

The term “coloring pigments” must be understood as white or colored particles, inorganic or organic, of any shape, which are insoluble and intended to color or dye the lips.

Pigments can be white or colored, inorganic and/or organic.

Among the inorganic pigments which can be used, mention may be made in a non-limiting manner of titanium dioxide, optionally surface-treated, zirconium or cerium oxide, as well as zinc, iron or chromium oxide (black, yellow or red), manganese violet, ultramarine blue, chromium hydrate and ferric blue, or metallic powders, such as aluminum powder or copper powder. The pigments can also be chosen from nanopigments formed from metal oxides, such as titanium dioxide, zinc oxide, iron oxide, zirconium oxide and cerium oxide, and mixtures thereof. By “nanopigments” we mean pigments whose average particle size range is between 1 nm and 500 nm, such as for example particle sizes between 10 nm and 100 nm.

Among the organic pigments that can be used, we can cite, without limitation, carbon black, D&C type pigments and lacquers, such as lacquers based on cochineal carmine and barium, strontium, calcium or aluminum. For example, Red 33 (disodium 5-amino-4-hydroxy-3-(phenylazo)-naphthalene-2,7-disulfonate) and Red 202 (bis[2-(3-carboxy-2-hydroxynephthylazo)-5-methylbenzenesulfonate calcium) can be used as a D&C type pigment.

The organic pigment can also be a diketopyrrolopyrrole (DPP) such as those described in documents EP-A-542669, EP-A-787730, EP-A-787731 and WO-A-96/08537.

The organic pigment can be chosen from bio-pigments such as BioChromaDerm® or BioChromaEyes® supplied by Biotic Phocea in France.

Preferably, the coloring pigment can be chosen from metal oxides such as titanium dioxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide and chromium oxide; manganese violet; Prussian blue; ultramarine blue; chromium hydrate; ferric blue; aluminum powder; copper powder; carbon black; D&C type pigments; lacquers; pearl pigments; and their mixtures.

By “pearl pigments”, we mean iridescent particles of any shape, such as particles produced by certain shellfish in their shell or even synthesized.

The pearl agents can be chosen from white pearl agents, such as mica coated with titanium dioxide or bismuth oxychloride, colored pearl agents, such as mica coated with iron oxide, mica coated with ferric blue or chromium oxide, mica coated with titanium oxide and an organic pigment of the aforementioned type, and pearling agents based on bismuth oxychloride.

In one embodiment, the microneedle may include high refractive index particles, interference particles, reflection particles, and light absorbing particles, particularly non-transparent particles or light path modifying particles. , as a coloring pigment, to avoid reflection. These particles can allow coloring or skin pigmentation of the skin or lips thanks to the optical properties of the particles.

In another embodiment, the (a-2) coloring agent may be selected from dyes. Dyes can be chosen from natural direct dyes and synthetic direct dyes.

A direct dye is a colored substance that does not require the use of an oxidizing agent to reveal its color.

In one embodiment, the (a-2) coloring agent may be selected from natural direct dyes.

The term “natural direct dye” means any dye or dye precursor of natural origin, produced by extraction (and optionally by purification) from a plant matrix or from an animal such as an insect. , optionally in the presence of natural compounds such as ash or ammonia.

As natural direct dyes, we can cite quinone dyes (such as lawsone and juglone), alizarin, purpurin, laccaic acid, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, indigoids such as indigo, sorghum, isatin, betanin, curcuminoids (such as curcumin), spinulosin, different types of chlorophyll and chlorophyllin, hematoxylin, hematein, brazilein, brazilin, safflower tinctures (such as carthamine), flavonoids (such as rutin, quercetin, catechin, epicatechin, morin, apigenidin and sandalwood), anthocyanins (such as apigeninidin and apigenin), carotenoids, tannins, orceins, sandalins and cochineal carmine.

It is also possible to use extracts or decoctions containing one or more natural direct tinctures, in particular extracts based on henna, curcuma longa extract, sorghum leaf sheath extract, haematoxylon campechianum extract, tea extract green, pine bark extract, cocoa extract, rosewood extract.

It is preferable that the natural direct dye is selected from the group consisting of curcuminoids, santalines, chlorophyllin, hematoxylin, hematein, brazilein, brazilin, sorghum, laccaic acid, lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, indigoids, isatin, spinulosin, apigenin, orcein, betanin, flavonoids, anthocyanins, and extracts or decoctions containing these compounds.

Alternatively, the natural direct dyes may be preferably chosen from, for example, hydroxylated quinones, indigoids, hydroxyflavones, santalins A and B, isatin and its derivatives, and brasilin and its hydroxylated derivative.

The hydroxylated quinones are preferably mono- or polyhydroxylated benzoquinones, naphthoquinones, and anthraquinones which are optionally substituted with groups such as alkyl, alkoxy, alkenyl, chloro, phenyl, hydroxyalkyl, and carboxyl.

The naphthoquinones are preferably lawsone, juglone, flavioline, naphtazarin, naphthopurpurin, lapachol, plumbagin, chloroplumbagin, droserone, shikonin, 2-hydroxy-3-methyl-1, 4-naphthoquinone, 3,5-dihydroxy-1,4-naphthoquinone, 2,5-dihydroxy-1,4-naphthoquinone, 2-methoxy-5-hydroxy-1,4-naphthoquinone and 3-methoxy-5-hydroxy-1,4-naphthoquinone.

The benzoquinones are preferably spinulosin, atromentin, aurentioglyocladine, 2,5-dihydroxy-6-methylbenzoquinone, 2-hydroxy-3-methyl-6-methoxybenzoquinone, 2,5-dihydroxy-3,6 -diphenylbenzoquinone, 2,3-dimethyl-5-hydroxy-6-methoxybenzoquinone and 2,5-dihydroxy-6-isopropylbenzoquinone.

The anthraquinones are preferably alizarin, quinizarin, purpurin, carminic acid, chrysophanol, kermesic acid, rhein, aloe emodin, pseudopurpurin, quinizarincarboxylic acid, emodin of frangula, 2-methylquinizarin, 1-hydroxyanthraquinone and 2-hydroxyanthraquinone.

The indigoids are preferably indigo, indirubin, isoindigo and Tyrian purple.

The hydroxyflavones are preferably quercetin and morin.

In another embodiment, the (a-2) coloring agent may be selected from synthetic direct dyes.

The term “synthetic direct dye” means any dye or dye precursor produced by chemical synthesis.

Direct dyeing may be selected from the group consisting of acidic (anionic) direct dyes, basic (cationic) direct dyes, and neutral (non-ionic) direct dyes.

Non-limiting examples of synthetic dyes include neutral (non-ionic), anionic (acidic) and cationic (basic) dyes such as azo, methine, carbonyl, azine, nitro(hetero)aryl or tri(hetero) direct dyes. arylmethane, porphyrins and phthalocyanines, alone or in mixture.

More particularly, azo dyes contain a functional group -N=N- whose two nitrogen atoms are not simultaneously involved in a cycle. However, it cannot be excluded that one of the two nitrogen atoms of the sequence -N=N- is involved in a cycle.

The dyes of the methine family are more particularly compounds comprising at least one sequence chosen from >C=C< and -N=C<, the two atoms of which are not simultaneously involved in a cycle. However, it is specified that one of the nitrogen or carbon atoms in the sequences can be involved in a cycle. More particularly, the dyes of this family result from compounds of the following types: true methine (comprising one or more of the aforementioned -C=C- sequences); azomethine (comprising at least one or more -C=N- sequences) with, for example, azacarbocyanines and their isomers, diazacarbocyanines and their isomers, tetraaza-carbocyanines; mono- and diarylmethane; indoamines (or diphenylamines); indophenols; and indoanilines.

With regard to the dyes of the carbonyl family, we can cite, for example, the synthetic dyes chosen from the dyes acridone, benzoquinone, anthraquinone, naphthoquinone, benzanthrone, anthranthrone, pyranthrone, pyrazolanthrone, pyrimidinoanthrone, flavanthrone, indanthrone, flavone, (iso)violanthrone, isoindolinone, benzimidazolone, isoquinolinone, anthrapyridone, pyrazoloquinazoline, perinone, quinacridone, quinophthalone, naphthalimide, anthrapyrimidine, diketopyrrolopyrrole or coumarin.

With regard to dyes of the cyclic azine family, mention may be made in particular of azine, xanthene, thioxanthene, fluorindine, acridine, (di)oxazine, (di)thiazine or pyronine dyes.

Nitro(hetero)aromatic dyes are more particularly direct nitrobenzene or nitropyridine dyes.

With regard to porphyrin or phthalocyanine type dyes, cationic or non-cationic compounds optionally comprising one or more metals or metal ions, such as, for example, alkali and alkaline earth metals, zinc and silicon can be used. .

As examples of particularly suitable synthetic direct dyes, mention may be made of nitrobenzene dyes, azo, azomethine or methine direct dyes, azacarbocyanines, such as tetraazacarbocyanines (tetraazapentamethines), quinone and in particular anthraquinone, naphthoquinone or benzoquinone, or the direct tinctures azine, xanthene, triarylmethane, indoamine, phthalocyanine and porphyrin, alone or in mixture. even more preferably, these synthetic direct dyes are chosen from nitrobenzene dyes, azo, azomethine or methine direct dyes and tetraazacarbocyanines (tetraazapentamethines); alone or in mixtures.

Among the direct azo, azomethine, methine or tetraazapentamethine dyes which can be used according to the present invention, mention may be made of the cationic dyes described in patent applications WO 95/15144, WO 95/01772 and EP 714 954; FR 2 189 006, FR 2 285 851, FR-2 140 205, EP 1 378 544 and EP 1 674 073.

Thus, we can particularly cite direct cationic dyes corresponding to the following formulas:

in which :

D represents a nitrogen atom or the -CH group,

R ₁ and R ₂ , which are identical or different, represent a hydrogen atom; a C ₁ -C ₄ alkyl radical which may be substituted by a -CN, -OH radical or an -NH ₂ radical or may form, with a carbon atom of the benzene ring, a heterocycle optionally comprising oxygen or nitrogen which may be substituted by one or more C ₁ -C ₄ alkyl radicals; or a 4'-aminophenyl radical,

R ₃ and R' ₃ , which are identical or different, represent a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a cyano radical, a C ₁ alkyl radical -C ₄ , a C ₁ alkoxy radical -C ₄ an acetyloxy radical,

X ^- represents an anion, preferably chosen from chloride, methyl sulfate and acetate,

A represents a group chosen from the following structures:
in which R ₄ represents a C ₁ -C ₄ alyl radical which can be substituted by a hydroxyl radical;

in which :

R ₅ represents a hydrogen atom, a C ₁ -C ₄ alkoxy radical or a halogen atom, such as bromine, chlorine, iodine or fluorine,

R ₆ represents a hydrogen atom or a C ₁ -C ₄ alkyl radical or forms, with a carbon atom of the benzene ring, a heterocycle optionally comprising oxygen and/or optionally substituted by one or more alkyl groups in C ₁ -C ₄ ,

R ₇ represents a hydrogen atom or a halogen atom, such as bromine, chlorine, iodine or fluorine,

D ₁ and D ₂ , which are identical or different, represent a nitrogen atom or the -CH group,

m = 0 or 1,

X ^- represents a cosmetically acceptable anion preferably chosen from chloride, methyl sulfate and acetate,

E represents a group chosen from the following structures:

in which R' represents a C ₁ -C ₄ alkyl radical;

when m = 0 and when D ₁ represents a nitrogen atom, then E can also designate a group with the following structure:

in which R' represents a C ₁ -C ₄ alkyl radical.

Synthetic direct dye can be chosen from fluorescent dyes. Two or more types of fluorescent dyes can be used in combination.

The use of certain fluorescent dyes can make it possible to obtain, on dark hair, more visible colors than with traditional hydrophilic or hydrophobic direct dyes. Additionally, these fluorescent dyes, when applied to dark hair, can also help lighten hair without damaging it.

In this document, the term “fluorescent dyes” means fluorescent compounds and optical brighteners. In at least one embodiment, the fluorescent dye is soluble in the skin or lips.

Fluorescent dyes are fluorescent compounds that absorb visible radiation, for example wavelengths ranging from 400 to 800 nm, and are capable of re-emitting light in the visible range at a longer wavelength.

According to one embodiment, the fluorescent shades useful for the present invention re-emit orange-colored fluorescent light. They have, for example, a maximum re-emission wavelength of between 500 and 700 nm.

Non-limiting examples of fluorescent dyes include compounds known in the art, for example those described in Encyclopedia of Industrial Chemistry by Ullmann, Release 2004, 7th edition, chapter “Fluorescent Dyes”.

The optical brighteners of the present disclosure, also known as "brighteners", or "fluorescent brighteners", or "fluorescent brightening agents" or "FAAs", or "fluorescent whitening agents", or "whiteners", or "fluorescent whiteners", are colorless compounds that are transparent because they do not absorb in visible light but only in ultraviolet light (wavelength ranges from 200 to 400 nanometers) and convert the absorbed energy into fluorescent light of longer wavelength emitted in the visible part of the spectrum, generally in the blue and/or green, that is to say in wavelength ranges ranging from 400 to 550 nanometers.

Optical brighteners are known in the art, they are for example described in Encyclopedia of Industrial Chemistry by Ullmann (2002), “Optical Brighteners” and in Encyclopedia of Chemical Technology by Kirk-Othmer (1995): “Fluorescent whitening agents ".

Fluorescent dyes which may be used in the present invention include compounds known in the art, for example those described in French Patent No. 2,830,189.

The soluble fluorescent compounds which may in particular be cited include those belonging to the following families: naphthalimides, coumarins, xanthenes and in particular xanthenodiquinolizines and azaxanthenes; naphtholactams; azlactones; oxazines; thiazines; dioxazines; azo compounds; azomethines; methines; pyrazines; stilbenes; ketopyrroles; and pyrenes.

Where appropriate, fluorescent dyes are preferred, more particularly those re-emitting orange-colored fluorescent light.

In terms of ionic nature, direct dyeing can be chosen from the group consisting of acidic direct dyes, basic direct dyes and neutral direct dyes, which covers all possible types of direct dyes, such as nitro dyes and HC dyes as well as named. Acid direct dyes have an anionic moiety in their chemical structure. Basic direct dyes have a cationic moiety in their chemical structure. Neutral direct dyes are non-ionic.

In a preferred embodiment, the (a-2) coloring agent can be selected from dyes, preferably natural direct dyes, and more preferably coloring plant extracts.

Coloring plant extracts here refer to plant extracts capable of coloring. As coloring plant extracts, we can mention: carrot extract, gardena florida fruit extract, saffron extract, orange extract and tomato extract, in addition to those explained above for natural direct dyeing.

In particular, the (a-2) coloring agent can be chosen from the following compounds and their mixtures.

Color Trade name Chemical name Black Sunpuro C33-7001 Black Iron Oxide Iron oxide Black Unipure Triple Black Lc990 Iron oxide Black Unipure Black Lc902 Carbon black Black Wd-Cb2 Carbon black Black Black Nf Iron oxide Blue Suncroma Iron Blue C38-5410 Ferric ferrocyanide Blue Unipure Blue Lc 621 Blue 1 Lake Blue Unipure Blue Lc 686 Ultramarine blue Blue Unipure Blue Lc 520 Carmine Bordeaux Suncroma D&C Red 34 Ca Lake C24-012 Red 34 Lake Green Unipure Green Lc 788 Chromium Oxide Green Orange Suncroma Fd&C Yellow 6 Al Lac C70-5270 Yellow 6 Lake Pink Suncroma D&C Red 28 Al Lake C14-6623 Red 28 Lake Pink Dell Red C-14-6634 / Suncroma D&C Red 22 Al Lake C14-6634 Red 22 Lake Pink Unipure Pink Lc 589 Overseas Red Unipure Red Lc 3079 Gold Red 7 Red Carmine Covalac W 3508 / Cosmetic Carmine 09350 / Carmine Rmam 52% Carmine Red Unipure Red Lc 320 Carmihpc 54% Carmine Red Suncroma D&C Red 6 Ba Lake C-19-012 Red 6 Lake Red Suncroma D&C Red 6 Na Salt C19-6619 Na Red Salt 6 Red Suncroma D&C Red 7 Ca Lake C-19-003 Red 7 Lake Red Suncroma D&C Red 7 Ca Lake C19-011 Red 7 Lake Red Suncroma D&C Red 7 Ca Lake C19-025 Red 7 Lake Red Suncroma D&C Red 30al Lake C37-038 Red 30 Lake Red D&C Red 33 K7057 Red 33 Red Suncroma D&C Red 33 Al Lake C17-6444 Red 33 Lake Red Suncroma Fd&C Red 40 Al Lake C37-6340 Red 40 Lake Red Sunpuro C33-8001 Red Iron Oxide Iron oxide Red Unipure Red Lc 383 Iron oxide Purple Unipure Violet Lc 581 Manganese violet Purple Unipure Violet Lc 587 Ultramarine purple Purple Unipure Blue Lc 520 Carmine White Hombitan Anatase Ff Pharma Titanium dioxide White HOMBITAN AFDC300 Titanium dioxide White Tipaque Pf-671 Titanium dioxide White Tipaque Pfc407 Titanium dioxide White Sachtleben Rc 402 Titanium dioxide White KRONOS 1171 Titanium dioxide White Tipaque Cr-50 Titanium dioxide YELLOW Suncroma Fd&C Yel 5 Al Lk C69-4424 Yellow 5 Lake YELLOW Fd&C Yel 5 Al W001 Yellow 5 Lake YELLOW Suncroma Fd&C Yel 5 Al Lk C69002 Yellow 5 Lake YELLOW Unipure Yellow Lc124 Yellow 10 Lake YELLOW Sunpuro C33-9001 Yellow Iron Oxide Iron oxide YELLOW Suncroma Fd&C Yellow 6 Al Lac C70-5270 Yellow 6 Lake

The amount of the (a-2) coloring agent in the microneedle of the microneedle sheet according to the present invention is not limited.

The quantity (dry basis) of the (a-2) coloring agent(s) in the (a) particle having at least one micro-protrusion may be 0.01% by weight or more, preferably of 0.1% by weight or more, and more preferably of 1% by weight or more, relative to the total weight of the (a) particle. The quantity (dry basis) of the (a-2) coloring agent(s) in the (a) particle having at least one micro-protrusion may be 20% by weight or less, preferably 15 % by weight or less and, more preferably, 10% by weight or less, relative to the total weight of the (a) particle. Thus, the quantity (dry basis) of the (a-2) coloring agent(s) in the (a) particle having at least one micro-protuberance can be from 0.01% to 20% by weight , preferably from 0.1% to 15% by weight, and more preferably from 1% to 10% by weight, relative to the total weight of the (a) particle.

(Cosmetic active ingredient)

the (a) particle having at least one micro-protuberance may also comprise at least one cosmetic active ingredient.

The type of cosmetic active ingredient is not limited. The cosmetic active ingredient may be selected from the group consisting of hyperpigmentation agents such as tranexamic acid, kojic acid, etc., whitening agents, antioxidants, cleansing agents, anti-aging agents, treatment agents. skin texture, hair growth agents such as aminexil and combinations thereof. As examples of the anti-aging agent, mention may be made of antioxidants, moisturizers, free radical scavengers, keratolytic agents such as alpha or beta hydroxy acids, vitamins such as vitamin C and its derivatives. and vitamins E and its derivatives, anti-elastase and anti-collagenase agents, proteins, fatty acid derivatives, steroids, trace elements, whitening agents, vegetable oils such as coconut oil. almond, algae and plankton extracts, enzymes and coenzymes, flavonoids and ceramides, and mixtures thereof.

(Preparation)

The (a) particle having at least one micro-protrusion can be prepared, for example, by a molding process or a droplet process produced by air blowing. These methods are known for the preparation of microneedles. For example, in the molding process, a mixture of a solvent, at least one water-soluble polymer or a water-dispersible polymer, and at least one dye may be poured into one or more cavities to prepare one or more micro-protrusions of one or more molds which can be prepared, for example, by silicones. When completely dried under vacuum to remove the solvent, the solid micro-protrusion(s) can be collected in the cavity(ies) of the mold(s) by vacuum suction.

(Oil)

The composition according to the present invention comprises (b) at least one oil. Two or more (b) oils may be used in combination. Thus, a single type of oil or a combination of different types of oils can be used.

Here, “oil” means a compound or fatty substance which is in the form of a liquid or paste (not solid) at room temperature (25°C) under atmospheric pressure (760 mmHg). As oils, those generally used in cosmetics can be used alone or in combination. These oils can be volatile or non-volatile.

The (b) oil may be a non-polar oil such as a hydrocarbon oil, a silicone oil or the like; a polar oil such as a vegetable or animal oil and an ester oil or an ether oil; or a mixture of these.

The (b) oil may be selected from the group consisting of oils of vegetable or animal origin, synthetic oils, silicone oils, hydrocarbon oils and fatty alcohols.

As examples of vegetable oils, we can cite apricot oil, linseed oil, camellia oil, macadamia nut oil, corn oil, mink, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond, rapeseed oil, sesame oil, soybean oil, peanut oil and mixtures thereof.

Examples of animal oils include squalene and squalane.

Examples of synthetic oils include alkane oils such as isododecane and isohexadecane, ester oils, ether oils and artificial triglycerides.

The ester oils are preferably liquid esters of saturated or unsaturated, linear or branched C ₁ -C ₂₆ aliphatic monoacids or polyacids and of saturated or unsaturated, linear or branched C ₁ -C _{26 aliphatic monoalcohols or polyalcohols,} the total number of carbon atoms of the esters being greater than or equal to 10.

Preferably, for esters of monoalcohols, at least one of the alcohol and the acid from which the esters of the present invention originate is branched.

Among the monoesters of monoacids and monoalcohols, mention may be made of ethyl palmitate, ethylhexyl palmitate, isopropyl palmitate, dicaprylyl carbonate, alkyl myristates such as isopropyl myristate or myristate ethyl stearate, isocetyl stearate, 2-ethylhexyl isononanoate, isononyl isononanoate, isodecyl neopentanoate and isostearyl neopentanoate.

It is also possible to use esters of C ₄ -C ₂₂ dicarboxylic or tricarboxylic acids and of C ₁ -C _{22 alcohols,} as well as esters of monocarboxylic, dicarboxylic or tricarboxylic acids and of dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy. non-sugar C ₄ -C ₂₆ alcohols.

Mention may in particular be made of the following compounds: diethyl sebacate; isopropyl lauroyl sarcosinate; diisopropyl sebacate; bis(2-ethylhexyl) sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; bis(2-ethylhexyl) adipate; diisostearyl adipate; bis(2-ethylethylethylyl) maleate; triisopropyl citrate; triisocetyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; neotyl glycol diheptanoate; Diethylene glycol diisononanoate.

As ester oils, it is possible to use sugar esters and diesters of C ₆ - C ₃₀ and preferably C ₁₂ - C ₂₂ fatty acids. It is recalled that the term "sugar » designates oxygenated hydrocarbon compounds containing several alcohol functions, with or without aldehyde or ketone functions, and comprising at least 4 carbon atoms. These sugars can be monosaccharides, oligosaccharides or polysaccharides.

Examples of suitable sugars which may be mentioned include sucrose, glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose and their derivatives, particularly alkylated derivatives, such as methyl derivatives, for example methylglucose.

The sugar esters of fatty acids can be chosen in particular from the group comprising the esters or mixtures of esters of the sugars described above and of linear or branched, saturated or unsaturated C ₆ - C _{30 fatty acids,} and preferably in C ₁₂ - C _22. If unsaturated, these compounds may have one to three conjugated or unconjugated carbon-carbon double bonds.

The esters according to this variant can also be selected from monoesters, diesters, triesters, tetraesters, polyesters and mixtures thereof.

These esters can be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates, or mixtures of the latter such as, in particular, mixed esters of oleopalmitate, oleostearate and palmitostearate, as well as tetraethyl pentaerythrityl hexanoate.

More particularly, monoesters and diesters are used and in particular monooleates or dioleates, stearates, behenates, oleopalmitates, linoleates, linolenates and oleostearates of sucrose, glucose or methylglucose.

An example that can be mentioned is the product marketed under the name Glucate® DO by the company Amerchol which is a methylglucose dioleate.

As examples of preferred ester oils, mention may be made, for example, of diisopropyl adipate, dioctyl adipate, 2-ethylhexyl hexanoate, ethyl laurate, cetyl octanoate, octyldodecyl octanoate, isodecyl neopentanoate, myristyl propionate, 2-ethylhexyl 2-ethylhexanoate, 2-ethylhexyl-octanoate, 2-ethylhexyl caprylate/caprate, methyl palmitate, 2-ethylhexyl palmitate ethyl, isopropyl palmitate, dicaprylyl carbonate, isopropyl lauroyl sarcosinate, isononyl isononanoate, ethylhexyl palmitate, isohexyl laurate, hexyl laurate, isocetyl stearate , isopropyl isostearate, isopropyl myristate, isodecyl oleate, glyceryl tri(2-ethylhexanoate), pentaerythrithyl tetra(2-ethylhexanoate), 2-ethylhexyl succinate, sebacate diethyl, cetearyl isononanoate and mixtures thereof.

As examples of artificial triglycerides, mention may be made, for example, of capryl caprylyl glycerides, glyceryl trimyristate, glyceryl tripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate , glyceryl tri(caprate/caprylate) and glyceryl tri(caprate/caprylate/linolenate).

Examples of silicone oils include linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane and the like; cyclic organopolysiloxanes such as cyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like; and their mixtures.

Preferably, the silicone oil is chosen from liquid polydialkylsiloxanes, in particular liquid polydimethylsiloxanes (PDMS) and liquid polyorganosiloxanes comprising at least one aryl group.

These silicone oils can also be organomodified. The organomodified silicones which can be used for the present invention are silicone oils as defined above and comprise in their structure one or more organofunctional groups attached via a hydrocarbon group.

Organopolysiloxanes are defined in more detail in Walter Noll’s Chemistry and Technology of Silicones (1968), Academic Press. They can be volatile or non-volatile.

When they are volatile, the silicones are more particularly chosen from those having a boiling point of between 60°C and 260°C, and more particularly from:

(i) cyclic polydialkylsiloxanes comprising from 3 to 7 and preferably from 4 to 5 silicon atoms. These are, for example, octamethylcyclotetrasiloxane sold in particular under the name Volatile Silicone® 7207 by Unioncarbure or Silbione® 70045 V2 by Rhodia, decamethylcyclopentasiloxane sold under the name Volatile Silicone® 7158 by Unioncarbure, Silbione® 70045 V5 by Rhodia , and dodecamethylcyclopentasiloxane sold under the name Silsoft 1217 by Momentive Performance Materials, and mixtures thereof. We can also cite cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type, such as Silicone Volatile® FZ 3109 marketed by the company Union Carbide, of formula:

Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organosilicon compounds, such as the mixture of octamethylcyclotetrasiloxane and tetramethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1,1'-bis(2,2 ',2',2',3,3'-hexatrimethylsilyloxy)neopentane; And

(ii) linear volatile polydialkylsiloxanes containing 2 to 9 silicon atoms and having a viscosity less than or equal to 5×10 ^-6 m ² /s at 25 °C. An example is decamethyltetrasiloxane marketed in particular under the name SH 200 by the company Toray Silicone. Silicones belonging to this category are also described in the article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics . The viscosity of silicones is measured at 25°C in accordance with ASTM 445 Annex C.

Non-volatile polydialkylsiloxanes can also be used. These non-volatile silicones are more particularly chosen from polydialkylsiloxanes, among which we can mainly cite polydimethylsiloxanes containing terminal trimethylsilyl groups.

Among these polydialkylsiloxanes, the following commercial products may be cited, without limitation:

- Silbione ^® oils from the 47 and 70 047 ranges or Mirasil ^® oils sold by Rhodia, for example 70 047 V 500 000 oil;

- oils from the Mirasil ^® range sold by the company Rhodia;

- oils from the 200 range from the Dow Corning company, such as DC200 with a viscosity of 60,000 mm ² /s; And

- Viscasil ^® oils from General Electric and certain oils from the SF range (SF 96, SF 18) from General Electric.

We can also cite polydimethylsiloxanes containing dimethylsilanol end groups known under the name dimethiconol (CTFA), such as the 48 series oils from the company Rhodia.

Among the silicones containing aryl groups, mention may be made of polydiarylsiloxanes, in particular polydiphenylsiloxanes and polyalkylarylsiloxanes such as a phenyl silicone oil.

The phenyl silicone oil can be chosen from phenyl silicones of the following formula:

in which

R ₁ to R ₁₀ are, independently of each other, saturated or unsaturated, linear, cyclic or branched C ₁ -C ₃₀ hydrocarbon radicals, preferably C ₁ -C ₁₂ hydrocarbon radicals and more preferably, hydrocarbon radicals in C ₁ -C ₆ , in particular methyl, ethyl, propyl or butyl radicals, and

m, n, p and q are, independently of each other, integers from 0 to 900 inclusive, preferably from 0 to 500 inclusive and more preferably, from 0 to 100 inclusive,

provided that the sum n+m+q is not 0.

The products marketed under the following names are examples that can be cited:

- Silbione® oils from the 70 641 range from Rhodia;

- oils from the Rhodorsil® 70 633 and 763 ranges from Rhodia;

- Dow Corning 556 Cosmetic Grade Fluid oil from Dow Corning;

- silicones from Bayer's PK range, such as the PK20 product;

- certain oils from the General Electric SF range, such as SF 1023, SF 1154, SF 1250 and SF 1265.

As phenyl silicone oil, phenyl trimethicone (R ₁ to R ₁₀ are methyl; p, q and n = 0; m = 1 in the formula above) is preferable.

Organomodified liquid silicones may in particular contain polyethyleneoxy and/or polypropyleneoxy groups. We can thus cite the KF-6017 silicone offered by Shin-Etsu, and the Silwet® L722 and L77 oils from the Union Carbide company.

Hydrocarbon oils can be chosen from:

- linear or branched lower alkanes, optionally cyclic, in C ₆ - C _16. Examples which can be mentioned include hexane, undecane, dodecane, tridecane and isoparaffins, for example isohexadecane, isododecane and isodecane; And

- linear or branched hydrocarbons containing more than 16 carbon atoms, such as liquid paraffins, liquid petroleum jelly, polydecenes and hydrogenated polyisobutenes such as Parleam® and squalane.

As preferred examples of hydrocarbon oils, mention may be made, for example, of linear or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oil (for example, liquid paraffin), paraffin, petroleum jelly or petrolatum, naphthalenes, and the like; hydrogenated polyisobutene, isoeicosane and decene/butene copolymer and mixtures thereof.

The term “fat” in fatty alcohol means the inclusion of a relatively large number of carbon atoms. Thus, alcohols which have 4 or more carbon atoms, preferably 6 or more, and preferably 12 or more carbon atoms, are included in the scope of fatty alcohols. Fatty alcohol can be saturated or unsaturated. Fatty alcohol can be linear or branched.

The fatty alcohol may have the structure R-OH in which R is chosen from saturated and unsaturated, linear and branched radicals containing from 4 to 40 carbon atoms, preferably from 6 to 30 carbon atoms and more preferably from 12 to 20 carbon atoms. In at least one embodiment, R may be chosen from C ₁₂ -C ₂₀ alkyl and C ₁₂ -C ₂₀ alkenyl groups. R may or may not be substituted by at least one hydroxyl group.

As examples of fatty alcohol, mention may be made of lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, oleyl alcohol, linoleyl alcohol, palmitoleyl alcohol, arachidonyl alcohol, erucyl alcohol and mixtures thereof.

It is preferable that the fatty alcohol is a saturated fatty alcohol.

Thus, the fatty alcohol can be chosen from saturated or unsaturated, linear or branched C ₆ -C ₃₀ alcohols, preferably saturated, linear or branched C ₆ -C ₃₀ alcohols, and more preferably, C 6 -C 30 alcohols. ₁₂ -C ₂₀ saturated, linear or branched.

The term “saturated fatty alcohol” here refers to an alcohol having a long aliphatic saturated carbon chain. It is preferable that the saturated fatty alcohol is chosen from any saturated C ₆ - C ₃₀ fatty alcohols, linear or branched. Among the saturated C ₆ - C ₃₀ fatty alcohols, linear or branched, saturated C ₁₂ - C ₂₀ fatty alcohols, linear or branched can be used preferably. Any saturated C ₁₆ - C ₂₀ fatty alcohol, linear or branched, can be more preferably used. Branched C ₁₆ - C ₂₀ fatty alcohols can be used even more preferentially.

As examples of saturated fatty alcohols, mention may be made of lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol and mixtures thereof. In one embodiment, cetyl alcohol, stearyl alcohol, octyldodecanol, hexyldecanol, or a mixture thereof (e.g., cetearyl alcohol) as well as behenyl alcohol, may be used. as a saturated fatty alcohol.

According to at least one embodiment, the fatty alcohol used in the composition according to the present invention is preferably chosen from octyldodecanol, hexyldecanol, and mixtures thereof.

the (b) oil can be chosen from a combination of volatile oil and non-volatile oil, preferably a combination of volatile non-silicone oil and fatty alcohol, and more preferably a combination of volatile hydrocarbon oil such as such as isododecane and isohecadecane and unsaturated fatty alcohol such as oleyl alcohol.

The quantity of the (b) oil(s) in the composition according to the present invention may be 50% by weight or more, preferably 60% by weight or more and, more preferably, 70% by weight or more, compared to the total weight of the composition.

The quantity of the (b) oil(s) in the composition according to the present invention may be 95% by weight or less, preferably 90% by weight or less and, more preferably, 85% by weight or less, relative to the total weight of the composition.

The quantity of the (b) oil(s) in the composition according to the present invention can be from 50% to 95% by weight, preferably from 60% to 90% by weight and, more preferably, from 70% to 95% by weight. 85% by weight, relative to the total weight of the composition.

(Organic lipophilic gelling agent)

The composition according to the present invention comprises (c) at least one organic lipophilic gelling agent. Two or more (c) organic lipophilic gelling agents may be used in combination. Thus, a single type of organic lipophilic gelling agent or a combination of different types of organic lipophilic gelling agents can be used.

The term “lipophilic” here means substances soluble in oils at a concentration of at least 1% by weight relative to the total weight of the oils at room temperature (25°C) and atmospheric pressure (10 ⁵ Pa).

The term “gelling agent” here refers to substances capable of thickening or gelling oils.

The (c) organic lipophilic gelling agent used in the present invention can be selected from styrene block copolymers, semi-crystalline polymers, glutamide-based compounds, polyamides and mixtures thereof.

Styrene block copolymers are hydrocarbon-based block copolymers. Styrene block copolymers are obtained from at least one styrene monomer and at least one olefin. The olefin may in particular be an ethylenically unsaturated elastomeric monomer. Examples of olefins which may be mentioned include ethylene carbide monomers, particularly containing one or two ethylenic unsaturations and containing from 2 to 5 carbon atoms, such as ethylene, propylene, butadiene, isoprene or pentadiene. Advantageously, the styrene block copolymer is an amorphous block copolymer of styrene and olefin.

Block copolymers comprising at least one styrene block and at least one block comprising units chosen from butadiene, ethylene, propylene, butylene and isoprene or a mixture thereof are especially preferred. According to a preferred embodiment, the styrene block copolymer is hydrogenated to reduce residual ethylenic unsaturations after polymerization of the monomers.

According to a preferred embodiment, the styrene block copolymer comprises at least one diblock copolymer, which is preferably hydrogenated, preferably chosen from styrene ethylene/propylene copolymers, styrene-ethylene-butadiene copolymers and styrene ethylene/butylene copolymers . The diblock polymers are notably sold under the name Kraton® GI 701 E by the company Kraton Polymers.

According to another preferred embodiment, the styrene block copolymer comprises at least one triblock copolymer, which is preferably hydrogenated, preferably chosen from styrene ethylene/propylene-styrene copolymers, styrene-ethylene/butadiene-styrene copolymers, styrene copolymers -isoprene-styrene and styrene-butadiene-styrene copolymers. The triblock polymers are notably sold under the names Kraton® G1650, Kraton® G1652, Kraton® G1657, Kraton® DI 101, Kraton® DI 102 and Kraton® DI 160 by the company Kraton Polymers.

The term “semi-crystalline polymers” here designates polymers comprising a crystallizable portion, a chain or a pendant sequence in the skeleton, and an amorphous part in the skeleton and having a reversible phase change temperature of first order, in particular a melting point (solid-liquid transition). When the crystallizable part is a sequence of the polymer backbone, this crystallizable sequence has a chemical nature different from that of the amorphous sequences; in this case, the semi-crystalline polymer is a block polymer, for example of the diblock, triblock or multiblock type.

In addition to crystallizable chains or sequences, polymer sequences are amorphous. The term “crystallizable chain or sequence” here designates a chain or sequence which, if it were alone, would go from the amorphous state to the crystalline state reversibly, depending on whether the temperature is above or below the melting point.

According to a specific embodiment of the present invention, the semi-crystalline polymer is chosen from the homopolymers obtained by polymerization of at least one monomer having a crystallizable chain, chosen from C ₁₄ - C alkyl (meth)acrylates _24, C ₁₁ - C ₁₅ perfluoroalkyl (meth)acrylates by alkyl, N-(C ₁₄ to C ₂₄ ) (meth)acrylamides with or without fluorine atom, vinyl esters having alkyl or perfluoroalkyl chains in C ₁₄ to C ₂₄ , vinyl ethers having C ₁₄ to C ₂₄ alkyl or perfluoroalkyl chains, C ₁₄ to C ₂₄ α-olefins or para-alkylstyrenes with a C ₁₄ to C ₂₄ alkyl group, and among copolymers of these monomers obtained by copolymerization of these monomers with a hydrophilic monomer, preferably other than methacrylic acid, such as, for example, N-vinylpyrrolidone, hydroxyethyl acrylate, hydroxyethyl methacrylate or acrylic acid. These copolymers may be, for example, copolymers of C ₁₄ -C ₂₄ alkyl acrylate, of C ₁₄ -C ₂₄ alkyl methacrylate, of C 14 -C 24 alkyl methacrylate or of C ₁₄ -C ₂₄ alkyl methacrylate. C ₁₄ -C ₂₄ alkyl with N-vinylpyrrolidone, hydroxyethyl acrylate, hydroxyethyl methacrylate or acrylic acid, or mixtures thereof.

The semi-crystalline polymers of the composition of the present invention may be non-crosslinked or partially crosslinked. Preferably, the semi-crystalline polymers of the composition according to the present invention are non-crosslinked.

According to a specific embodiment of the present invention, the semi-crystalline polymer is a homopolymer resulting from the polymerization of a monomer having a crystallizable chain chosen from C ₁₄ -C ₂₄ alkyl acrylates and alkyl methacrylates. in C ₁₄ -C ₂₄ . Mention may in particular be made of those sold under the name Intelimer® by Landec, described in the brochure Intelimer® Polymers , Landec IP22. These polymers are in solid form at room temperature. They carry crystallizable side chains and correspond to saturated homopolymers of C ₁₄ -C ₂₄ alkyl acrylate or methacrylate. Mention may be made more particularly of the stearyl acrylate homopolymer (Intelimer IPA-13.1) (INCI name: Poly C10-30 alkylacrylate) or the behenyl acrylate homopolymer (Intelimer IPA-13.6) (INCI name: Poly C10 -30 alkyl acrylate).

The glutamide compounds of the present invention are known to comprise a type of organic gelling agents. Preferably, the glutamide compounds of the present invention are non-polymeric.

Preferably, the glutamide-based compounds are non-polymeric and are chosen from: a low molecular weight dialkyl N-acylglutamide carrying a linear alkyl chain, chosen in particular from di(C2-C6)alkyl N-acylglutamides in which the acyl group comprises a linear C8 to C22 alkyl chain, preferably such as lauroylglutamic acid dibutylamide (or dibutyl lauroyl glutamide), and/or a low molecular weight dialkyl N-acylutamide carrying a branched alkyl chain, chosen in particular from di(C2-C6)alkyl N-acylglutamides in which the acyl group comprises a branched C8 to C22 alkyl chain, preferably such as N-2-ethylhexanoylglutamic acid dibutylamide

(or dibutyl ethylhexanoyl glutamide), and mixtures thereof.

Preferably, among the non-polymeric glutamide-based compounds that can be used, there are combinations of at least one low molecular weight dialkyl N-acylglutamide carrying a linear alkyl chain, chosen in particular from (C2-C6) dialkyl N-acylglutamides in which the acyl group comprises a linear C8 to C22 alkyl chain such as lauroylglutamic acid dibutylamide (dibutyl lauroyl glutamide), with at least one low molecular weight dialkyl Nacylglutamide carrying a branched alkyl chain, chosen in particular among (C2-C6)dialkyl Nacyacyalkyllutamides in which the acyl compound group comprises a C8 to C22 branched alkyl chain such as dibutyl ethylhexanoyl glutamide of N-2-ethylhexanoyl glutamic acid and preferably with a solvent capable of forming hydrogen bonds with these two glutamide-based compounds.

In preferred embodiments, the glutamide compound suitable for use in the present invention is Dibutyl Lauroyl Glutamide, known under the trade name GP-1 and sold by the Ajinomoto Company.

For the purposes of the present invention, the term “polyamide” designates a compound containing at least two amide repeat units, preferably at least three amide repeat units and better still ten amide repeat units.

In particular, the (c) organic lipophilic gelling agent of the present invention comprises at least one polyamide. The inventors of the present invention have surprisingly discovered that the use of polyamides as (c) organic lipophilic gelling agent can confer a very preferable viscoelasticity to the composition according to the present invention.

The polyamides of the present invention may be polyamide polycondensates. The term “polycondensate” designates in the terms of the present invention a polymer obtained by polycondensation, namely by chemical reaction between monomers having different functional groups chosen in particular from the acid, alcohol and amine functions.

The lipophilic polyamide polycondensates may in particular be chosen from polyamide polymers comprising a) a polymer skeleton which comprises hydrocarbon repeat units provided with at least one non-pending amide unit, and optionally b) at least one pendant fatty chain comprising 6 to 120 carbon atoms, preferably 8 to 120 carbon atoms, and more preferably 12 to 70 carbon atoms, and/or at least one terminal fatty chain which can be functionalized, comprising at least 4 carbon atoms and linked to these hydrocarbon patterns.

The term “functionalized chains” within the meaning of the present invention designates an alkyl chain comprising one or more functional or reactive groups chosen in particular from amide, hydroxyl, ether, oxyalkylene or polyoxyalkylene, halogen, including fluorinated or perfluorinated, ester, siloxane, polysiloxane. In addition, the hydrogen atoms of one or more fatty chains can be substituted at least partially by fluorine atoms.

The term “hydrocarbon repeat units” in the terms of the present invention designates a unit comprising from 2 to 80 carbon atoms, and preferably from 2 to 60 carbon atoms, carrying hydrogen atoms and optionally carbon atoms. oxygen, which can be linear, branched or cyclic, saturated or unsaturated. These units further comprise at least one amide group which is advantageously non-pending and which is found in the polymeric skeleton.

Advantageously, the pendant chains are directly connected to at least one of the nitrogen atoms of the polymer skeleton.

The lipophilic polyamide polycondensate may comprise, between the hydrocarbon units, silicone units or C ₂ -C ₃ oxyalkylene units.

Furthermore, the lipophilic polyamide polycondensate of the composition of the present invention advantageously comprises from 40 to 98% of fatty chains relative to the total number of amide units and fatty chains and more preferably from 50 to 95%.

Preferably, the pendant fatty chains are linked to at least one of the nitrogen atoms of the amide units of the polymer. In particular, the fatty chains of this polyamide represent 40 to 98% of the total number of amide units and fatty chains, and more preferably 50 to 95%.

Advantageously, the lipophilic polyamide polycondensate has an average molecular weight of less than 100,000 (in particular ranging from 1,000 to 100,000), in particular less than 50,000 (in particular ranging from 1,000 to 50,000), and more particularly ranging from 1,000 to 30,000, preferably from 2,000 to 20,000, and more preferably from 2,000 to 10,000.

Lipophilic polyamide polycondensate is not soluble in water or has a solubility of less than 1 g/l or 0.1 g/l in water, particularly at 25°C and atmospheric pressure. In particular, it does not include an ionic group.

As preferred lipophilic polyamide polycondensates which can be used in the present invention, mention may be made of polyamides branched by pendant fatty chains and/or terminal fatty chains comprising from 6 to 120 carbon atoms and more particularly from 8 to 120 and in particular from 12 to 68 carbon atoms, each terminal fatty chain being connected to the polyamide skeleton by at least one linking group L. The linking group L can be chosen from ester, ether, amine, urea, urethane groups , thioester, thioether, thiourea, thiourethane. Preferably, these polymers comprise a fatty chain at each end of the polyamide skeleton.

These polymers are preferably polymers resulting from a polycondensation between a dicarboxylic acid comprising at least 32 carbon atoms (which in particular comprises from 32 to 44 carbon atoms) with an amine chosen from diamines which comprise at least 2 carbon atoms (in particular from 2 to 36 carbon atoms) and triamines containing at least 2 carbon atoms (in particular from 2 to 36 carbon atoms). The diacid is preferably a dimer originating from an ethylenically unsaturated fatty acid containing at least 16 carbon atoms, preferably from 16 to 24 carbon atoms, such as oleic, linoleic or linolenic acid. The diamine is preferably ethylene diamine, hexylene diamine and hexamethylene diamine. Triamine is for example ethylene triamine. For polymers comprising one or 2 terminal carboxylic acid groups, it is advantageous to esterify them with a monoalcohol comprising at least 4 carbon atoms, preferably from 10 to 36 carbon atoms and more preferably from 12 to 24 and even more preferably from 16 to 24, for example 18 carbon atoms.

The lipophilic polyamide polycondensate of the composition according to the present invention may in particular be chosen from polymers corresponding to the following formula (A):

in which :

n is an integer varying from 1 to 30,

R' ₁ represents independently at each occurrence a fatty chain and is chosen from an alkyl or alkenyl group comprising at least 4 carbon atoms and in particular from 4 to 24 carbon atoms;

R' ₂ independently represents at each occurrence a divalent hydrocarbon chain comprising from 1 to 52 carbon atoms;

R' ₃ represents at each occurrence independently a divalent hydrocarbon group, saturated or unsaturated, cyclic or acyclic, optionally substituted and/or optionally interrupted by one or more heteroatoms preferably from oxygen and nitrogen comprising at least one carbon atom , R' ₃ represents in particular a linear or branched alkylene chain (C ₁ -C ₈ ); preferably linear alkylene (C ₁ -C ₆ ) such as ethylene;

R' ₄ represents independently at each occurrence: a hydrogen atom, an alkyl group comprising 1 to 10 carbon atoms, or a direct link with at least one group chosen between R' ₃ and another R' ₄ in such a way that when said group is another R' _4, the nitrogen atom to which R' ₃ and R' ₄ are connected is part of a heterocyclic structure defined by R' ₄ -N-R' _3, provided that at least 50% of R' ₄ represents a hydrogen atom, and

L represents a linking group preferably chosen from an ester or ether or amine or urea or urethane or thioester or thioether or thiourea or thiourethane group, optionally substituted by at least one group R' ₁ as defined above.

According to one embodiment, these polymers are chosen from polymers corresponding to formula (A) in which the linking group L represents an ester group -C(O)-O- or -O-C(O)-.

These polymers are more particularly those described in document US-A-5783657 from Union Camp.

Each of these polymers satisfies in particular the following formula (B):

in which :

- m designates an integer of an amide group such that the number of ester groups represents 10 to 50% of the total number of ester and amide groups;

- R ₁ represents independently at each occurrence an alkyl or alkenyl group comprising at least 4 carbon atoms and in particular from 4 to 24 carbon atoms;

- R ₂ represents at each occurrence independently a C ₄ to C ₄₂ hydrocarbon group provided that 50% of the R ₂ groups represent a C ₃₀ to C ₄₂ hydrocarbon group;

- R ₃ represents independently at each occurrence a divalent hydrocarbon group, saturated or unsaturated, cyclic or acyclic, optionally substituted and/or optionally interrupted by one or more heteroatoms preferably from oxygen and nitrogen comprising at least one carbon atom , in particular R ₃ represents a linear or branched alkylene chain (C ₁ -C ₈ ); preferably a linear alkylene (C ₁ -C ₆ ) such as ethylene; And

- R ₄ represents independently at each occurrence a hydrogen atom, a C ₁ to C ₁₀ alkyl group or a direct link with R ₃ or with another R ₄ such that the nitrogen atom to which R are linked ₃ and R ₄ is part of a heterocyclic structure defined by R ₄ -NR ₃ , with at least 50% of R ₄ representing a hydrogen atom.

In the particular case of formula (B), the terminal fatty chains possibly functionalized within the meaning of the present invention are terminal chains linked to the last nitrogen atom of the polyamide skeleton.

In particular, the ester groups of formula (B), which form part of the terminal and/or pendant fatty chains within the meaning of the present invention, represent from 15 to 40% of the total number of ester and amide groups and in particular from 20 to 40%. 35%.

In addition, m advantageously represents an integer ranging from 1 to 5 and more particularly greater than 2.

Preferably, R ₁ is a C ₁₂ to C ₂₂ and preferably C ₁₆ to C ₂₂ alkyl group. Advantageously, R ₂ can be a divalent hydrocarbon group, saturated or unsaturated, cyclic or acyclic, in particular R ₂ represents a linear or branched alkylene chain (C ₁₀ -C ₄₂ ). Preferably, at least 50% and, more preferably, at least 75% of the R ₂ radicals are groups comprising 30 to 42 carbon atoms. The other R ₂ are C ₄ to C ₁₉ and even C ₄ to C ₁₂ hydrocarbon groups.

Preferably, R ₃ represents a C ₂ to C ₃₆ hydrocarbon group or a polyoxyalkylene group and R ₄ represents a hydrogen atom. Preferably, R ₃ represents a C ₂ to C ₁₂ hydrocarbon group.

Hydrocarbon groups can be linear, cyclic or branched, saturated or unsaturated. In addition, the alkyl and alkylene groups can be linear or branched, saturated or unsaturated.

In general, the polymers of formula (B) are in the form of mixtures of polymers, these mixtures may also contain a synthesis product which corresponds to a compound of formula (B) where n is equal to 0, i.e. i.e. a diester.

According to a particularly preferred form of the present invention, a mixture of copolymers of a C36 diacid condensed on ethylene diamine will be used; the terminal ester groups result from the esterification of the endings of the remaining acid by cetyl, stearyl alcohol or their mixtures (also called cetylstearyl) (INCI name: Ethylenediamine/Stearyl Dimer Dilinoleate Copolymer). Its average molar mass by weight is preferably 6000, and even more preferably 4000. These mixtures are sold in particular by ARIZONA CHEMICAL under the trade names UNICLEAR 80 and UNICLEAR 100 VG respectively in the form of one to 80% (in material active) in a mineral oil and 100% (in active ingredient). These mixtures are also sold by CRODA under the trade name OLEOCRAFT LP-10-PA-(MV) respectively at 99.7% (active material) with a preservative. They have a softening point between 88°C and 94°C.

With regard to polyamide polycondensates which satisfy general formula (A), mention may also be made of polymers comprising at least one terminal fatty chain linked to the polymeric skeleton by at least one tertiary amide linking group (also called polyamide amide-terminated or ATPA). For more information on these polymers, refer to US 6503522.

According to a particularly preferred form of the present invention, use will be made more particularly of a copolymer of hydrogenated linoleic diacid, ethylenediamine, di(C14-C18)alkylamine(s) (INCI name: Ethylenediamide/Hydrogenated Dimer Dilinoleate Copolymer Bis-Di-C14-C18 Alkyl Amide). This copolymer is notably sold under the trade name SYLVACLEAR A200V by ARIZONA CHEMICAL.

According to another embodiment, the polyamide corresponding to formula (A) can also be a poly(ester-amide) with ester ends (poly(ester-amide) or ETPEA), such as for example those for which the preparation is described in document US 6552160.

According to a particularly preferred form of the present invention, use will be made more particularly of a copolymer of hydrogenated linoleic diacid, ethylenediamine, neopentyl glycol and stearyl alcohol (INCI name: Bis-Stearyl Ethylenediamine/Neopentyl Glycol/Stearyl Hydrogenated Dimer Dilinoleate Copolymer). This copolymer is notably sold under the trade name SYLVACLEAR C75 V by ARIZONA CHEMICAL.

As polyamide polycondensates which can be used in the present invention, mention may also be made of those which contain at least one terminal fatty chain linked to the polymeric skeleton by at least one ether or polyether linking group (we then speak of ether-terminated poly(ether)amide). These polymers are for example described in document US 6399713.

The polyamides in accordance with the present invention advantageously have a softening temperature greater than 65°C and which can go up to 190°C. Preferably, it has a softening temperature of between 70 and 130°C and preferably between 80 and 105°C. Polyamide is in particular a non-waxy polymer.

As polyamide polycondensates which can be used in the present invention, mention may also be made of polyamide resins resulting from the condensation of an aliphatic dicarboxylic acid and a diamine (including compounds which have more than 2 groups carbonyl and 2 amine groups), the carbonyl and amine groups of the adjacent unit units being condensed by an amide bond. These polyamide resins include those marketed under the Versamid brand by General Mills, Inc. and Henkel Corp. (Versamid 930, 744 or 1655) or by Olin Mathieson Chemical Corp., under the brand Onamid in particular Onamid S or C. These resins have an average molar mass ranging from 6000 to 9000. For more information on these polyamides, see refer to documents US 3645705 and US 3148125. More specifically, Versamid 930 or 744 is used.

The polyamides sold by Arizona Chemical under the references Uni-Rez (2658, 2931, 2970, 2621, 2613, 2624, 2665, 1554, 2623, 2662) can also be used and the product sold under the reference Macromelt 6212 by Henkel. For more information on these polyamides, refer to document US 5500209.

It is also possible to use polyamide resins from plants such as those described in patents US 5783657 and US 5998570.

Preferably, the lipophilic polyamide polycondensate is a copolymer of a C36 diacid condensed on ethylene diamine; the terminal ester groups result from the esterification of the remaining acid terminals by cetyl, stearyl alcohol or mixtures thereof.

The quantity of the organic gelling agent(s) in the composition according to the present invention may be 1% by weight or more, preferably 2% by weight or more, and more preferably 3% by weight or more, relative to the total weight of the composition.

The quantity of the organic gelling agent(s) in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less and, more preferably , 5% by weight or less, relative to the total weight of the composition.

The quantity of the organic gelling agent(s) in the composition according to the present invention may be from 1% to 15% by weight, preferably from 2% to 10% by weight, and more preferably from 3% to 5% by weight, relative to the total weight of the composition.

(Water soluble particle)

The composition according to the present invention comprises (d) at least one water-soluble particle. Two or more (d) water-soluble particles can be used in combination. Thus, a single particle type or a combination of different water-soluble particle types can be used.

The (d) water-soluble particle is different from the (a) particle having at least one micro-protrusion.

The expression "soluble in water" here means having a solubility of at least 1 g/L, preferably at least 10 g/L, and more preferably at least 100/L, in water at a pH of 7 at room temperature (25 °C) and atmospheric pressure (10 ⁵ Pa).

Preferably, the (d) water-soluble particles are insoluble in oil, that is to say they have a solubility less than 1 g/l, preferably less than 0.1 g/l , in oil.

The (d) water-soluble particle can have any shape: platelet, spherical, oblong or multiangular, whatever its crystallographic shape (e.g. lamellar, cubic, hexagonal, orthorhombic, etc.).

In a preferred embodiment, the (d) water-soluble particle may function as a water-soluble exfoliating particle. The (d) water-soluble particle as an exfoliating particle can physically disrupt a keratinous substance such as the skin, especially the stratum corneum. In this embodiment, the (d) water-soluble particle may be in the form of a hard, sharp-edged or rough surface particle. The sharp-edged particle may have a polypyramid shape. Furthermore, the sharp-edged particle can be in the form of a tetrahedron-shaped or pyramid-shaped microstructure. In addition, it is preferable that the surface of the particle is rough. Furthermore, the surface of the particle may be planar and/or may be hollow. Sharp edges or rough surface can cause a change in the surface of a keratinous substance such as the structure of the stratum corneum. The (d) water-soluble particle can be further dissolved by contact with water. After the (d) water-soluble particle is dissolved, the (a-2) coloring agent can be effectively penetrated into a keratinous substance such as skin and lips.

In specific embodiments of the present invention, the (d) water-soluble particle may have an aspect ratio of at least 1.1, preferably at least 1.2, and more preferably of at least 1.5, even more preferably at least 2, and in particular at least 2.5. In other embodiments of the present invention, the (d) water-soluble particle may have an aspect ratio of 10 or less, preferably 6 or less, and more preferably 4 or less. The side ratio can be measured by technology common in the art, for example, image analysis using an electron microscope.

In other specific embodiments of the present invention, the (d) water-soluble particle may have an average circularity determined by an image analysis method of 0.95 or less, preferably 0, 9 or less, and more preferably 0.85 or less, and even more preferably 0.8 or less. In other embodiments of the present invention, the water-soluble particles have an average circularity determined by an image analysis method of 0.5 or greater, preferably 0.55 or greater, more preferably 0.6 or more, and even more preferably 0.65 or more.

The “average circularity” can be determined by an image analysis process. In particular, the "average circularity" may be an arithmetic average of the circularity obtained by image analysis of a scanning electron microscope (SEM) image of not less than 2,000 particles observed at a magnification of 1,000 per detection secondary electrons using a scanning electron microscope (SEM).

The “circularity” of each particle is a value determined by the following formula:

C = 4πS / L ²

where C represents circularity, S represents an area (projected area) of the particle in the image, and L represents a length of a periphery (perimeter) of the particle in the image. When the average circularity approaches 1, the shape of each particle becomes more spherical.

The (d) water-soluble particle may have an average primary particle size of 10 μm or more, preferably 30 μm or more, more preferably 50 μm or more, and even more preferably 100 μm or more, and in particular 200 μm or more. The average primary particle size of the (d) water-soluble particle may be 1 mm or less, preferably 800 μm or less, and more preferably 600 μm or less, and even more preferably 500 μm or less.

The term “average primary particle size” used here represents an average diameter in volume average size which is given by the statistical particle size distribution at half the population, denoted by D ₅₀ . For example, the volume average size average diameter can be measured by a laser diffraction particle size distribution analyzer, such as Mastersizer 2000 from Malvern Corp.

Water-soluble particle (d) substances are not particularly limited as long as they dissolve upon contact with an aqueous component, such as water. However, in the cosmetic process according to the present invention, water is applied after the composition according to the present invention is applied to a keratinous substance such as skin and lips, and (c) the water-soluble particle is dissolved, and the (a-2) coloring agent which is released from the (a) particle having at least one micro-protuberance is penetrated into the keratinous substance.

Accordingly, the (d) water-soluble particle may comprise a polysaccharide, monosaccharide, amino acid or salt thereof, sugar alcohol, ascorbic acid or a mixture thereof.

The polysaccharide may include disaccharides, such as sucrose, lactose, maltose, and trisaccharides, such as raffinose, and mucopolysaccharides, such as hyaluronic acid, chondroitin sulfate, and heparin. Monosaccharide may include pentose, hexose and heptose, such as glucose, dextrose, galactose, mannose and glucuronic acid. Sugar alcohols may include sorbitol and glucamines. Ascorbic acids may include vitamin C.

The quantity of the water-soluble particle(s) in the composition according to the present invention may be 0.1% by weight or more, preferably 0.5% by weight or more, and more preferably 1% by weight or more, relative to the total weight of the composition.

The amount of the water-soluble particle(s) in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less and, more preferably, 5% by weight or less, relative to the total weight of the composition.

The quantity of the water-soluble particle(s) in the composition according to the present invention may be from 0.1% to 15% by weight, preferably from 0.5% to 10 % by weight and, more preferably, from 1% to 5% by weight, relative to the total weight of the composition.

(Optional ingredients)

The composition to be used for the cosmetic process according to the present invention may comprise, in addition to the aforementioned ingredients, optional ingredients generally used in cosmetics, specifically, surfactants or emulsifiers, hydrophilic thickeners, inorganic lipophilic thickeners, natural derivative extracts of animals or plants, waxes and the like, within a range which does not affect the effects of the present invention.

The composition to be used for the cosmetic process according to the present invention may comprise the optional additive(s) above in an amount of 0.01% to 50% by weight, preferably 0.05% to 30% by weight. weight, and more preferably from 0.1% to 10% by weight, relative to the total weight of the composition.

(Preparation)

The composition to be used for the present invention may be prepared, for example, by mixing the above essential ingredients and optional ingredient(s), if necessary, as explained above.

The method and means for mixing the above essential and optional ingredients are not limited. Any conventional method and means may be used to mix the above essential and optional ingredients to prepare the composition to be used for the present invention.

EXAMPLES

The present invention will be described in more detail using examples. However, these examples should not be interpreted as limiting the scope of the present invention. The examples below are presented as non-limiting illustrations in the field of the present invention.

Reference 1

(Preparation of particles presenting a micro-protuberance)

The particles exhibiting a micro-protrusion were prepared using a composition comprising the ingredients shown in Table 2.

Ingredient Concentration (% w/w) Hyaluronic acid (30 kDa) 10 Red 33 1 Water 89

The composition shown in Table 1 was poured into cavities of a mold where each of the cavities has a micro-protrusion shape and dries at room temperature. Then, the composition in the form of the micro-protrusion in each of the cavities was removed from the mold. The shape of the micro-protrusion is shown in Table 3.

Shape Base width (μm) 200 Height (μm) 370 Head angle (°) 30

Reference 2

(Preparation of the anhydrous composition)

An anhydrous composition was prepared by mixing the ingredients shown in Table 4.

Ingredient Concentration (% w/w) Particles prepared in reference 1 10.00 Sucrose 0.90 Oleyl alcohol 8.02 Ethylenediamine/Stearyl Dimeric Dilinoleate Copolymer 4.45 Isododecane 76.63

Example 1

(Treatments)

The anhydrous composition prepared in reference 2 was applied to the surface (1×1 cm ² ) of human cadaver skin. Then, the anhydrous composition was massaged with fingers for 1 minute. After the massage, the anhydrous composition was left on the skin for 15 minutes. Then the skin surface treated with the anhydrous composition was wiped with dry thin paper.

A photo of the surface of the skin was taken with a digital camera with a microscope at 100 times magnification before application of the anhydrous composition (see Fig. ) and just after wiping off the anhydrous composition (cf. ).

Then, water was placed on the surface of the skin treated with the anhydrous composition, followed by massage with the fingers. Then, the water-treated skin surface was wiped with a dry thin paper.

A snapshot of the skin surface was taken with a digital camera with a microscope at 100 times magnification immediately after wiping (see Fig. ).

Then, the skin surface was washed twice with 5 wt% sodium laureth sulfate (SLES) aqueous solution and a snapshot of the skin surface was taken with a digital camera with an optical microscope. a 100 times magnification just after each of the two washing steps (cf. and 5).

Then, Scotch ^TM tape was applied to the skin surface and removed from the skin surface 20 times to remove the stratum corneum of the skin. After the ^20th tape takeoff, a snapshot of the skin surface was taken with a digital camera with a microscope at 100 times magnification (cf. ).

[Ratings]

As shown in the , the skin surface treated with the process according to the present invention was successfully colored with red over the entire treatment area.

As shown in the , the red color was still clearly and uniformly observed after applying water to the treated skin surface and wiping it, although some color on the treated skin surface was removed.

Furthermore, as shown in Figures 4-6, the color was still light and covered the skin surface well even after washing twice with SLES aqueous solution and removing the stratum corneum with tape peeling for 20 times. , which indicates the lasting coloring effectiveness and uniform coloring of the epidermis with the process according to the present invention.

Claims (10)

Cosmetic process of coloring the interior of a keratinous substance such as skin and lips, comprising the steps:
(1) application to the keratinous substance of a composition comprising
(a) at least one particle having at least one micro-protuberance, comprising
(a-1) at least one water-soluble or water-dispersible polymer, and
(a-2) at least one coloring agent,
(b) at least one oil,
(c) at least one organic lipophilic gelling agent, and
d) at least one water-soluble particle, other than (a) particle having at least one micro-protrusion;
And
(2) applying water to the keratinous substance, to which the composition has been applied, to release the (a-2) coloring agent from the (a) particle having at least one micro-protuberance. Cosmetic process according to claim 1, wherein the micro-protrusion is in the form of a cone or a pyramid. Cosmetic process according to claim 1 or 2, in which the micro-protuberance has a height of 100 to 600 microns, preferably 200 to 500 microns, and more preferably 300 to 400 microns. Cosmetic process according to any one of claims 1 to 3, in which the base of the micro-protuberance has a width of 50 to 500 microns, preferably 100 to 300 microns, and more preferably 150 to 250 microns. Cosmetic process according to any one of claims 1 to 4, in which the (a-1) water-soluble or water-dispersible polymer is selected from hyaluronic acids, monosaccharides, disaccharides, oligosaccharides, polysaccharides, dextrins, dextrans, polyethylene glycols, polyvinyl alcohols, poly(methyl vinyl ether/maleic anhydride), polyvinyl pyrrolidone, poly(methyl/vinyl ether/maleic acid) (PMVE/MA) and their esters, poly(methyl/vinyl ether/maleic anhydride) (PMVE/ MAH), and their mixtures. Cosmetic process according to any one of claims 1 to 5, in which the (a-2) coloring agent is selected from dyes, preferably natural direct dyes, and more preferably coloring plant extracts. Cosmetic process according to any one of claims 1 to 6, wherein the (c) organic lipophilic gelling agent is selected from styrene block copolymers, semi-crystalline polymers, glutamide-based compounds, polyamides and mixtures thereof , and preferably polyamides. A cosmetic process according to any one of claims 1 to 7, wherein the (d) water-soluble particle comprises a polysaccharide, monosaccharide, amino acid or salt thereof, sugar alcohol, ascorbic acid or salt thereof -these, or a mixture of these. Cosmetic process according to any one of claims 1 to 8, further comprising the step of pushing the (a) particle having at least one micro-protuberance in the keratinous substance, between step (1) and step (2). Cosmetic composition for coloring the interior of a keratinous substance such as the skin and the lips, comprising:
(a) at least one particle having at least one micro-protuberance, comprising
(a-1) at least one water-soluble or water-dispersible polymer, and
(a-2) at least one coloring agent;
(b) at least one oil;
(c) at least one organic lipophilic gelling agent; And
(d) at least one water-soluble particle, other than (a) particle having at least one micro-protrusion.