Solid compositions comprising surfactant microspheres

Abstract

The inventors have advantageously incorporated microspheres comprising glycine betaine derivatives, with a volume diameter d(50) of between 0.5 and 20 µm, into cosmetic compositions, without temperature constraints, while preserving the efficacy and sensory properties of these glycine betaine derivatives. Thus, the present invention relates to a solid cosmetic composition comprising, in a physiologically acceptable manner, microspheres of glycine betaine derivatives, with a volume diameter d(50) of between 0.5 and 20 µm, preferably between 1 and 10 µm, and more preferably between 2 and 8 µm. Abstract figure: Figure 2

Description

Title of the invention: Solid compositions comprising surfactant microspheres Technical field

[0001] The present disclosure relates to the field of formulation of cosmetic compositions. Prior art

[0002] Ingredients play an essential role in the formulation of cosmetic products, whether hair, hygiene or makeup products. Each ingredient provides specific properties, contributing to the effectiveness and sensory experience of users.

[0003] However, these cosmetic ingredients pose challenges during their formulation. Some of them are sensitive to factors such as heat, pH, light or oxygen. Others require specific reaction conditions, such as heating. Finding the right balance between formulation efficiency, raw material compatibility and process simplification is a major challenge for cosmetic formulators.

[0004] Typically, cosmetic ingredients that require heating of the reaction mixture impose significant constraints. Indeed, this increase in temperature may be incompatible with the introduction of other components into the formulation and thus risks altering the properties of the heat-sensitive ingredients.

[0005] Furthermore, the formulation of these ingredients to be heated may also require the addition of additional ingredients, either to form an emulsion or to be co-solubilized, thus complicating the formulation.

[0006] Finally, if the heating is not carried out at a temperature suitable for the active ingredient, phase separation problems between the constituents may occur, altering the texture and performance of the product or resulting in a non-uniform distribution of the ingredient in the product.

[0007] Typically, despite undeniable properties which contribute to the quality of cosmetic products intended for hair and skin, the formulation of cationic surfactants, which are glycine betaine derivatives in their current commercial form (CosmeGreen™ ES 1822+ and CosmeGreen™ MB 1618 marketed by the company Surfactgreen), in solid cosmetic compositions, raises various problems:

[0008] To be used in hot-cast solid galenics, glycine betaine derivatives such as Cosmegreen must be melted at 80°C and mixed with phases fats at the same temperature, and / or in glycerin to be mixed with other ingredients. Crystallization must be controlled to avoid phase separations between the constituents.

[0009] Their use is limited in extruded solid galenics, because the extrusion temperature is lower than the melting temperature of Cosmegreen. Dispersion in the solid phase is then poor, and their performance as a conditioner of the finished product is poor, or even non-existent.

[0010] However, consumers are increasingly demanding solid cosmetic compositions, for their durability (solid products require less plastic packaging, which reduces waste) and their ease of transport.

[0011] It is therefore necessary to develop solid cosmetic compositions which can incorporate these glycine betaine derivatives, without the need to heat them or only with moderate heating, while preserving their properties in terms of efficacy and stability. Summary

[0012] The inventors have advantageously incorporated microspheres comprising glycine betaine derivatives, with a volume diameter d(50) of between 0.5 and 20 μm, into cosmetic compositions, without temperature constraints, while preserving the efficacy and sensory properties of these glycine betaine derivatives.

[0013] These microspheres can therefore advantageously be implemented in any type of solid galenic, in varied proportions, without the addition of co-formulants, necessary for integration into the formula, nor a heating step. Their “ready to use” nature simplifies the formulation process. In addition, the absence of heating or the implementation of moderate heating for their formulation allows significant energy savings during the formulation processes.

[0014] Furthermore, the glycine betaine derivatives in the form of microspheres according to the invention can be formulated with a priori incompatible active ingredients, such as heat-sensitive active ingredients, which would otherwise be unusable in a formulation requiring a heating step.

[0015] Advantageously, the integration of this technology within a solid galenic does not affect the integrity of the microspheres. Indeed, the inventors have demonstrated that an extrusion process used to formulate a solid shampoo from syndet, comprising these microspheres does not alter their structure. After solubilization of the shampoo in water, and therefore during use of the shampoo, the microspheres remain intact.

[0016] Furthermore, and unexpectedly, the inventors have demonstrated that the formulation of the glycine betaine derivatives in the form of a microsphere according to the invention allows to improve the properties of the cosmetic ingredient, both during its application and its cosmetic properties.

[0017] Thus, the present invention relates to a solid cosmetic composition comprising, in a physiologically acceptable manner, microspheres of glycine betaine derivatives, with a volume diameter d(50) of between 0.5 and 20 μm, preferably between 1 and 10 μm, and preferably between 2 and 8 μm.

[0018] Advantageously still, the spherical shape, with a volume particle size d(50) of between 0.5 and 20 μm, allows easy mechanical adhesion to hair of 30 μm (fine hair) to 70 μm (thick hair). The particle size / hair size ratio acts in favor of the adhesion of the particle to the hair. This adhesion allows better resistance to washing of the particles when rinsing a shampoo, for example. Indeed, the ingredient will be able to be deposited by friction on the hair and adhere to it. The deposit is therefore uniform on the surface of the hair and resists rinsing with water.

[0019] Thus, the present invention is particularly interesting in the hair field, and can also be used in the field of personal hygiene.

[0020] This is also true for animal hair. Typically, cat hair will have an average diameter of approximately 30 μm and dog hair will have a diameter of between 15 and 150 microns, depending on the breed of dog. Also, the solid cosmetic compositions according to the invention may find an application in the veterinary field.

[0021] Finally, the inventors compared a solid shampoo made from syndet comprising a glycine betaine derivative as commercially available (i.e., without being formulated in the form of microspheres) to a solid shampoo made from syndet comprising microspheres of a glycine betaine derivative according to the invention. It was demonstrated during a consumer test that shaping the cosmetic ingredient in the form of microspheres makes it possible to improve its properties during its application (improvement in obtaining foam, sensoriality during application and improvement in rinsing) but also from a cosmetic point of view (improvement in detangling, hair protection, cleaning, shine, styling, softness, character).

[0022] Thus, the subject of the present invention is the use of microspheres of glycine betaine derivatives according to the invention to improve the performance of said cosmetic ingredient. Brief description of the drawings

[0023] Other characteristics, details and advantages will appear on reading the detailed description below, and on analyzing the attached drawings, in which: Fig.l

[0024] [Fig.l] shows in optical microscopy carried out on a Paralux L110 S2 Trino 1600X microscope equipped with a DinoEye eyepiece camera, a microsphere according to the invention of the Cosmegreen surfactant on a hair fiber. Fig. 2

[0025] [Fig.2] shows in optical microscopy carried out on a Paralux L110 microscope S2 Trino 1600X equipped with a DinoEye eyepiece camera, the clusters of the Cosmegreen surfactant when formulated in its commercial form in a solid shampoo. Fig. 3

[0026] [Fig.3] shows in optical microscopy carried out on a Paralux L110 S2 microscope Trino 1600X equipped with a DinoEye eyepiece camera, the presence of Cosmegreen microspheres after solubilization of the solid shampoo in water. Fig. 4

[0027] [Fig.4] shows in optical microscopy carried out on a Paralux L110 S2 microscope Trino 1600X equipped with a DinoEye eye camera, the presence of Cosmegreen microspheres on a hair before rinsing. Fig. 5

[0028] [Fig.5] shows, in optical microscopy carried out on a Paralux L110 S2 microscope Trino 1600X equipped with a DinoEye eyepiece camera, the presence of Cosmegreen microspheres on a hair after rinsing. Detailed description

[0029] The present invention therefore relates to a solid cosmetic composition comprising, in a physiologically acceptable manner, microspheres of glycine betaine derivatives, with a volume diameter d(50) of between 0.5 and 20 pm, preferably between 1 and 10 pm, and preferably between 2 and 8 pm.

[0030] According to one embodiment, the glycine betaine derivatives represent at least 80% by mass of said microspheres.

[0031] According to this embodiment, each microsphere is composed mainly of glycine betaine derivatives.

[0032] Microsphere composed mainly of glycine betaine derivatives

[0033] A microsphere composed mainly of glycine betaine derivatives is understood to mean a microsphere composed of at least 80% by mass of glycine betaine derivatives, relative to the total mass of the microsphere, preferably at least 81%, preferably at least 82%, preferably at least 83%, preferably at least 84%, preferably at least 85%, preferably at least 86%, preferably at least 87%, preferably at least 88%, preferably at least 89%, preferably at least 90%, relative to the total mass of the microsphere, preferably at least 91%, preferably at least 92%, preferably at least 93%, preferably at least 94%, preferably at least 95%, preferably at least 96%, preferably at least 97%, preferably at least 98%, preferably at least 99% by mass of glycine betaine derivatives, relative to the total mass of the microsphere. Preferably again, the microsphere is composed of 100% by mass of glycine betaine derivatives, relative to the total mass of the microsphere.

[0034] According to one embodiment, each microsphere is composed of a glycine betaine derivative or a mixture of glycine betaine derivatives.

[0035] According to this embodiment, the cosmetic ingredient microspheres do not comprise waxes.

[0036] The cosmetic ingredient microsphere may comprise, in a minor manner, one or more of the surfactants and / or one or more of the colloids used during the process of manufacturing the microspheres. They are to be distinguished from the glycine betaine derivative(s) forming the microsphere.

[0037] Thus, according to this embodiment, each microsphere of cosmetic ingredient comprises a content of less than 20% by mass of at least one surfactant and / or at least one colloid, relative to the total mass of the microsphere, preferably, a content of less than 19%, preferably less than 18%, preferably less than 17%, preferably less than 16%, preferably less than 15%, preferably less than 14%, preferably less than 13%, preferably less than 12%, preferably less than 11% by mass, preferably less than 10% by mass, relative to the total mass of the microsphere, preferably, a content of less than 9%, preferably less than 8%, preferably less than 7%, preferably less than 6%, preferably less than 5%, preferably less than 4%, preferably less than 3%, preferably less than 2%,preferably less than 1% by mass of at least one surfactant and / or at least one colloid, relative to the total mass of the microsphere.

[0038] Thus, according to this embodiment, each microsphere is composed of at least one glycine betaine derivative which is not a wax, and optionally at least one surfactant and / or at least one colloid. This means that each microsphere does not comprise any amphiphilic product, waxes, stabilizer or other additives which are not the cosmetic ingredient or a mixture of cosmetic ingredients and optionally one or more surfactants and / or colloids.

[0039] According to this embodiment, the microspheres are not microspheres composed of a core of active material and a coating, i.e., the microspheres according to the invention do not have a core-shell structure.

[0040] Indeed, the cosmetic ingredient microspheres according to the invention are solid and the cosmetic ingredient(s) are distributed over the entire volume of the microsphere, including its periphery, without distinction between core and shell. In other words, the cosmetic ingredient(s) are present both at the periphery and in the volume of the microsphere. Preferably, the cosmetic ingredient(s) are distributed uniformly over the entire volume of the microsphere, including its periphery.

[0041] When the cosmetic ingredient microspheres comprise, in a minority manner, one or more of the surfactants and / or one or more of the colloids used during the process for manufacturing the microspheres (and not surfactants qualified as cosmetic ingredients within the meaning of the present invention), the liposoluble surfactants will be equally distributed over the entire volume of the microsphere including its periphery, without distinction between core and shell. The water-soluble surfactants and the colloids will be present at the periphery and / or at the interface. However, and even in the presence, in a minority manner, of one or more of the surfactants and / or one or more of the colloids used during the process for manufacturing the microspheres, the microspheres do not have a core / shell structure.

[0042] Microspheres comprising at least one glycine betaine derivative and at least one wax

[0043] According to another embodiment, each microsphere comprises at least one wax and at least one glycine betaine derivative.

[0044] In the same way as previously, and according to this embodiment, each microsphere may comprise, in a minor manner, one or more of the surfactants and / or one or more of the colloids used during the process of manufacturing the microspheres. They are to be distinguished from the glycine betaine derivative(s) forming the microsphere.

[0045] Thus, according to one embodiment, a microsphere comprises a content of less than 20% by mass of at least one surfactant and / or at least one colloid, relative to the total mass of the microsphere, preferably, a content of less than 19%, preferably less than 18%, preferably less than 17%, preferably less than 16%, preferably less than 15%, preferably less than 14%, preferably less than 13%, preferably less than 12%, preferably less than 11% by mass, preferably less than 10% by mass of at least one surfactant and / or at least one colloid, relative to the total mass of the microsphere, preferably, a content of less than 9%, preferably less than 8%, preferably less than 7%, preferably less than 6%, preferably less than 5%, preferably less than 4%, preferably less than 3%, preferably less than 2%, preferably less than 1% by mass of at least one surfactant and / or at least one colloid, relative to the total mass of the microsphere.

[0046] According to one embodiment, each microsphere comprises from 1 to 10% by mass of at least one glycine betaine derivative, from 90 to 99% by mass of at least one wax and from 0 to 20% by mass of at least one surfactant and / or at least one colloid.

[0047] According to one embodiment, each microsphere comprises from 10 to 20% by mass of at least one glycine betaine derivative, from 80 to 90% by mass of at least one wax and from 0 to 20% by mass of at least one surfactant and / or at least one colloid.

[0048] According to one embodiment, each microsphere comprises from 20 to 30% by mass of at least one glycine betaine derivative, from 70 to 80% by mass of at least one wax and from 0 to 20% by mass of at least one surfactant and / or at least one colloid.

[0049] According to one embodiment, each microsphere is composed of 30 to 40% by mass of at least one glycine betaine derivative, 70 to 80% by mass of at least one wax and 0 to 20% by mass of at least one surfactant and / or at least one colloid.

[0050] According to one embodiment, each microsphere is composed of 40 to 50% by mass of at least one glycine betaine derivative, 50 to 60% by mass of at least one wax and 0 to 20% by mass of at least one surfactant and / or at least one colloid.

[0051] According to one embodiment, each microsphere is composed of 50 to 60% by mass of at least one glycine betaine derivative, 40 to 50% by mass of at least one wax and 0 to 20% by mass of at least one surfactant and / or at least one colloid.

[0052] According to one embodiment, each microsphere is composed of 60 to 70% by mass of at least one glycine betaine derivative, 30 to 40% by mass of at least one wax and 0 to 20% by mass of at least one surfactant and / or at least one colloid.

[0053] According to one embodiment, each microsphere is composed of 70 to 80% by mass of at least one glycine betaine derivative, 20 to 30% by mass of at least one wax and 0 to 20% by mass of at least one surfactant and / or at least one colloid.

[0054] According to one embodiment, each microsphere is composed of 80 to 90% by mass of at least one glycine betaine derivative, 20 to 10% by mass of at least one wax and 0 to 20% by mass of at least one surfactant and / or at least one colloid.

[0055] According to one embodiment, each microsphere is composed of 90 to 99% by mass of at least one glycine betaine derivative, 1 to 10% by mass of at least one wax and 0 to 20% by mass of at least one surfactant and / or at least one colloid.

[0056] According to this embodiment, each microsphere is composed of at least one glycine betaine derivative, at least one wax and optionally at least one surfactant and / or at least one colloid. This means that each microsphere does not contain any amphiphilic product, stabilizer or other additives other than wax or a mixture of waxes, a glycine betaine derivative or a mixture of glycine betaine derivatives and possibly one or more surfactants and / or colloids.

[0057] According to this embodiment also, the microspheres are not microspheres composed of a core of active material and a coating, i.e., the microspheres according to the invention do not have a core-shell structure.

[0058] Indeed, the microspheres according to the invention are solid and the glycine betaine derivative(s), the wax(es) and any colloids or surfactants are distributed over the entire volume of the microsphere, including its periphery, without distinction between core and shell. In other words, the glycine betaine derivative(s), the wax(es) and any colloids or surfactants are present both at the periphery and in the volume of the microsphere. Thus, and preferably, the glycine betaine derivative(s), the wax(es) and any colloids or surfactants are distributed uniformly over the entire volume of the microsphere, including its periphery.

[0059] Volume particle size distribution

[0060] The volume diameter d(50) refers to the median diameter of particles in the particle size distribution. According to the commonly accepted definition, the median diameter corresponds to the theoretical opening of a sieve such that 50% of the particles, by volume, have a diameter greater than and 50% a diameter less than the d(50).

[0061] The volume diameter d(50) is measured by laser diffraction granulometry. For this, the sample to be analyzed is previously diluted in water with the addition of a non-ionic dispersant. An observation by optical microscopy is carried out upstream to ensure the deagglomeration of the particles. The measurement is carried out on a Fritsch Analysette 22 NeXT Nano granulometer with an obscuration of between 5 and 15%. The results are interpreted using Mie theory.

[0062] According to one embodiment, the volume diameter d(50) is between 1 and 10 pm and preferably between 2 and 8 pm. This embodiment is particularly advantageous in capillary applications.

[0063] According to one embodiment, the diameters d(10) and d(90), also measured by laser diffraction granulometry, are as follows: - the diameter d(10) is between 0.1 and 2.5 pm, preferably less than 1 pm - the diameter d(90) is between 8 and 20 pm, preferably less than 10 pm.

[0064] The terms d(10) and d(90) also refer to parameters in the particle size distribution. D(10) corresponds to the theoretical opening of a sieve such that 10% of the particles, by volume, have a diameter less than d(10), and that the d(90) corresponds to the theoretical opening of a sieve such that 90% of the particles, by volume, have a diameter less than d(90).

[0065] Glycine betaine derivatives

[0066] The microspheres may be composed of a glycine betaine derivative or a mixture of glycine betaine derivatives.

[0067] Glycine betaine derivatives are described in application FR3099058.

[0068] According to one embodiment, the glycine betaine derivatives are glycine betaine ester or amide salts comprising from 14 to 24 carbon atoms.

[0069] According to one embodiment, the glycine betaine derivatives are of formula [Chem 1] Xn-[(CH3)3N+-CH2-COZ-R]n where: Z denotes an oxygen atom or a -NH group, R is a linear or branched, saturated or unsaturated alkyl group comprising from 14 to 24 carbon atoms, preferably, the radical R is chosen from the groups myristyl (C14:0), cetyl (C16:0), palmitoleyl (C16:1), stearyl (C18:0), oleyl (Cl8:1), linoleyl (Cl8:2), linolenyl (Cl8:3), arachidyl (C20:0), arachidonyl (C20:4), behenyl (C22:0), 2-hexyldecyl, 2-octyldodecyl and 2-decyltetradecyl, and preferably the radical R is chosen from the groups arachidyl (C20:0) or behenyl (C22:0). X is an organic or inorganic anion, preferably, fanion X is chosen from a chloride, a sulfate, a perchlorate, an alkylsulfate ion, in particular decylsulfate or laurylsulfate, an arylsulfonate ion, in particular benzenesulfonate, paratoluenesulfonate, an alkylsulfonate ion, in particular triflate, methanesulfonate, ethanesulfonate, decylsulfonate, laurylsulfonate, camphorsulfonate, or a sulfosuccinate ion, preferably from alkylsulfonates and arylsulfonates, more particularly from methanesulfonate, triflate, paratoluenesulfonate and camphorsulfonate ions, better still, X is the methanesulfonate ion. and n is 1 or 2.

[0070] According to one embodiment, the glycine betaine derivatives are in the form of a composition comprising: (a) at least one glycine betaine ester salt of formula [Chem 2] Xn-[(CH3)3N+-CH2-COO-R]n where R is a linear or branched, saturated or unsaturated alkyl group comprising from 14 to 24 carbon atoms and preferably from 18 to 22 carbon atoms, (b) at least one fatty alcohol of formula R-OH, (c) an organic or inorganic acid of formula XH, and (d) a glycine betaine salt of formula [Chem 3] Xn-[(CH3)3N+-CH2-COOH]n, where X is an organic or inorganic union and n is 1 or 2.

[0071] According to this embodiment, the glycine betaine derivatives in the form of composition includes: (a) from 15 to 45% by weight, preferably from 20 to 30%, more preferably from 25 to 30% by weight, of glycine betaine ester salt, (b) from 55 to 70% by weight, for example from 60 to 65% or from 65 to 70% by weight, of fatty alcohol, (c) from 0 to 5% by weight, for example from 0 to 1% by weight of organic or inorganic acid, (d) from 0 to 3% by weight, for example from 0 to 1% by weight, of glycine betaine salt, (e) from 0 to 15% by weight, for example from 2 to 10% by weight, of dialkyl ether.

[0072] According to one embodiment, the glycine betaine derivatives are in the form of a composition comprising: (a) one or more glycine betaine amide salt(s) of formula [Chem 4] Xn-[(CH3)3N+-CH2-CONH-R]n where R is a linear or branched, saturated or unsaturated alkyl group comprising from 14 to 24 carbon atoms and preferably from 16 to 22 carbon atoms; (b) one or more alkylammonium salt(s) of formula [Chem 5] Xn- [NH3+R]n where R is a linear or branched, saturated or unsaturated alkyl group comprising from 14 to 24 carbon atoms and preferably from 16 to 22 carbon atoms; (c) one or more glycine betaine ester salts of formula [Chem 6] Xn-[(CH3)3N+-CH2-COOR']n where R' is a linear or branched, saturated or unsaturated alkyl radical containing from 4 to 8 carbon atoms; and (d) glycine betaine of formula [Chem 7] (CH3)3N+-CH2-COO ; where X is an organic or inorganic anion and n is 1 or 2.

[0073] By way of illustration, the glycine betaine derivatives as defined above are CosmeGreen™ ES 1822+ and CosmeGreen™ MB 1618 marketed by the company SurfactGreen. These cationic surfactants are in the form of granules and correspond, in the present application, to the name “Cosmegreen” or “Cosmegreen in its commercial form”, i.e., in the form of granules and not in the form of microspheres according to the present invention.

[0074] Waxes

[0075] By "wax" is meant a lipophilic compound, solid at room temperature (25°C), with a reversible solid / liquid state change, either by melting, glass transition or by softening between 40°C and 120°C.

[0076] The term "solid" means an object characterized on a macroscopic scale by a determined volume and shape, constant in the absence of any external force or extreme condition.

[0077] The melting point will be measured by any technique known to those skilled in the art.

[0078] Generally, the melting point of the cosmetic ingredient can be measured at using a differential scanning calorimeter (DS C), for example the calorimeter sold under the name DSC 30 by the METTLER Company.

[0079] According to one embodiment, the waxes may be chosen from (i) hydrocarbon waxes, optionally substituted, in particular hydroxylated, (ii) fluorinated waxes, (iii) silicone waxes and mixtures thereof.

[0080] Among the hydrocarbon waxes, mention may be made of hydrocarbon waxes whose melting point is advantageously greater than 40°C, for example greater than 55°C.

[0081] Generally, the melting point of the wax can be measured using a differential scanning calorimeter (DS C), for example the calorimeter sold under the name DSC 30 by the METTLER Company.

[0082] Examples of hydrocarbon waxes that may be mentioned include linear hydrocarbon waxes or primary, secondary or tertiary fatty acid esters. The hydrocarbon waxes may be chosen from linear hydrocarbon waxes. Examples of linear hydrocarbon waxes that may be mentioned include: substituted linear alkanes, unsubstituted linear alkanes, unsubstituted linear alkenes, substituted linear alkenes. An unsubstituted compound is composed solely of carbon and hydrogen and the substituents do not contain carbon atoms. Linear hydrocarbon waxes include linear paraffin waxes, such as S&P® 206, S&P® 173 and S&P® 434 paraffins from Strahl & Pitsch.

[0083] The hydrocarbon waxes can be chosen from esters of fatty acids, saturated or unsaturated, or derived from unsaturated fatty acids which have been previously hydrogenated in order to become saturated.

[0084] The wax can thus be chosen from the esters: - capric acid (in CIO), lauric acid (in C12), myristic acid (in C14), palmitic acid (in C16), stearic acid (in C18), arachidic acid (in C20), palmitoleic acid (in C16), oleic acid (in C18), linoleic acid (C18), linolenic acid (C18), arachidonic acid (C20); and - fatty alcohols, primary, secondary (such as ethylene glycol) or tertiary (such as glycerol), C2 to C22, advantageously C6 to C18, - ricinoleic acid (Cl8) or hydrogenated ricinoleic acid; - fatty alcohols, primary, secondary (such as ethylene glycol) or tertiary (such as glycerol), C2 to C22, advantageously C6 to C22, better still C16 to C22 and mixtures thereof.

[0085] These esters have melting points which can vary depending on the alcohol incorporated from 23°C to 85°C. The waxes selected according to the present invention will be those having a melting point above 40°C.

[0086] Mention may be made of esters (i) of myristic acid and ethylene glycol or glycerol (ii) of stearic acid and primary and linear C6 fatty alcohols or ethylene glycol or glycerol, (iii) esters of stearic acid and primary and linear C8 fatty alcohols, (iv) esters of stearic acid and primary and linear C10 fatty alcohols, (v) esters of stearic acid and primary and linear C12 fatty alcohols, (vi) esters of stearic acid and primary and linear C14 fatty alcohols, (vii) esters of stearic acid and primary and linear C16 fatty alcohols, (viii) esters of stearic acid and primary and linear C18 fatty alcohols, (ix) esters of ricinoleic acid, hydrogenated or not, and of primary and linear C16 fatty alcohols or of ethylene glycol or of glycerol, (x) esters of ricinoleic acid, hydrogenated or not, and of primary and linear C18 fatty alcohols and (xi) esters of ricinoleic acid, hydrogenated or not,and primary and linear C22 fatty alcohols.,

[0087] According to one embodiment, the wax is chosen from esters of myristic acid and ethylene glycol or glycerol, esters of stearic acid and primary and linear C18 fatty alcohols or ethylene glycol or glycerol, esters of ricinoleic acid, hydrogenated or not, and primary and linear C22 fatty alcohols or ethylene glycol or glycerol, hydrogenated palm oil. Advantageously, mention may be made of glycerol tristearate and glycerol trimyristate.

[0088] Mention may be made of the ester of stearic acid and of primary and linear C16 fatty alcohol with a Tm between 52 and 57°C, the ester of stearic acid and of primary and linear C18 fatty alcohol with a Tm between 54 and 60°C, the esters of hydrogenated ricinoleic acid and of primary and linear C16 fatty alcohols with a Tm between 62 and 66°C, the esters of hydrogenated ricinoleic acid and of primary and linear C18 fatty alcohols with a Tm between 67 and 71°C, the esters of hydrogenated ricinoleic acid and of primary and linear C22 fatty alcohols with a Tm between 71 and 75°C.

[0089] Particularly advantageous waxes for the invention may be mentioned in Table 1 below:

[0090] [Tables 1] Trade name Chemical name IN CI Chemical name or description CAS number Castor 22L73 Hydrogenated Cast or oil Behenyl esters Hydrogenated castor oil - Castor 16L64 Hydrogenated cast or oil cetyl esters Dynasan 118 Tristearin 2,3-di(octadecanoyloxy)propyl octadecenoate, C57H110O6 555-43-1 Olive 18L.57 Hydrogenated oliv e oil stearyl esters Hydrogenated olive oil Dynasan P60F Hydrogenated Pal mOil Hydrogenated palm oil ( 68514-74-9 / 8033-29-2 Hydrogenated vegetable oil Softisan 154 Shellac SSB 63 Shellac Shellac 9000-59-3 Dynasan 114 Trimyristin l,3-di(tetradecanoyloxy)propan-2-yl tetradecanoate (Glycerol trimyristate),C45H86O6 555-45-3 Lipoxol 6000 PEG-135 Polyethylene glycol,HO-(CH2CH2O) 135'H 25322-68-3 Copemicia cerifera cera Carnauba wax 8015-86-9 EUPHORBIA CE RIFERA CERA or Candelilla wax Candellila wax 8006-44-8 Cera alba Beeswax 8012-89-3 Imwitor 960 K Glyceryl Stearate SE Octadecanoic acid, reaction products with 11099-07-3 1,2,3-propanetriol (1:1), neutralized Imwitor 49 Glyceryl stearate Glyceryl monostearate, Octadecanoic acid, monoester with 1,2,3-propanetriol, C21H42O4 31566-31-1 Oryza Sativa Cera / Oryza Sative Bran Wax Cire de riz Huile de coco hydrogenate Macadamia Integri folia Wax Cire de macadamia Rhus Succedanea F ruit Cera Cire de Sumac Rhus Vemiciflua Peel Cera Cire de baies de Sumac Hydrogenated jojo ba wax or hydrogenated jojoba oil Huile de jojoba hydrogenate Hydrogenated sunf lower seed oil Huile de tournesol hydrogenate Helianthus Annuus Seed wax Cire de tournesol Citrus Aurantium Dulcis Peel Cera Cire d'écorce d'orange Acacia Decurrens Flower Cera Cire de mimosa Jasminum Grandifl orum Flower Cera Cire de jasmin Rosa Damascena F lower Cera Cire de rose de Damas Myrica Pubescens Fruit Cera Cire de baie de Myrica Camellia Sinensis Leaf Wax Cire de feuilles de thé vert Lanolin Cera Cire de lanoline

[0091] According to one embodiment, the waxes are chosen from hydrogenated castor oil, 2,3-di(octadecanoyloxy)propyloctadecenoate, hydrogenated olive oil, hydrogenated palm oil, shellac, 1,3-di(tetradecanoyloxy)propan-2-yl, camauba wax, candellila wax, beeswax, Glyceryl Stearate SE, Glyceryl Stearate, rice wax, hydrogenated coconut oil, macadamia wax, sumac wax, sumac berry wax, hydrogenated jojoba oil, hydrogenated sunflower oil, sunflower wax, orange peel wax, mimosa wax, jasmine wax, damask rose wax, Myrica berry wax, leaf wax green tea and lanolin wax,

[0092] According to one embodiment, the waxes are chosen from hydrogenated olive oil, hydrogenated castor oil, 2,3-di(octadecanoyloxy)propyloctadecen oate, rice wax, macadamia wax, candellila wax, camauba wax, hydrogenated jojoba oil.

[0093] According to a preferred embodiment, the waxes are chosen from hydrogenated olive oil and hydrogenated castor oil.

[0094] Process for obtaining microspheres according to the invention

[0095] The microspheres according to the invention may be obtained by the process as described in patent EP2894978.

[0096] According to one embodiment, the method for obtaining the microspheres according to the present invention comprises the following steps: (I) Heating a fatty phase comprising (i) at least one wax, and / or (ii) at least one glycine betaine derivative, at a reaction temperature higher than the melting temperature of said at least one wax and / or said at least one glycine betaine derivative; (II) Heating a first aqueous phase comprising at least one water-soluble surfactant and at least one protective colloid, at said reaction temperature implemented in step (I), with mechanical stirring; (III) Incorporation of said fatty phase into said first aqueous phase while maintaining the reaction temperature, under mechanical stirring, so as to form a stable oil-in-water emulsion; (IV) Addition dropwise, with mechanical stirring, of said emulsion previously formed into a second aqueous phase comprising at least one water-soluble surfactant and / or at least one protective colloid, the temperature of said second phase being lower than the melting temperature of said wax and / or said at least one glycine betaine derivative.

[0097] The glycine betaine derivative and the wax are as defined above.

[0098] According to one embodiment, the heating temperature of the fatty phase is greater than 30°C.

[0099] “Stable” means an emulsion whose particle size does not change over the time of the process, or the time required for transfer into the aqueous phase.

[0100] Thus, the process allows the production of microspheres according to the invention, i.e., with a volume diameter d(50) of between 0.5 and 100 m, and composed either mainly of glycine betaine derivatives, or of at least one glycine betaine derivative and at least one wax.

[0101] These microspheres are as defined above and are suspended in said second aqueous phase.

[0102] The mere fact that the emulsion obtained in step (III) is added dropwise makes it possible to obtain the microspheres according to the invention. The use of a protective colloid in the first aqueous phase combined with the dropwise addition of the emulsion makes it possible to further improve the formation of the microspheres, whereas the sole presence of a protective colloid without dropwise addition does not make it possible to produce microspheres.

[0103] Fatty phase

[0104] The fatty phase of the process consists of either: - a glycine betaine derivative or a mixture of glycine betaine derivatives, or - (i) at least one wax and (ii) at least one glycine betaine derivative.

[0105] This means that said fatty phase does not contain any amphiphilic product, stabilizer, surfactant or co-surfactant, or other additives which are not wax and / or the glycine betaine derivative.

[0106] The proportions of said at least one wax and said at least one glycine betaine derivative may vary depending on the desired contents of said at least one wax and said at least one glycine betaine derivative within the fatty phase. A person skilled in the art is able to determine the proportions.

[0107] The glycine betaine derivatives and waxes are as described above.

[0108] According to one embodiment of the process, the reaction temperature is at least 10°C higher than the melting temperature of said at least one wax and / or said at least one cosmetic ingredient.

[0109] First and second aqueous phase

[0110] According to one embodiment of the process, the surfactant(s) of the first aqueous phase and / or of the second aqueous phase is or are chosen from non-ionic surfactants, cationic surfactants and anionic surfactants.

[0111] According to one embodiment, the surfactant(s) of the first aqueous phase and / or of the second aqueous phase is or are chosen from polyoxyethylene stearyl ethers, sodium lauryl sulfonate, polyoxyethylene copolymers polyoxypropylene (AB, AB A, BAB form), sorbitan esters and Potassium Cetyl Phosphate.

[0112] Mention may be made, as surfactant(s) of the first aqueous phase and / or of the second aqueous phase, of steareth 21, Pluronic®, Tween® and Span® which are soluble in water and capable of forming an oil-in-water emulsion, and Synperonic®.

[0113] These surfactants are well known to those skilled in the art.

[0114] Thus steareth 21 is a polyoxyethylene stearyl ether comprising 21 units ethylene oxide per molecule whose CAS number is 9005-00-9. It is commercially available from BASF under the brand name Eumulgin S 21®.

[0115] Pluronic® is the brand under which BASF markets polyoxyethylene polyoxypropylene copolymers also called poloxamers.

[0116] Tween® and Span® are the brands under which Croda markets oxyethylenated sorbitan fatty acid esters. Synperonic® is the brand under which Croda markets polyethylene polypropylene glycol copolymers.

[0117] Amphisol K® is the brand under which DSM markets Potassium Cetyl Phosphate.

[0118] The first aqueous phase as well as the second aqueous phase in accordance with the invention may comprise from 0.1 to 2.5% by mass, relative to the total mass of said aqueous phase, of at least one surfactant in accordance with the invention, preferably from 0.1 to 1% by mass, and more particularly from 0.25 to 0.5% by mass relative to the total mass of said aqueous phase.

[0119] According to one embodiment of the method, the protective colloid is chosen from maltodextrins, polyvinylpyrrolidone, xanthan gum, carboxymethylcellulose, pectin, starches and its derivatives, guar gum, acacia gum and polyvinyl alcohol (PVA).

[0120] According to one embodiment of the method, the protective colloid is chosen from acacia gum and polyvinyl alcohol (PVA).

[0121] The first aqueous phase as well as the second aqueous phase in accordance with the invention may comprise from 0 to 5% by mass, relative to the total mass of said aqueous phase, of at least one colloid in accordance with the invention, preferably from 0.05 to 2.5% by mass, and more particularly from 0.1 to 2% by mass relative to the total mass of said aqueous phase.

[0122] According to one embodiment, the second aqueous phase does not contain any additional solvent other than those previously described, which makes it possible to use the fewest possible additives and to obtain microspheres that are as ecological as possible.

[0123] According to one embodiment, the temperature of the second phase is 10°C to 5°C lower than the crystallization temperature of said at least one wax and / or said at least one glycine betaine derivative.

[0124] The stirring speed in step III depends on the quantity of emulsion to be produced and the desired particle size and the person skilled in the art will be able to set it based on his general knowledge. Thus, for batches of approximately 1 to 5 kg, the speed is 1,500-2,000 rpm for a particle size d(50) of 15-20 μm and 5,000-6,000 rpm for a particle size d(50) of less than 10 μm.

[0125] According to one embodiment of the process, the stirring speed in step III is 1,500 - 6,000 rpm, advantageously between 2,000 and 5,000 rpm with the IKA® Eurostar Power control-visc 6000 mixer equipped with a 45 mm diameter deflocculating blade.

[0126] The “drop by drop” transfer rate in step IV of the process depends on the quantity of dispersion to be prepared and a person skilled in the art will be able to set it based on his general knowledge. Thus, for batches of approximately 0.5 to 1 kg of second aqueous phase, the flow rate is between 10 and 40 ml / min and for batches of approximately 50 kg, the flow rate can be up to 10 liters / min.

[0127] Suspension of microspheres according to the invention

[0128] The production process described above makes it possible to obtain an aqueous suspension comprising at least 25% by mass of microspheres relative to the total mass of the suspension. Preferably, the suspension comprises at least 30% by mass of microspheres relative to the total mass of the suspension.

[0129] This is achieved by adding at least one part and at most two parts of the emulsion obtained in step (III) to one part of the second aqueous phase.

[0130] Powder

[0131] According to one embodiment, the microspheres according to the invention are in a dry form, such as a powder.

[0132] According to one embodiment, the dry form is obtained by freeze-drying or atomization, preferably by freeze-drying of the dispersion of microspheres previously obtained.

[0133] According to one embodiment, the dry form comprises the microspheres according to the invention in a content of at least 90% by mass relative to the total mass of the dry form.

[0134] The powder may comprise, in addition to the microspheres, one or more ingredients chosen from preservatives, stabilizers, buffers, anti-caking agents, flow agents and mixtures thereof.

[0135] Physiologically acceptable medium.

[0136] The physiologically acceptable medium is preferably cosmetically or dermatologically acceptable. The term “physiologically acceptable medium” or “cosmetically acceptable” or “dermatologically acceptable” means any medium which does not exhibit deleterious side effects and in particular which does not produce no redness, inflammation, heating, tightness or tingling unacceptable to a user of cosmetic or dermatological products. The environment is thus compatible with keratin materials from humans or animals.

[0137] Keratin materials

[0138] The keratin materials will be, for human beings, the skin, the mucous membranes, the scalp, the hair, the hair system, the eyelashes, the eyebrows, the lips, the nails, preferentially, the skin, the mucous membranes, the scalp, the hair.

[0139] For animals, keratin materials will be hair.

[0140] Solid galenic

[0141] Advantageously, the microspheres according to the invention, in suspension form or in dry form, can be used in any type of solid galenic.

[0142] By way of illustration, for solid galenics, mention will be made of soaps, syndets, solid shampoos or solid shower gels preferably obtained from soap or syndet, balms, solid or semi-solid sticks, powders to be reconstituted for the formation of a cosmetic product (the powder can be in any form such as granules, microbeads, glitter, etc.).

[0143] According to a preferred embodiment, the cosmetic composition is in the form of a solid shampoo, preferably obtained from syndet.

[0144] These solid galenics may be obtained by any method known to those skilled in the art for the preparation of solid galenics. It has in fact been advantageously demonstrated that the microspheres according to the invention could be incorporated into solid galenics without modification of the process for obtaining the solid galenic or deterioration of the microspheres.

[0145] Typically, solid galenics can be obtained by extrusion or by hot casting.

[0146] Advantageously, the spherical shape and the volume particle size d(50) between 0.5 and 20 pm, preferably between 1 and 1 Opm, preferably between 2 and 8 pm allow easy mechanical attachment to hair from 30 pm (fine hair) to 70 pm (thick hair) and this as illustrated in [Fig.l]. The particle size / hair size ratio acts in favor of the adhesion of the particle to the hair. This adhesion allows better resistance to washing of the particles when rinsing a shampoo for example.

[0147] Thus, the composition according to the present invention is preferably useful for formulating hygiene and care products for the scalp and / or hair.

[0148] It will also be useful for the formulation of hygiene and animal hair care products.

[0149] Hygiene and care of the scalp and / or hair

[0150] The compositions suitable for the hygiene and care of the scalp and / or hair may be presented in any appropriate form in the field, such as soaps, syndets, solid shampoos or solid shower gels, preferably obtained from soap or syndet, dry shampoos, syndets, solid or dry conditioners, solid or dry detanglers.

[0151] According to one embodiment, the composition is in the form of a solid shampoo, preferably obtained from syndet.

[0152] According to one embodiment, the solid shampoo is obtained by extrusion.

[0153] According to one embodiment, the cosmetic ingredient is a glycine derivative betaine or a mixture of glycine betaine derivatives as defined above, preferably CosmeGreen™ ES 1822+ or CosmeGreen™ MB 1618 from SurfactGreen, or a mixture thereof.

[0154] The invention also relates to a process for the care and / or hygiene of keratin materials, in particular the scalp and / or hair, consisting of applying to said keratin materials, in particular the scalp and / or hair, a cosmetic composition comprising the microspheres of active ingredients according to the invention.

[0155] Face and body _ Hygiene

[0156] The composition according to the invention is also useful for formulating facial and body hygiene products. Mention will be made, by way of illustration, among the galenic forms suitable for hygiene and / or care of the face and / or body, solid soaps, syndets, deodorants.

[0157] The invention also relates to a method for cleaning and / or removing make-up or a method for caring for keratin materials, in particular the skin, consisting of applying to said keratin materials, in particular the skin, a cosmetic composition comprising the microspheres of active ingredients according to the invention.

[0158] Process for obtaining solid shampoo

[0159] The present invention also relates to a process for obtaining a solid shampoo, comprising: - the mixture of raw syndet and microspheres according to the invention to obtain a paste, - extrusion of the previously obtained paste, - the cutting and / or molding of said dough if necessary.

[0160] According to one embodiment, the raw syndet in the mixing step is in the form of chips. In addition to the raw syndet and the microspheres according to the invention, any type of ingredient conventionally used in the manufacture of a solid shampoo by extrusion may be integrated into the mixture. Mention may be made, by way of illustration, of conditioners, surfactants, perfumes, colorants, etc.

[0161] Use

[0162] The inventors have demonstrated that the formulation of glycine betaine derivatives in the form of microspheres according to the invention makes it possible to improve the performance of glycine betaine derivatives, both during its application and for its cosmetic properties.

[0163] Indeed, the inventors compared a solid shampoo prepared from syndet and comprising a glycine betaine derivative, CosmeGreen™ ES 1822+ as commercially available (i.e., without being formulated in the form of microspheres) to a solid shampoo prepared from syndet and comprising the microspheres of CosmeGreen™ ES1822+ according to the invention. It was demonstrated during a consumer test that the shaping of CosmeGreen™ ES 1822+ in the form of microspheres makes it possible to improve its properties during its application (improvement of obtaining foam, sensoriality during application and improvement of rinsing) but also from a cosmetic point of view (improvement of detangling, protection of the hair, cleaning of shine, styling, softness, character).

[0164] More particularly, it has been demonstrated that: - The production of foam is improved; - The sensoriality during application is improved: (the product is considered more pleasant to use, easier to apply and provides a finer foam); - Rinsing is improved; - Detangling is improved; - The product does not dry out the hair; - Hair protection is improved; - Cleaning is improved; - The shine is improved; - Styling is improved; - Softness is improved; - the nourishing character is improved.

[0165] Thus, the present invention also relates to the use of microspheres of glycine betaine derivatives, with a volume diameter d(50) of between 0.5 and 20 pm, preferably between 1 and 10 pm, and preferably between 2 and 8 pm, to improve the cosmetic performance of glycine betaine derivatives.

[0166] According to one embodiment, the cosmetic performances are chosen from obtaining foam, sensoriality, rinsing, detangling, hair protection, cleaning, shine, styling, softness, nourishing character.

[0167] The invention is illustrated in a non-limiting manner by the examples below. Examples

[0168] Example 1: Process for obtaining a dispersion of microspheres comprising at least one glycine betaine derivative and at least one wax.

[0169] The process as described in Example 1 makes it possible to obtain microspheres comprising at least one glycine betaine derivative and at least one wax.

[0170] The ingredients and proportions used in the process are described in the table below.

[0171] [Tables2] Emulsion 1st aqueous phase Fatty phase 2nd aqueous phase 90% Demineralized water 10% INAVEA ORIGINAL (acacia gum)** 95% Phytowax 10L40 (hydrogenated olive oil) *** 5% CosmeGreen ESI822+* 95% Demineralized water 5% INAVEA ORIGINAL (acacia gum)** * Surfactant; **Protective colloid; *** Wax

[0172] CosmeGreen ES1822+ *is a glycine betaine derivative.

[0173] The volume ratio between the fatty phase and the first aqueous phase in the emulsion is 40 / 60.

[0174] The volume ratio between the emulsion and the second aqueous phase in the dispersion is 60 / 40.

[0175] The “drop by drop” emulsion transfer rate is 300ml / min.

[0176] The diameter D(50) of the microspheres produced is 15pm.

[0177] Material used

[0178] [Tables3] Reactor s Agitator s Speed ​​Reactor 1: 2.5 L stainless steel Mixer IKA® Eurostar Power control-visc 6000, deflocculating blade D 45 mm 1,300 rpm Reactor 2: 2.5 L stainless steel Mixer RS ​​Lab, propeller with 4 inclined blades 800-1,000 rpm

[0179] Protocol

[0180] The microsphere suspension is manufactured according to the following successive steps 1-6:

[0181] 1 / Loading reactor 1 with the ingredients of the first aqueous phase indicated above at a temperature of 65°C.

[0182] 2 / Preparation of the fatty phase by melting the wax at 70°C and adding then the CosmeGreen™ ES 1822+.

[0183] 3 / Addition of the previously melted fatty phase in said reactor 1, for 1 minute, stirring in an IKA Eurostar stirrer at 1300 rpm, then for 7 minutes.

[0184] 4 / Production of the second aqueous phase in reactor 2 with the ingredients indicated above, while stirring with an RS Lab stirrer, at speed 800 rpm.

[0185] 5 / Addition drop by drop of the emulsion present in reactor 1 into the reactor 2 under high speed 1000 rpm.

[0186] 6 / Obtaining a suspension of microspheres of size 15 pm, to which we adds 1% of Euxyl K712 preservative by mass relative to the total mass of the suspension.

[0187] This process allows the following microsphere suspensions to be obtained:

[0188] Suspension 1

[0189] [Tables4] Trade name INCI % - Aqua 68.61 Phytowax 10L40 Hydrogenated Olive Oil Decyl Ester 23.72 INAVEA Original Acacia Senegal Gum 5.42 CosmeGreen ES 1822+ CH Behenyl Alcohol 1.25 Arachidyl Alcohol Betaine Euxyl K 712 Aqua 1 Sodium benzoate Potassium sorbate

[0190] The microspheres are suspended in an aqueous medium, the aqueous medium further comprising a preservative (Euxyl K 712). The aqueous suspension 30.39% by mass of microspheres relative to the total mass of the suspension.

[0191] Each micro sphere comprises: - 78.06% by mass of wax, relative to the total mass of the microsphere, the wax being a hydrogenated olive wax; - 4.11% by mass of the cationic surfactant CosmeGreen ES 1822+, relative to the total mass of the microsphere; - 17.83% by mass of the colloid, relative to the total mass of the microsphere, the colloid being the residual colloid used in the process.

[0192] Another suspension was obtained by the process described above, the fatty phase being composed of a mixture of hydrogenated olive oil and hydrogenated castor oil.

[0193] Another suspension was obtained by the process described above, the fatty phase being composed of a mixture of hydrogenated olive oil and hydrogenated castor oil. The suspension is described below.

[0194] Suspension 2

[0195] [Tables5] Trade name INCI % - Aqua 68.61 Phytowax 18L57 Hydrogenated Olive Oil Stearyl Ester 11.86 Phytowax 22L73 Elydrogenated Castor Oil Behenyl Ester 11.86 INAVEA Original Acacia Senegal Gum 5.42 CosmeGreen ES 1822+ CH Behenyl Alcohol 1.25 Arachidyl Alcohol Betaine Euxyl K 712 Aqua 1 Sodium benzoate Potassium sorbate

[0196] The microspheres are suspended in an aqueous medium, the aqueous medium further comprising a preservative (Euxyl K 712). The aqueous suspension comprises 30.39% by mass of microspheres relative to the total mass of the suspension.

[0197] Each micro sphere comprises: - 78.06% by mass of waxes, relative to the total mass of the microsphere, the waxes being a mixture of hydrogenated olive oil and hydrogenated castor oil; - 4.11% by mass of the cationic surfactant CosmeGreen ES 1822+, relative to the total mass of the microsphere; - 17.83% by mass of the colloid, relative to the total mass of the microsphere, the colloid being the residual colloid used in the process.

[0198] Example 2 _: Process for obtaining a dispersion of microspheres according to the invention composed mainly of glycine betaine derivatives

[0199] In this example, cosmetic ingredient microspheres were obtained, the microspheres being composed mainly of glycine betaine derivatives.

[0200] The ingredients and proportions used in the process are described in the table below.

[0201] [Tableauxô] Emulsion 1st aqueous phase Fatty phase 2nd aqueous phase 99% Demineralized water 1% PVA* Buffer solution qsp pH4.3 100% CosmeGreen ES 1822 +* 95% Demineralized water 5% INAVEA ORIGINAL (acacia gum)** Buffer solution qsp pH 4.3 * Surfactant; **Protective colloid; *** Active ingredient

[0202] CosmeGreen ES 1822+ is a glycine betaine derivative.

[0203] The volume ratio between the fatty phase and the first aqueous phase in the emulsion is 30:70.

[0204] The volume ratio between the emulsion and the second aqueous phase in the dispersion is 65:35.

[0205] The emulsion transfer rate in "drop by drop" is 400ml / min. The dry extract of the dispersion obtained in example 2 is 21.5%.

[0206] The diameter D(50) of the produced microspheres is 3.1pm. The D(10) is 0.6pm and the D(90) is 8.5pm.

[0207] Material used

[0208] [Tables7] Reactor s Agitator s Speed ​​Reactor 1: 5 L stainless steel Mixer IKA® Eurostar Power control-visc 6000, deflocculating blade D 45 mm 600 rpm Reactor 2: 5 L stainless steel Ultra-Turrax IKA T50, rod S50N-G45F 10,000 rpm

[0209] Protocol

[0210] The microsphere suspension is manufactured according to the following successive steps 1-6:

[0211] 1 / Loading reactor 1 with the ingredients of the first aqueous phase indicated above at a temperature of 85°C.

[0212] 2 / Preparation of the fatty phase by melting the CosmeGreen™ at 90°C ES 1822+.

[0213] 3 / Addition of the previously melted fatty phase in said reactor 1, for 1 minute with stirring in an Ultra-Turrax IKA T50 at 3,000 rpm, then for 5 minutes at 10,000 rpm.

[0214] 4 / Production of the second aqueous phase in reactor 2 with the ingredients indicated above, with stirring using an IKA Eurostar stirrer, at speed 600 rpm.

[0215] 5 / Addition drop by drop of the emulsion present in reactor 1 into the reactor 2 under high speed 600rpm.

[0216] 6 / Obtaining a suspension of Cosmegreen microspheres of size 3.1pm such as described below, to which 1% of Euxyl K712 preservative is added by mass relative to the total mass of the suspension.

[0217] Suspension 3

[0218] [Tables8] Trade name INCI % - Aqua 75.8 CosmeGreen ES 1822+ Behenyl Alcohol 19.85 Arachidyl Alcohol Betaine INAVEA Original Acacia Senegal Gum 1.77 Buffer solution Aqua 1.15 Sodium Lactate Lactic acid Euxyl K 712 Aqua 1 Sodium benzoate Potassium sorbate Kuraray-Poval 4-88 LV Polyvinyl alcohol 0.43

[0219] The microspheres are suspended in an aqueous medium, the aqueous medium further comprising a preservative (Euxyl K 712) and a buffer solution. The aqueous suspension comprises 22.05% by mass of microspheres relative to the total mass of the suspension 3.

[0220] Each micro sphere comprises: - 90.02% by mass of the cationic surfactant CosmeGreen ES 1822+, relative to the total mass of the microsphere; - 8.03% by mass of the colloid (acacia gum) and 1.95% by mass of the surfactant (PVA), relative to the total mass of the microsphere, the colloid and the surfactant being the residual colloid and surfactant used in the process.

[0221] The microsphere suspensions thus obtained may be lyophilized, for example in a CRYOTEC benchtop pilot lyophilizer, to obtain microsphere powder. A person skilled in the art will be able to determine the cycle necessary for drying the suspensions obtained.

[0222] Example 3 _: Solid shampoo comprising a surfactant in the form of microspheres

[0223] A solid shampoo obtained from syndet, comprising as surfactant a glycine betaine derivative, and more particularly CosmeGreen ES 1822+ was manufactured, the surfactant CosmeGreen ES 1822+ CH being in the form of a suspension of microspheres according to the invention and as obtained by the process described in Example 2. The suspension of microspheres used in this example is suspension 3 as obtained by the process described in Example 2 and more particularly described in Table 8.

[0224] The raw syndet comes in the form of chips which are introduced into the mixer. These chips are the product of a saponification or neutralization reaction.

[0225] The suspension of microspheres according to the invention, the perfume and possibly a colorant are then added to the mixer.

[0226] The mixer is a double Z-arm mixer which allows mechanical work at room temperature.

[0227] The mixture obtained is homogeneous and granular.

[0228] The next step is a refining step during which the previously obtained mixture is passed through a refiner which will compact it into lumps.

[0229] Refining is carried out by a twin-screw machine, equipped with cooling to keep the product at a constant temperature, approximately at room temperature.

[0230] The lumps obtained in the previous step are ground by multi-roll calenders. The spacing of the crushers is between 0 and 5 mm, and the person skilled in the art knows how to adapt the spacing according to the product to be obtained.

[0231] At this stage, the preparation is homogeneous with a soft texture.

[0232] The next step is an extrusion step, through a plodder which will compact the soap by forcing it through a die, being pushed by an endless screw.

[0233] The extruder is a duplex extruder, i.e. 2 stages with 2 screws, is equipped with a vacuum bell. The extruder is also cooled, thanks to a liquid refrigerant circuit between 5 and 15°C. At its end is the extrusion cone (and the die) the only part of the machine which is heated, between 50 and 70°C, to ensure the sliding and smoothing of the soap through the die.

[0234] Thus extruded, the syndet is cut into plugs by a guillotine cutter. The shape of the die is defined by the shape of the mold.

[0235] The bung is shaped by the press, using multi-cavity molds. The presses are in fact equipped with multi-cavity molds which are cooled (up to 20°C).

[0236] After the bond shaping operation, the surplus called crashes is automatically removed for recycling.

[0237] Example 4: Comparison of the properties of a solid shampoo comprising the surfactant CosmeGreen ES1822+ as commercially available (Le., without being formulated in the form of microspheres) with those of a solid shampoo comprising the surfactant CosmeGreen ES1822+ in the form of microspheres according to the invention

[0238] The properties of a solid shampoo obtained from syndet and comprising the surfactant CosmeGreen ES 1822+ as commercially available (i.e., without being formulated in the form of microspheres) were compared with that of a solid shampoo obtained from syndet and comprising the surfactant CosmeGreen ES 1822+ in the form of microspheres according to the invention and obtained according to the process as described in Example 2. The solid shampoos (commercial form of Cosmegreen and microspheres of Cosmegreen) were obtained according to the process described in Example 5. The suspension of microspheres used in this example is suspension 3 as obtained by the process described in Example 2 and more particularly described in Table 3. In its current commercial form, Cosmegreen has beneficial properties for hair and skin. These properties are mainly attributed to its mechanical effects.

[0239] Despite undeniable properties which contribute to the quality of cosmetic products intended for hair and skin, the formulation of Cosmegreen in different cosmetic preparations (liquid or solid) in its current commercial form raises various problems:

[0240] To be used in hot-cast solid galenics, the Cosmegreen surfactant must be melted at 80°C and mixed with fatty phases at the same temperature, and / or in glycerin to be mixed with other solids. Crystallization must be controlled to avoid phase separations between the constituents.

[0241] For its use in extruded solid galenics, the use of Cosmegreen is limited, because the extrusion temperature is lower than the melting temperature of Cosmegreen. Its dispersion in the solid phase is then poor, and its performance as a conditioner of the finished product is poor, or even non-existent.

[0242] The surfactant microspheres according to the invention offer the possibility of formulating the surfactant in these various galenic forms without heating constraints.

[0243] Solid shampoo comprising the surfactant CosmeGreen ES 1822+ as commercially available (i.e., without being formulated in the form of microspheres)

[0244] When manufacturing solid shampoo from syndet, the extrusion temperature is approximately 65°C. This extrusion temperature is lower than the 80°C melting temperature of Cosmegreen. Thus, Cosmegreen in its commercial form will not be mixed homogeneously but will be dispersed in fairly large packets (a few tens to hundreds of μm) in the mixture allowing the solid shampoo to be obtained, as visible in [Fig.2]. These aggregates and this non-homogeneity in the mixture will considerably reduce the effectiveness of the surfactant.

[0245] Indeed, when applying the shampoo with water, the constituents conventionally present in a shampoo dissolve in the water, playing their role one by one. The Cosmegreen will be deposited by friction on the surface of the hair in clumps. However, the size of the Cosmegreen clumps is significantly greater than that of a hair, causing them to be eliminated during rinsing. This considerably reduces the presence of Cosmegreen on the surface of the hair, which weakens its performance, which is partly linked to the quantity deposited.

[0246] Solid shampoo comprising the surfactant Cosmegreen in the form of microspheres according to the invention

[0247] The microsphere format according to the invention allows direct and homogeneous incorporation of the Cosmegreen surfactant into the constituents of the mixture with a view to extrusion, and allows the production of a solid shampoo with Cosmegreen uniformly distributed throughout the mass.

[0248] Advantageously, the extrusion process does not alter the microspheres which remain intact after solubilization of the shampoo in water ([Fig.3]).

[0249] When used by the consumer, Cosmegreen is deposited by friction on the hair and adheres. The deposit is uniform on the surface of the hair ([Fig.4]), and resists rinsing with water ([Fig.5]).

[0250] Indeed, the spherical shape and the d(50) particle size of 4.7 pm allow easy mechanical adhesion to hair from 30 pm (fine hair) to 70 pm (thick hair) as illustrated in [Fig.l]. Thus, the particle size / hair size ratio acts in favor of the adhesion of the particle to the hair. This adhesion allows better resistance to washing of the particles when rinsing a shampoo for example.

[0251] Thus, it clearly appears that Cosmegreen in the form of microspheres according to the invention can easily be incorporated into a solid galenic such as a solid shampoo obtained from syndet, without it being necessary to heat them, unlike its commercial form, while preserving its properties in terms of efficiency and stability. Advantageously, the microspheres are not altered by the extrusion process.

[0252] Example 7: Comparison of the performance of the Cosmegreen surfactant as commercially available (Le., without being formulated in the form of microspheres) with that of the Cosmegreen surfactant in the form of microspheres according to the invention

[0253] The objective of the test was to evaluate the acceptability, tolerance and effectiveness of three solid shampoos A, B and C. The formulas of these three compositions are reproduced below.

[0254] The methodology is reproduced below.

[0255] [Tables9] Description of the panel Panel of 24 people 17 women 7 men Average age: 44 years between 28 and 69 years Inclusion criteria Healthy volunteers Female or male volunteers Volunteers aged 18 to 75 years Duration of the test 21 days Instructions for use Apply at least 3 times a week to the scalp and hair: wet the solid shampoo and hair well then rub, massage thoroughly and rinse

[0256] Product A is a solid shampoo, obtained from syndet and comprising Cosmegreen as commercially available (i.e., without being formulated in the form of microspheres).

[0257] [TableauxlO] Ingredient % by mass compared to the total mass of the product TENSIANOL SCI 96 Cosmegreen ES 1822+ 2 Glycerin 4811 RSPO MB 2

[0258] Glycerin was introduced into the formulation because Cosmegreen ES 1822+ does not mix well on its own. Glycerin improves workability and allows Cosmegreen ES 1822+ to be incorporated into the syndet.

[0259] Product B is a solid shampoo obtained from syndet and not including Cosmegreen.

[0260] [T ables 11] Ingredient % by mass relative to the total mass of the product TENSIANOL SCI 100

[0261] Product C is a solid shampoo obtained from syndet and comprising Cosmegreen in the form of microspheres according to the invention. The microspheres are in the form of an aqueous suspension. The aqueous suspension of microspheres used in this example is suspension 3 as obtained by the process described in example 2 and more particularly described in table 8.

[0262] [Tablesl2] Ingredient % by mass compared to the total mass of the product TENSIANOL SCI 90 Aqueous suspension 3 dicrospheres of Cos megreen ES 1822+ 10

[0263] Solid shampoos A, B and C were obtained according to the process as described in example “.

[0264] For each of these compositions, the following criteria were evaluated:

[0265] [Tables 13] Criteria Rating Tolerance Mention a sign of intolerance or a feeling of discomfort such as tingling, redness, tightness, etc. Overall satisfaction The overall judgment of the product had to be categorized as "very good", "good", "bad", "very bad". The smell is pleasant The volunteers had to indicate, for each of these statements, whether they were: "TOTALLY AGREE" "AGREE" "NOT TOTALLY AGREE" "NOT AGREE" The product foams well upon application The product is easy to apply The product facilitates detangling The product produces a fine foam The product is easy to rinse The product does not dry out the hair A weighted average of the scores awarded The product protects the hair was then calculated. The product gently cleanses the hair The hair is shiny The hair is easy to style The hair is less oily The scalp seems to be balanced The product prevents my hair from getting greasy The hair is soft The product does not weigh down the hair The hair is supple The hair is light The hair is nourished

[0266] Product A results

[0267] [Tablesl4] Criteria Rating Tolerance No signs of intolerance were observed No sensation of discomfort was reported Overall satisfaction Overall judgment of the product: Very good 12.5% ​​Good: 3.5% Bad: 42% Very bad: 8%

[0268] [Tables 15] COMPLETELY AGREE D NOT COMPLETELY AGREE NOT AVERAGE WEIGHTED AGREE D AGREE D The smell is pleasant 4.55 18.18 27.27 50.00 22.73 The product foams well upon application 58.33 12.50 8.33 20.83 70.83 The product is pleasant to use 39.13 30.43 21.74 8.70 69.57 The product is easy to apply 41.67 33.33 20.83 4.17 75.00 The product facilitates detangling 22.22 16.67 33.33 27.78 38.89 The product provides a fine lather 29.17 45.83 20.83 4.17 75.00 The product is easy to rinse 47.83 43.48 8.70 0.00 91.30 The product does not dry out the hair 12.50 54.17 20.83 12.50 66.67 The product protects the hair 13.64 36.36 45.45 4.55 50.00 The product gently cleanses the hair 30.43 43.48 26.09 0.00 73.91 The hair is shiny 8.70 56.52 26.09 8.70 65.22 The hair is easy to style 25.00 37.50 25.00 12.50 62.50 The hair is less greasy 20.83 50.00 25.00 4.17 70.83 The scalp seems to be balanced 8.33 62.50 25.00 4.17 70.83 The product prevents my hair from getting greasy again 17.39 34.78 30.43 17.39 52.17 Hair is soft 25.00 37.50 20.83 16.67 62.50 The product does not weigh down the hair 29.17 37.50 25.00 8.33 66.67 Hair is supple 29.17 45.83 12.50 12.50 75.00 Hair is light 33.33 41.67 16.67 8.33 75.00 Hair is nourished 17.39 43.48 21.74 17.39 60.87 ,

[0269] Product A Conclusions:

[0270] [Tables 16] Conclusion The product presented: Very good dermatological tolerance Good cosmetic acceptability Significant items (>74%): •The product is easy to apply •The product provides a fine foam •The product is easy to rinse •The hair is supple •The hair is light

[0271] The acceptability of product A is shared. Product A is considered 50% good (sum of "very good" and "good") and is considered 50% bad (sum of "bad" and "very bad").

[0272] 29% of volunteers would buy the product, compared to 71% who would not.

[0273] Product B results

[0274] [Tablesl7] Criteria Rating Tolerance No signs of intolerance were observed No sensation of discomfort was reported Overall satisfaction Overall judgment of the product: Very good 8% Good: 54% Bad: 34% Very bad: 4%

[0275] [Tables 18] ALL AGREE NOT ALL AGREE NOT WEIGHTED AVERAGE AGREE AGREE The smell is pleasant 8.33 20.83 41.67 29.17 29.17 The product foams well when applied 29.17 62.50 4.17 4.17 91.67 The product is pleasant to use 25.00 54.17 16.67 4.17 79.17 The product is easy to apply 29.17 54.17 12.50 4.17 83.33 The product facilitates detangling 23.81 47.62 14.29 14.29 71.43 The product provides a fine lather 25.00 58.33 12.50 4.17 83.33 The product is easy to rinse 33.33 66.67 0.00 0.00 100.00 The product does not dry out the hair 30.43 43.48 21.74 4.35 73.91 The product protects the hair 21.74 39.13 34.78 4.35 60.87 The product gently cleanses the hair 33.33 58.33 8.33 0.00 91.67 The hair is shiny 25.00 50.00 25.00 0.00 75.00 The hair is easy to style 26.09 43.48 26.09 4.35 69.57 The hair is less greasy 18.18 54.55 22.73 4.55 72.73 The scalp seems to be balanced 16.67 54.17 25.00 4.17 70.83 The product prevents my hair from getting greasy again 13.04 47.83 30.43 8.70 60.87 Hair is soft 25.00 45.83 29.17 0.00 70.83 The product does not weigh down the hair 25.00 45.83 25.00 4.17 70.83 Hair is supple 25.00 50.00 20.83 4.17 75.00 Hair is light 25.00 50.00 20.83 4.17 75.00 Hair is nourished 13.04 52.17 26.09 8.70 65.22 ,

[0276] Conclusions product B:

[0277] [Tablesl9] Conclusion The product presented: Very good dermatological tolerance Good cosmetic acceptability Significant items (>74%): •The product foams well upon application •The product is pleasant to use •The product is easy to apply •The product produces a fine foam •The product is easy to rinse •The product gently cleanses the hair •The hair is shiny •The hair is supple •The hair is light

[0278] Product B is considered 62% good (sum of “very good” and “good”) and is considered 38% bad (sum of “bad” and “very bad”).

[0279] 37% of volunteers would buy the product, compared to 63% who would not.

[0280] Product results C

[0281] [Tables20] Criteria Rating Tolerance No signs of intolerance were observed 1 feeling of discomfort was reported Overall satisfaction Overall judgment of the product: Very good 42% Good: 37% Bad: 17% Very bad: 4%

[0282] [Tables21] COMPLETELY AGREE D NOT COMPLETELY AGREE NOT AVERAGE WEIGHTED AGREE D AGREE D The smell is pleasant 4.17 16.67 50.00 29.17 20.83 The product lathers well upon application 39.13 43.48 13.04 4.35 82.61 The product is pleasant to use 43.48 39.13 13.04 4.35 82.61 The product is easy to apply 50.00 45.83 0.00 4.17 95.83 The product facilitates detangling 19.05 57.14 19.05 4.76 76.19 The product provides a fine lather 41.67 45.83 8.33 4.17 87.50 The product is easy to rinse 54.17 45.83 0.00 0.00 100.00 The product does not dry out the hair 33.33 45.83 12.50 8.33 79.17 The product protects the hair 17.39 60.87 17.39 4.35 78.26 The product gently cleanses the hair 29.17 62.50 4.17 4.17 91.67 The hair is shiny 25.00 50.00 20.83 4.17 75.00 The hair is easy to style 45.45 31.82 18.18 4.55 77.27 The hair is less greasy 16.67 45.83 33.33 4.17 62.50 The scalp seems to be balanced 20.83 50.00 20.83 8.33 70.83 The product prevents my hair from getting greasy 8.70 47.83 30.43 13.04 56.52 The hair is soft 29.17 54.17 16.67 0.00 83.33 The product does not weigh down the hair 21.74 52.17 21.74 4.35 73.91 Hair is supple 20.83 54.17 20.83 4.17 75.00 Hair is light 20.83 45.83 29.17 4.17 66.67 Hair is nourished 17.39 60.87 13.04 8.70 78.26 ,

[0283] Product C is considered 79% good (sum of “very good” and “good”) and is considered 21% bad (sum of “bad” and “very bad”).

[0284] 67% of volunteers would buy the product, compared to 33% who would not.

[0285] Table

[22] Conclusion The product presented: Very good dermatological tolerance Good cosmetic acceptability Significant items (>74%): •The product foams well upon application •The product is pleasant to use •The product is easy to apply •The product facilitates detangling •The product produces a fine foam •The product is easy to rinse •The product does not dry out the hair •The product protects the hair •The product gently cleanses the hair •The hair is shiny •The hair is easy to style •The hair is soft •The hair is supple •The hair is nourished

[0286] Thus, product C has the best performance, compared to products A and B.

[0287] As demonstrated by the consumer test, the microspheres according to the invention advantageously make it possible to improve the qualities and properties of the surfactant.

[0288] Indeed, and by comparison with the solid shampoo comprising Cosmegreen as commercially available (i.e., without being formulated in the form of microspheres), it was demonstrated in the present consumer test that the shaping of Cosmegreen in the form of microspheres makes it possible to improve the properties of the surfactant, both for its application and for its cosmetic properties, as summarized in Table 23 below.

[0289]

[0290] Improvements in application and sensoriality during application were observed: - Improvement in obtaining foam (weighted average of 70.83 for product A for the criterion “the product foams well on application” vs 82.61 for product C); - Improvement of sensoriality during application (weighted averages, respectively, of 69.57, 75 and 75 for the criteria “the product is pleasant to use”, “the product is easy to apply” and “the product provides a fine foam” for product A vs 82.61, 95.83 and 87.50 for product C); - Improvement during rinsing (weighted average of 91.30 for product A for the criterion “the product foams well upon application” vs 100 for product C). Improvement of cosmetic properties: - Improved detangling (weighted average of 38.89 for product A vs 76.19 for product C); - The product does not dry out the hair (weighted average of 66.67 for product A vs 79.17 for product C); - Improved hair protection (weighted average of 50.00 for product A vs 78.26 for product C); - Improved cleaning (weighted average of 73.91 for product A vs. 91.67 for product C) - Improved shine (weighted average of 65.22 for product A vs 75 for product C); - Improved styling (weighted average of 91.30 for product A vs. 77.27 for product C) - Improved softness (weighted average of 91.30 for product A vs. 83.33 for product C); - Improvement of the nourishing character (weighted average of 60.87 for product A vs 78.26 for product C).

[0291] Product A Product B Product C The product is easy to apply The product is easy to apply The product is easy to apply The product is easy to rinse The product is easy to rinse The product provides a fine foam The product provides a fine foam The product provides a fine foam The product foams well when applied The product foams well when applied The product gently cleanses the hair The product gently cleanses the hair The product is pleasant to use The product is pleasant to use The hair is supple The hair is supple The hair is supple The hair is shiny The hair is shiny The hair is easy to style The hair is soft The hair is nourished The product makes detangling easier The product does not dry out the hair The product protects the hair

Claims

Claims

1. Solid cosmetic composition comprising, in a physiologically acceptable medium, microspheres of glycine betaine derivatives, with a volume diameter d(50) of between 0.5 and 20 pm, preferably between 1 and 10 pm, and preferably between 2 and 8 pm.

2. Solid cosmetic composition according to claim 1, characterized in that the glycine betaine derivatives represent at least 80% by mass of said microspheres.

3. Solid cosmetic composition according to claim 2, characterized in that the microspheres do not comprise waxes.

4. Solid cosmetic composition according to claim 1, characterized in that the microspheres comprise at least one glycine betaine derivative and at least one wax.

5. Composition according to any one of claims 1 to 4, characterized in that the glycine betaine derivatives are glycine betaine ester or amide salts, and preferably glycine betaine ester or amide salts of 14 to 24 carbon atoms, and preferably the glycine betaine derivatives are of formula (I) [Chem 1] Xn-[(CH3)3N+-CH2-COZ-R]n where: Z denotes an oxygen atom or an -NH group, R is a linear or branched, saturated or unsaturated alkyl group comprising 14 to 24 carbon atoms, preferably the radical R is chosen from the myristyl (C14:0), cetyl (C16:0), palmitoleyl (C16:1), stearyl (C18:0) groups, oleyl (C18:1), linoleyl (C18:2), linolenyl (C18:3), arachidyl (C20:0), arachidonyl (C20:4), behenyl (C22:0), 2-hexyldecyl, 2-octyldodecyl and 2-decyltetradecyl, X is an organic or inorganic anion, and n is 1 or 2.

6. Composition according to claim 4, characterized in that the wax is chosen from hydrogenated castor oil, 2,3-di(octadecanoyloxy)propyloctadecenoate, hydrogenated olive oil, hydrogenated palm oil, shellac, 1,3-di(tetradecanoyloxy)propan-2-yl, carnauba wax, candelilla wax, beeswax, Glyceryl Stearate SE, Glyceryl Stearate, rice wax, hydrogenated coconut oil, macadamia wax, sumac wax, sumac berry wax, hydrogenated jojoba oil, hydrogenated sunflower oil, sunflower wax, orange peel wax, mimosa wax, jasmine wax, damask rose wax, myrica berry wax, green tea leaf wax and lanolin wax and mixtures thereof.

7. Composition according to any one of claims 1 to 6, characterized in that the microspheres are in the form of an aqueous suspension or powder.

8. Composition according to any one of claims 1 to 7, characterized in that it is in the form of soap, syndet, solid shampoo or solid shower gel, preferably obtained from soap or syndet, balm, solid or semi-solid stick, powder to be reconstituted for the formation of a cosmetic product, and preferably in the form of solid shampoo, preferably obtained from syndet.

9. Use of microspheres of glycine betaine derivatives, with a volume diameter d(50) of between 0.5 and 20 pm, preferably between 1 and 10 pm, and preferably between 2 and 8 pm, for improving the cosmetic performance of glycine betaine derivatives.

10. Use according to claim 9, characterized in that the cosmetic performances are chosen from obtaining foam, sensoriality, rinsing, detangling, hair protection, cleaning, shine, styling, softness, nourishing character.

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