FR2996752A1 - USE OF COSMETIC BALLS, PACKAGING AND ASSOCIATED COSMETIC BALLS. - Google Patents

Abstract

The invention relates to a use of a cosmetic ball comprising a base solution incorporating at least one cosmetic active ingredient further comprising at least one polymer capable of forming a structure according to the "egg-box" model mixed with said cosmetic active agent, the ball being spherified in a spherification bath with a source component of polyvalent ions for said spherification, the beads being preferably preserved in a neutral gelling agent, characterized in that it comprises the steps for: five balls, preferably a ball, - applying said beads to the skin, - pressing said beads against the skin until crushed; - Massage the skin with said crushed balls and / or spread them until penetration. The invention also relates to a packaging and a cosmetic ball associated therewith.

Description

TECHNICAL FIELD OF THE INVENTION [001] The field of the invention is that of cosmetology. More specifically, the invention relates to a process for obtaining cosmetic formulations, in particular but not exclusively without excipient, distributed in unit dose form. [2] In the field of the invention, a formulation is defined as being a preparation resulting from a mixture of different raw materials, in order to respond to a demand expressed, in general, in terms of properties. [3] In addition, a cosmetic product or active ingredient is any substance or mixture intended to be brought into contact with various superficial parts of the human body, in particular the epidermis, the hair and hair systems, the nails, the lips. ., for the purpose of cleaning, protecting, perfuming, maintaining in good condition, altering their appearance or smell. Cosmetics are, in particular, hygiene and beautification products which remain superficial in their actions, not acting below the barrier of the epidermis. [4] The typical composition of a contemporary cosmetic formulation is: surfactants, water-soluble polymers, thickeners, preservatives, antibacterials, antiseptics, emollients and moisturizers, pigments, propellants, fragrances, dyes, various additives. [5] Among the manufacturers of cosmetics, some seek to offer mainly, or even exclusively, nature-friendly products, containing neither preservatives nor synthetic additives, and being particularly rich in active plant ingredients. [6] Conventionally, products of this type incorporate high levels of vegetable oils, associated with the benefits of essential oils. [7] Furthermore, in the field of pharmacology or biotechnology, it is known to encapsulate in particular active ingredients in order to target their diffusion in the body. [8] As such, encapsulation techniques are nowadays more and more explored and used. [9] Recently, these techniques have been reconsidered for the development of molecular cooking for which we then speak of spherification This technique consists of the controlled gelation of a liquid which, immersed in a bath, will form spheres. [10] There are two types of spherification; basic spherification or normal phase encapsulation (which consists of immersing a liquid with a gelling agent in a spherification bath) and inverse spherification, where a liquid is immersed, for example, with calcium gluconalactate, a mixture of two salts of calcium (calcium gluconate and calcium lactate) in a gelling bath. These methods make it possible to obtain spheres of different sizes. [11] Normal encapsulation is a method that makes it possible to obtain semi-solid pearls of homogeneous consistency, in which the asset to be encapsulated is dissolved.

It makes it possible to obtain pearls without residual solid capsule on the surface. [12] This technique, also known as the extrusion method, consists of dropping a solution containing a gelling agent into a spherification bath containing a high concentration of calcium ions (calcium lactate or calcium carbonate). ). [013] On an industrial scale, this type of process is carried out by devices equipped with a pumping system of the alginate solution, propelled in a calcium bath by extrusion through nozzles of adjustable diameter, vibrating (adjustable vibration intensity), and with a controlled flow rate. The vibrations of the drip system make it possible to obtain small balls of relatively constant diameter. [014] In a very widespread manner, the solution used to form beads in the spherification bath is a solution of sodium alginate. [015] From algae, alginates are natural polymers that have structural roles. They are found in cells and in the extracellular matrix where they represent about 40% of the dry mass. They are for aquatic plants, what cellulose is for terrestrial plants. They give them the rigidity or flexibility needed to withstand the stresses of their natural environment (currents, pressure ...). [16] Their basic structure is composed of unbranched polysaccharides: [3-D-mannuronic acid (M) and o-L-guluronic acid (G), linked together. [17] Mainly extracted from the species Laminaria, Ascophyllum, and Fucus, which are harvested in Norway, Australia, Japan, France or South America, these polymers are in the form of fine and white powders. They are the most widely used natural thickeners in the fields of medical, pharmaceutical, bioprocesses, or food ... [18] They form biocompatible and thermally stable gels in the presence of calcium ions , and they then provide solutions for medical encapsulation. They serve as efficient vector systems in the controlled release of drugs or living materials such as cells, enzymes or hormones. [19] Food or cosmetic side, alginates are used for their thickening, stabilizing and gelling properties, but they are also found in the encapsulation of oils, aromas, or perfumes. They are indicated under the name E401. [20] Along the polymer, there is the distribution of M and G patterns: there are three types of different sequences: alternate M and G patterns, consecutive GG patterns, and consecutive MM patterns. [021] It is important to note that it is this distribution of the different structural blocks of the alginate which defines its physical properties. Indeed, the constituent polysaccharides of the polymer are in the carboxylate form in the molecule and must therefore be stabilized by a contra-ion. [22] When it is a monovalent cation such as Na +, an ion stabilizes a carboxylate (C00-). The molecules, free in solution, then form fluid solutions. [23] On the other hand, when it is a divalent cation, such as Ca2 +, 5r2 +, or Ba2 +, the counter-ion stabilizes two C00-, thus creating bridges between the different polymers (model of the "egg box"). These specific links allow the formation of rigid "branched" structures. However, these dimerizations are observed only between the guluronic residues of two polymer chains, hence the preference to have a sequence of at least 6 to 10 G units which follow each other. When the ratio calcium / carboxyl group is sufficient, the complexes formed become insoluble and can then create fibers, films or capsules. [24] The rigidity of the gel formed is therefore proportional to the amount and length of the GG blocks in the alginate, as well as to the proportion of monovalent or divalent ions.

The other two types of motifs (MGMG or MMMM) are not involved in this type of interaction.  They then form, whatever the operating conditions, relatively flexible portions.  [25] However, if the viscosity of the alginate gel is constant when its pH is between 6 and 8, it increases significantly when the solution is acidified (pH below 3.5). Under these conditions, many H bonds are are formed and predominate over the repulsive electrostatic forces of the molecules, which contributes to the increase of the viscosity of the gel.  This is therefore a special case of thick gel formation.  with sodium alginate.  [26] The "egg-to-egg" model, described for the first time by Morris et al.  in 1973, explains the branching and dimerization of alginate molecules, in the presence of divalent ions.  [27] This model highlights the association of two GG blocks via divalent cations, most often calcium ions.  By balancing the charges carried by the units G, these ions make it possible to create links between the polymer chains.  Studies have shown a ratio of 4: 1 between G units and Ca2 + ions.  The monomers are organized around Ca2 + ions, forming box-to-egg structures.  Only GG blocks would be responsible for the formation of these structures.  In fact, the conformation of the units G makes it possible to obtain folded GG blocks on themselves, and thus forming structures that can trap the Ca2 + ions (as illustrated by FIG. 1, (FI.  Stojanovic, A.  Belscak-Cvitanovic, V.  Manojlovic.  Encapsulation of thyme (Thymus serpyllum L. ) aqueous extract in calcium alginate beads.  J Sci Food Agric.  2011)).  STATE OF THE PRIOR ART [28] The state of the art reveals numerous encapsulation processes in alginate beads.  The existing techniques are however not dedicated to cosmetic applications, and are in any case not suitable for cosmetic applications.  In fact, the processes described by the prior art have one or more of the following disadvantages: they do not make it possible to obtain well-spherical and well-lasting beads; they are not suitable for obtaining beads whose application to the skin can be immediate, without leaving capsule residues on the skin; the beads obtained are either too hard and inapplicable on the skin, or too fragile, the procedures must be reviewed, or even rethought, with each modification of the formula, because of changes in the physicochemical and organoleptic properties of the beads, they do not make it possible to ensure a good conservation of the products and a stability of the textures; they are difficult to reconcile with the use of natural raw materials, in particular from organic farming, which do not undergo any chemical purification treatment and are inherently unprocessed and uncalibrated, which gives them variables depending on their supply, especially in terms of chemical composition, odor, color or texture.  [029] The state of the art proposes for example the document FR2964017 which proposes a preparation by separate conveying in a double jacket of a first internal liquid solution containing a first product, and a second external liquid solution containing a polyelectrolyte to be gelled.  This document proposes drops comprising an outer envelope and an internal product.  These drops are stored in a liquid.  The drops are formed by a liquid jet which is then broken up into drops.  This document is however not entirely satisfactory because the process appears complex and difficult to implement.  In addition the drops do not have a homogeneous constitution, so that the use of these drops to sizes of 1 to 10 mm is uncomfortable.  In addition, the drops do not have enough stability when they are outside the storage liquid.  WO2012089819 describes a similar system with the same limits.  [30] Also known is WO2006081313 which describes a process for producing hydrophilic beads based on gellan gum, salts, divalent cations and water.  The beads may comprise a cosmetic active.  However, this document is not satisfactory enough because the beads are for use in a composition and used with the composition to effect surface abrasion or as carriers of other ingredients.  SUMMARY OF THE INVENTION [31] The invention aims in particular to overcome the disadvantages of the prior art.  [032] More specifically, the object of the invention is to propose a method of spherification suitable for transforming cosmetic formulations so as to propose them in encapsulated form allowing a method of dispensing a unit dose application in the form of a ball.  [033] The invention also aims to provide such a method that is adapted to the use of natural raw materials, especially from organic farming.  Another object of the invention is to propose a new mode of application and distribution of cosmetic products.  These objectives, as well as others which will appear later, are achieved thanks to the invention which relates to a process for obtaining cosmetic beads, of the type comprising the steps of: - preparing a basic solution incorporating at least one polymer capable of forming a structure according to the "egg-to-egg" model; - incorporate in the base solution at least one cosmetic active; preparing a spherification bath with a divalent ion source component; performing a spherification phase of the basic solution incorporating said cosmetic active agent (s); characterized in that: - the step of preparing the basic solution is carried out with at least one polymer present in the solution with a mass concentration greater than or equal to 5g / I; the spherification phase comprises a step of preparing a spherification bath made with a component present with a mass concentration greater than or equal to 0.7 g / l in divalent ions, said component being intended to react with said polymer of the solution basic.  [035] More generally, the invention provides a process for obtaining cosmetic beads, of the type comprising the steps for: - preparing a basic solution incorporating at least one cosmetic active; - Incorporate in the base solution at least one polymer capable of forming a structure according to the model "egg-to-egg" in mixture with said cosmetic active; performing a spherification of the base solution in a spherification bath comprising a source of polyvalent ions; - Preferably keep the beads obtained in a neutral gel.  By "polyvalent" ions are meant at least bivalent ions.  In particular, the ratio of 4: 1 between G units and Ca 2+ ions can be adapted with ions, for example trivalent or tetravalent ions, remaining within the scope of the invention.  [037] Surprisingly, the Applicant has found that when the beads obtained are placed in a gel, it fills the interstices and covers the beads to protect them from various damage, including problems of oxidation, syneresis , evaporation of water and deformation of the beads.  [38] The oxidation problems are remedied because the preservative gel makes it possible to fill the interstices.  This allows the air to be expelled between the balls, thus limiting the oxidation and the deterioration of the balls.  Visually and olfactorily, a change in color and / or odor is very quickly observed.  Under these conditions, it is then impossible to be able to market pearls, unless you have a very short DLUO (1 to 2 months max).  The addition of natural antioxidants did not solve the oxidation problem and the most effective solution we worked on is the addition of a "protective" gel, which will not interfere with the application of pearls.  The DLUO can then be considerably increased and go to 18 months.  [39] In addition, the previously described syneresis problems are also masked.  Indeed, the residual water from the pearls will be captured by the gel and syneresis will be less marked.  In addition, in the absence of a protective gel, an equilibrium will tend to be created between the water concentration of the pearl and that of its medium (osmotic balance).  The pearl loses water.  Maintained in a gel rich in aqueous component, the pearl will be less likely to lose water because the osmotic pressure of the gel on the pearl and vice versa will be stable.  The water of the pearl will remain in the pearl.  [40] Similarly, the evaporation of water is limited by the preservation gel: in the absence of preserving gel, if a bottle is improperly closed or left open for an instant, the pearls tend to dry out.  After 2 weeks of use (recommended treatment for 3 weeks), the last beads become unusable because they are drier and therefore harder.  [41] The preservation gel is advantageously a viscosity gel.  The balls are then in suspension and no longer deform under the effect of the weight of the balls around.  They stay much more round.  Visually, the product is more attractive because the presentation is improved, and the consumer actually applies a round pearl on her face and not a distorted pearl.  [42] In addition, there is a homogenization of the osmotic pressure between the pearl and its gel.  Aqueous solutions of the preservation gel tend to migrate into the ball and thus keep it swollen.  [43] Advantageously, the water of the protective gel is replaced by an aloe vera solution whose pH is stabilized at about 5. 5, preferably with citric acid.  In addition, this gel may comprise two different preservatives, in particular potassium sorbate and sodium benzoate.  [044] In particular, the bead conservation gel comprises a neutral gelling agent.  By "neutral gelling agent" is meant a gelling agent having substantially no organoleptic or physicochemical interaction with respect to the other components of the ball, in particular, in view of the plurivalent ions.  In particular, gelling agents such as xanthan or gellan can be used as neutral gelling agents.  Surprisingly, the applicant is aware that the use of such neutral gelling agents makes it possible to preserve the essentially spherical shape of the balls.  In the absence of such gelling agents, the balls flatten by losing water: we speak of syneresis.  In the absence of such a gelling agent, the beads lose their spherical shape and flatten which induces aesthetic defects and a loss of efficiency.  Indeed the beads lose water and therefore active ingredients.  [45] More particularly, the preservative gelling agent is a gelling agent having an irreversible deformation during shearing such as gellan.  Thus, during the application, the applied stress will completely and irreversibly break the gel.  In this way, the polymers are dislocated and the gel liquefies immediately.  [46] Thus, the invention provides a method for obtaining cosmetic products, providing the following advantages in an increased manner over the prior art: - the products are presented in the form of balls, spherical and regular; the beads obtained allow their immediate (or delayed) application and leave no residue on the skin; it ensures a good preservation of the active formula over time; it allows the incorporation of essential oil type or vegetable oil assets, this according to multiple possibilities, without it being necessary to fundamentally change the operating mode; - It leads to a product whose packaging and application to the skin are particularly original and attractive to the user.  [47] According to an advantageous embodiment, the method comprises an intermediate step of forming the balls of dropping the basic solution incorporating said cosmetic active agent (s) in a cryogenic bath.  [48] Such an intermediate step makes it possible to form a considerable number of balls at one time.  [049] Indeed, the solution of dropping the base solution dropwise directly into the concentrated spheronization bath divalent ions generates a semi-batch process, which requires: - let the beads drip for preferably about 20 to 30 s in the spherification bath concentrated in divalent ions, - allow the balls to bubble for 1 to 2 minutes before recovering them, - rinse the beads, - repeat the operation as many times as necessary to reach the quantity of beads desired.  [050] Admittedly, this technique remains possible without departing from the scope of the invention.  [051] However, with the intermediate step using the cryogenic bath, it is possible to continuously pour a relatively large amount of the base solution into the cryogenic bath.  All of the cryopreserved beads are then dipped at once into a divalent ion concentrated spherification bath, from which they are also recovered at once to be all rinsed and conditioned.  [052] Thus, thanks to the implementation of such an intermediate step, the following advantages are obtained: - less manipulation of the base solution and / or the beads and / or the specification bath concentrated in divalent ions: it results in a saving of time; - more precise information on the time spent by the balls in the divalent ions concentrated spherification bath: all the balls remain there exactly the same time (which is not the case in the case of the drip directly in the bath spherification concentrated in divalent ions which generates a difference of the order of 30s between the first drops and the last formed); - possible preservation of cryopresilized, non-spherified beads (basic solution simply fixed in nitrogen in the form of beads), this easily thanks to a simple freezer: no evolution or degradation of the beads, which preserves the possibility of achieving productions on demand, with great responsiveness.  It is noted that, with the implementation of said intermediate step, the ball is no longer formed via its interaction with the divalent ions when it arrives in the spherification bath but by cryogenics.  The formation of the ball is therefore generated by the solidification of the drop when it enters the liquid nitrogen.  The chemical process allowing the spherification occurs only afterwards, when the balls are immersed in the spherification bath concentrated in divalent ions.  [53] Advantageously, the duration of presence of the beads in the spherification bath is between 30 seconds and 3 minutes.  Such a duration of presence in the spherification bath guarantees to obtain beads which have sufficient resistance over time, without agglomerating with each other, this without reaching an excessive hardness for application to the skin and without generating a forming a film on the surface of the ball that would be likely to leave a residue on the skin.  [54] Preferably, the step of preparing the spherification bath is carried out with calcium lactate at a mass concentration of calcium ions between 0.7 g / l and 4.4 g / l.  [55] Such a spherification bath is very effective and allows to obtain homogeneous beads.  The use of limewater as a spherification bath is however possible, but leads to more rigid beads, brittle and brittle than in a lactate solution.  It is important to note that the concentration of the calcium bath is to be expected as a function of the quantity of beads that it is desired to spherify (so as not to observe any depletion of the spherification bath before the total spherification of all the batch beads).  Thus, stoichiometric amounts will be defined depending on the type of alginate used (amount of GG blocks) and the volume of beads per bath.  [056] According to an advantageous solution, the step consisting in preparing a basic solution is carried out with at least one polymer capable of forming a structure according to the "box-to-egg" model belonging to the following group: alginates; - carrageenans; - pectins, - gellan.  [057] According to a particular embodiment, the method comprises a step of adding a second polymer in the base solution.  [058] In this case, said second polymer is preferably viscose, xanthan type, and has no physical or chemical interaction with the polymer capable of forming a structure according to the model "egg-to-egg".  [59] With such a second polymer in the base solution, a holding network is created which allows the homogeneous suspension of a fatty organic phase.  It is then possible to increase the amounts of vegetable oils and / or essential oils, as well as the quantities of butter and / or solid vegetable oils.  [60] According to one characteristic of the invention, the method therefore comprises a step of adding at least one asset belonging to the following group.  - vegetable oil; - Essential oil; - water soluble active; - fat-soluble active; - perfume; - flower water ; - dye.  [061] The invention also relates to a cosmetic ball obtained with a method as described above, characterized in that it comprises at least one cosmetic active belonging to the following group: - vegetable oil; - Essential oil ; - water soluble active; - fat-soluble active; - perfume; - flower water ; - dye.  [062] More generally, the invention relates to a cosmetic ball comprising a base solution incorporating at least one cosmetic active agent, characterized in that it further comprises at least one polymer capable of forming a structure according to the "box-to-box" model. eggs "in mixture with said cosmetic active, the ball being spherified in a spherification bath with a multi-source ion source component for said spherification, the beads being preferably stored in a neutral gelling agent.  [063] According to a preferred embodiment, such a ball comprises at least two distinct viscosity polymers.  [064] In this way, it is possible to propose cosmetic beads with relatively large proportions of natural products present in the form of fatty phase, this without excipient.  [065] According to an advantageous presentation, beads according to the invention are packaged in a container closed by a cap including a small spoon.  [066] The user is thus offered a packaging that facilitates the gripping and handling of the beads, while presenting the possibility of designing an aesthetically attractive container.  [67] Thus, the invention also relates to a package for cosmetic beads as described above or obtained by a method as described above, comprising a container and a cap, characterized in that the package comprises a gripping means for a sample of at least one ball, preferably a spoon.  [68] According to a variant, the gripping means is secured, preferably removably, to the container or lid.  [069] The invention also relates to the use of a ball as described above, preferably in a package as described above, characterized in that it consists, successively: - apply the ball to the skin; - press the ball against the skin to crush the ball, - massage the skin with the ball crushed until full penetration.  [070] More particularly, the invention relates to the use of a cosmetic ball comprising a base solution incorporating at least one cosmetic active further comprising at least one polymer capable of forming a structure according to the model "box-to-eggs In a mixture with said cosmetic active agent, the ball being spherified in a spherification bath with a multi-source ion source component for said spherification, the beads being preferably kept in a neutral gelling agent, characterized in that it comprises the steps for : - take less than five balls, preferably a ball, - apply said beads on the skin, - press said beads against the skin until crushed; - Massage the skin with said crushed balls and / or spread them until penetration.  [71] Preferably, the use is carried out with a ball taken and applied.  Advantageously, the sampling and / or application of said beads is carried out with a gripping device and / or a dispensing device such as a ball dispenser.  According to an interesting aspect, the gripping device is a spoon or a pliers.  The beads used preferably have a size of between 1 and 10 mm, preferably between 1 and 3 mm, more particularly 3 mm.  These sizes are more suitable for use according to the invention and for sampling a small number of beads.  Thus, the means for taking them is adapted to take less than five beads, preferably one or two balls, more particularly a single ball.  Thus, one can have a distribution of a constant dose, preferably a single dose of product.  [72] More particularly, the invention relates to a package of cosmetic beads preferably for use as described above, comprising a container and a cap, characterized in that the package comprises means for: - taking less than five balls , preferably a ball, and / or - apply said beads to the skin, and / or - press said beads against the skin until crushed.  [73] According to an interesting aspect, said means comprises a working portion disposed inside the package, when the latter is closed.  Thus, this part is less subject to contaminations that would be transmitted to the beads.  [74] Preferably, said means is integral, preferably removably, the cap.  Of course, said means may also be integral, preferably removably, the container.  [075] Advantageously, said means is a gripping device and / or a dispensing device such as a ball dispenser.  In particular, said means is a spoon or a plier.  According to a variant, said means is screwed or snapped onto the cap.  BRIEF DESCRIPTION OF THE FIGURES [076] Other features and advantages of the invention will emerge more clearly on reading the following description of a preferred embodiment of the invention, given by way of illustrative and nonlimiting example, and the accompanying drawings in which: - Figure 1 illustrates a polymer reacted with divalent ions to form a structure according to the model "egg-to-egg"; FIG. 2 schematically illustrates a device for carrying out a step of a method according to the invention; FIG. 3 illustrates in block diagram form the steps of a method according to the invention; - Figure 4 is a sectional view of a container for the packaging of beads according to the invention.  [077] For greater clarity, the identical or similar elements are marked with identical reference signs throughout the figures.  DETAILED DESCRIPTION OF AN EMBODIMENT [078] With reference to FIG. 2, a device that can be used for carrying out a method according to the invention comprises: a pumping system 1 of a solution base 2 incorporating at least one polymer capable of forming a structure according to the "egg-to-egg" model, such as an alginate solution; one or more nozzles 3, preferably of adjustable diameter, vibrating (with a frequency and / or an amplitude of adjustable vibrations, these vibrations contributing to obtain balls having a relatively constant diameter), and with a controlled flow, to deliver the basic solution 2 drip; a tank 4 containing a bath, described below, intended to receive the drops of the basic solution delivered by the nozzle or nozzles 3.  [079] According to a conceivable embodiment, the tank 4 contains a spherification bath prepared with a divalent ion source component, in which the drops bubble for a few minutes until obtaining beads of the desired hardness.  [080] According to a preferred embodiment, the tank 4 contains a cryogenic bath, in the form of liquid nitrogen, at -196 ° C.  [081] Thus, in contact with liquid nitrogen, the drop (a priori round or almost) freezes instantly, forming a ball.  It no longer evolves as long as it is stored at a maximum of -20 ° C.  [82] This step makes it possible to form a large quantity of balls at one time.  Indeed, all of the basic solution 2 contained in the pumping system will be poured dropwise into the liquid nitrogen.  At the end of this intermediate cryogenic step, all the cryogenic beads are dipped at once in the spherification bath prepared with a divalent ion source component.  The balls are collected together for rinsing and conditioning.  [83] As illustrated by FIG. 3, the main steps of a process according to the invention are successively: step A: preparation of a basic solution incorporating at least one polymer capable of forming a structure according to the model "Egg-box"; step B: incorporate in the base solution at least one cosmetic active agent; step C: pour in dropwise the basic solution incorporating the cosmetic active ingredient in a cryogenic bath; step D: immerse the beads in a spherification bath prepared with a divalent ion source component; step E: remove the beads from the spherification bath; step F: rinsing the beads; step G: conditioning of the balls.  [084] The method provides a step of preparing the base solution with at least one polymer present in the solution with a mass concentration greater than or equal to 5 g / l.  [85] The polymer at the origin of the spherification may be any dimerizable polymer (or mixture of such polymers) capable of forming stable, organized, bridged and branched structures with multivalent ions.  In this category are all the polymers allowing the formation of structure according to the "egg-to-egg" model: alginates, carrageenans (iota), pectins, gellan.  [86] In the case of a basic solution consisting of an alginate solution, the alginate concentration may vary from 0.5% by mass until saturation.  In the case where it is intended to incorporate in the base solution a cosmetic active comprising a fatty phase, the method may comprise a step of adding a second polymer in the base solution.  The second polymer is viscose, of the xanthan type, and has no physical or chemical interaction with the polymer capable of forming a structure according to the "box-egg" model.  [88] The purpose of this addition is to create a second structuring network.  It is therefore possible to use for this purpose any polymer or mixture of polymers having viscosifying properties, capable of creating a maintenance network for the additives (hydro and liposoluble) incorporated in the basic solution, and which is inert or presenting only very few interactions with bivalent (or more) ions present in the medium: xanthan, guar gum, carob, konjac, gellan. . .  [89] As indicated above, the process involves the use of a spherification bath incorporating a divalent ion source component, and therefore a step of preparing such a bath.  [90] According to the principle of the invention, this step of preparation of the spherification bath is carried out with a component (intended to react with the polymer of the basic solution) present with a mass concentration greater than or equal to 0.7 g / I divalent ions.  [91] According to a preferred solution, the component of the spherification bath is a source of calcium.  More specifically, the bath preparation is carried out with calcium lactate at a mass concentration of calcium ions of between 0.7 g / l and 4.4 g / l.  [092] However, it is noted that other sources of divalent ions can be used, such as magnesium, barium. . .  [093] With such a bath, the duration of presence of the beads in the spherification bath is between 30 seconds and 3 minutes, and preferably between 2 and 2.5 minutes.  [094] A method according to the invention makes it possible to obtain various and varied cosmetic beads, including one or more cosmetic active agents belonging to the following group - vegetable oil; - Essential oil; - water soluble active; - fat-soluble active; - perfume; - flower water; - dye.  [95] As already mentioned above, for formulations incorporating a fatty phase, the formulation of the beads preferably comprises at least two distinct viscosity polymers.  [96] Ball formulations with exclusively natural components may for example comprise: - for an "anti-wrinkle" treatment: vegetable oils of camelina, flax and hemp, immortal flower essential oil and lemongrass ; - for a "first wrinkles" treatment: vegetable rosehip rose oil and mandarin essential oil; - for a "sensitive skin" treatment: rose floral water, rose geranium essential oil and rosewood; - for a "stain-resistant" treatment: vegetable oils, bearberry macerate, vanilla macerate.  [97] Moreover, cosmetic beads according to the invention can be packaged in a container closed by a cap including a small spoon.  [98] An exemplary embodiment of such a container is illustrated in FIG.  [099] As shown in this figure, the beads B are stored in a cupola-shaped container 5, this container being covered with a cap 50 rising above the container so as to define an internal volume V overcoming the logs.  The upper part of the cap is separable from the base of the cap, this upper part constituting the handle 51 of a small spoon 52 which extends the handle 51 by extending within the volume V.  Of course, the small pellet 52 extends to such a height that it does not touch the balls when the cap, including the spoon, is present on the container.  The beads B are preferably coated with a neutral gelling agent G such as xanthan or gellan.  With such a container, the user can for example proceed as follows to perform a cosmetic treatment. - it separates the cap from the container; - he separates the spoon by removing it from the cap, - he introduces the spoon into the container so that a ball takes place in the teaspoon, then withdraws it from the container.  Then, he or she can successively: - apply the ball to the skin; - press the ball against the skin until crushing the ball; - massage the skin with the ball crushed until penetration preferably total.  After a few seconds of massage, all the material of the ball has penetrated your skin, and no residue remains on the surface of the skin.  DETAILED DESCRIPTION OF OTHER EMBODIMENTS During spherification, the ions make it possible to create ionic bonds between the polymers used for the spherification.  Depending on the nature of the polymers used, the nature of the ions allowing the formation of bridged structures is different.  In the case of sodium alginates, it is for example calcium, divalent cation which will allow the formation of these branched structures.  Any other type of divalent ion, such as Mn2 +, Co2 +, Cu2 +, Cd2 +, Fe2 + may also be used.  These ions showed positive results.  It is also possible to use trivalent ions such as A13 +, Fe3 +. . .  The formation of egg-box structures (implemented during the spherification), allows to imprison a cation of minimum valence of 2, between several polymer chains (or more precisely, between several GG units on the two polymers). of alginate which will associate in the case of alginates).  It is the nature of the polymer used that can determine the nature of the ion, the metal complex or the molecule that will generate these bridges.  In general, the polymers having carboxylic acid functions may optionally, depending on the distribution of the monomers along the chain, form bridged structures with cations of minimum valence 2 (alginates, pectins, gellan gum, xanthan, . . . ).  Alternatively, one can provide polymers compatible with multivalent anions, following a similar principle.  The polymers may be natural, synthetic or semisynthetic.  In particular, the preferred polymers are, for example: (1) protein-type polymers, such as wheat or soy proteins; keratin, for example keratin hydrolysates and keratin sulfonates; casein; albumin; collagen; glutelin; glucagon; gluten; zein; gelatines and their derivatives; (2) polymers derived from chitin or chitosan, such as anionic, cationic, amphoteric or nonionic polymers of chitin or chitosan; (3) polysaccharide polymers such as in particular (i) cellulosic polymers, such as hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, and quaternized cellulose derivatives; and (ii) starches and their derivatives; (4) acrylic polymers or copolymers such as polyacrylates, polymethacrylates and copolymers thereof; (5) vinyl polymers such as polyvinylpyrrolidones, copolymers of methyl vinyl ether and maleic anhydride, copolymer of vinyl acetate and crotonic acid, copolymers of vinylpyrrolidone and vinyl acetate copolymers of vinylpyrrolidone and caprolactam, polyvinyl alcohols; (6) polymers of natural origin, optionally modified, such as gum arabic, guar gum, xanthan derivatives, karaya gum; alginates, carrageenans, ulvans and other algal colloids; glycosaminoglycans, hyaluronic acid and its derivatives; shellac, sandaraque gum, dammars, elemis, copals; deoxyribonucleic acid; mucopolysaccharides, such as hyaluronic acid, chondroitin sulfate; and mixtures of these polymers.  (7) water-soluble polymers such as: caprolactams, pullulan, pectin, mannan and galactomannans, glucomannans and their derivatives.  It is also possible, in a dissociated manner or not, to use so-called gelling agents for the spherification of so-called gelling agents of structure.  By "spherification gelling agents" is meant natural, synthetic, or hemi-synthetic polymers having charged or neutral substituents but capable of evolving to an electronically charged form and balanced by a positive or negative counter ion.  These gelling agents are capable of creating a branched structure by creating ionic bonds with an external ingredient such as an ion, a metal complex or a charged molecule.  Of course, the polymers in question may be of marine, plant origin, derived from biotechnologies, or polysaccharides or synthetic polymers.  These polymers can be used alone or in combination with other polymers of nature, origin or different composition.  By "structure gelling agents" are meant molecules (polymeric or otherwise) participating in the suspension and homogeneous maintenance of oily and aqueous phases within the bead.  These gelling agents may have characteristics such as meeting the previously given definition of spherification gelling agents, but these are only special cases.  For example, it may be any natural, synthetic or semi-synthetic polymer that is compatible with the ingredients present in the formula, capable of modifying the characteristics of the pearl or gel, such that (not exhaustively) the texture, viscosity, stability, maintenance, application, or stability of the pearl.  These will preferably be neutral gelling agents and inert vis-à-vis gelling spherification.  The main purpose is to create a suspension network of pearl components, independent and autonomous vis-à-vis the first network formed by the spherifiers gelling.  They can be or film-forming, hydro or fat-soluble.  They may be used alone or in combination with other structural gelling agents.  The gel may further comprise antioxidants to better preserve the beads.  The first results available are positive.  By "antioxidant" is meant any compound capable of trapping free radicals present and generated in and by the medium or environmental stresses (storage, UV exposure, air. . . ), evolving into a stable, non-aggressive form.  These can be antioxidants of different chemical natures, natural, partially to totally synthetic, pure or mixed (unpurified vegetable extracts for example. . . ), or of different categories (primary, secondary, chelating, synergists. . . ).  The following antioxidants may especially be used in the context of the invention: phosphoric acid derivatives such as ethylene diamine tetra (methylenephosphonic acid), hexamethylene diamine tetra (methylenephosphonic acid), diethylene triamine penta (methylene phosphonic acid) and their salts and in particular their sodium salts; ethylene diamine tetracetic acid and its salts such as the sodium salt; guanosine; superoxydismutase; tocopherol (vitamin E) and its derivatives (acetate); ethoxyquin; lactoferrin; lactoperoxidase, and nitroxide derivatives; superoxide dismutases; glutathione peroxidase; plant extracts with antiradical activity such as the aqueous extract of wheat germ marketed by the company Silab under the reference Detoxiline; green tea; and their mixtures. These antioxidants allow an effective combination with the other components of the gel in the context of the formulation of beads according to the invention.  Alternatively it is possible to use phases of different nature in the ball according to the invention.  For this purpose, emulsions can be obtained by various processes: For example ultrasonic emulsions (Genialis solutions): suspension by mechanical stirring, micronization of the phase to be emulsified in the aqueous phase.  The structure gelling agent for maintaining this stable emulsion.  It is also possible to add emulsifiers of different nature: natural and / or partially to totally synthetic, waxes, mineral compounds. . .  The emulsion processes envisaged are conventional processes used in the cosmetics industry (heating, mixing, homogenization).  Many combinations can be envisaged without departing from the scope of the invention; the skilled person will choose one or the other depending on the economic, ergonomic, dimensional or other constraints that must be respected.

Claims (11)

REVENDICATIONS1. Use of a cosmetic ball comprising a base solution incorporating at least one cosmetic active ingredient further comprising at least one polymer capable of forming a structure according to the "egg-to-egg" model mixed with said cosmetic active, the ball being spherified in a spherification bath with a multi-source ion source component for said spherification, the beads being preferably kept in a neutral gelling agent, characterized in that it comprises the steps for: - taking less than five beads, preferably a ball applying said beads to the skin; pressing said beads against the skin until crushed; - Massage the skin with said crushed balls and / or spread them until penetration. 15 2. Use according to claim 1, characterized in that it is carried out with a ball taken and applied. 3. Use according to claim 1 or 2, characterized in that the sampling and / or application of said beads is carried out with a gripping device and / or a dispensing device such as a ball dispenser. 4. Use according to claim 3, characterized in that the gripping device is a spoon or a pliers. 25 5. Packaging cosmetic beads for use according to one of claims 1 to 4, comprising a container and a cap, characterized in that the package comprises means for: - taking less than five beads, preferably a ball, and / or - applying said beads to the skin, and / or - pressing said beads against the skin until crushed. said cosmetic beads being preferably stored in a neutral gelling agent. 35 6. Packaging according to claim 5, characterized in that said means comprises a working portion disposed inside the package, when the latter is closed. 7. Packaging according to claim 5 or 6, characterized in that said means is integral, preferably removably, the cap or container. 8. Packaging according to one of claims 5 to 7, characterized in that said means is a gripping device and / or a dispensing device such as a ball dispenser. 9. Packaging according to one of claims 5 to 8, characterized in that said means is a spoon or a pliers. 10. Packaging according to one of claims 5 to 9, characterized in that said means is screwed or latched on the cap. 11. A cosmetic ball comprising a base solution incorporating at least one cosmetic active ingredient further comprising at least one polymer capable of forming a structure according to the "egg-to-egg" model mixed with said cosmetic active agent, the ball being spherified in a spherification bath with a multi-source ion source component for said spherification, characterized in that the ball is stored in a neutral gelling agent.