FR3072026B1 - PARTICLE ASSEMBLIES, PREPARATION METHODS AND KITS COMPRISING THE SAME - Google Patents

Abstract

The present invention relates to a set of particles, identical or different, in which at least two particles are fixed to each other by means of a layer of solid adhesion solution at ambient temperature and atmospheric pressure, said particles being in particular chosen from solid or matrix particles and / or particles of the core / shell type, in particular capsules with a liquid core.

Description

PARTICLE ASSEMBLIES, PREPARATION METHODS, AND KITS INCLUDING THE SAME

The subject of the present invention is sets of macroscopic particles, especially in the form of complexes, as well as their methods of preparation. It also relates to kits comprising said sets of particles.

Compositions, in particular cosmetic, based on the use of macroscopic particles are known per se. As such, the Applicant manufactures and markets cosmetic compositions in the form of emulsions based on the use of macroscopic particles, namely bubbles or beads obtained via microfluidic or millifluidic processes.

The particles, in particular the bubbles or beads mentioned above, generally require the use of a wet medium, in particular in the form of a gel, to guarantee their stability and their preservation over time and during transport; they can not therefore be used alone. Moreover, these particles are free (i.e. independent of each other) and of relatively small size which does not allow easy grip.

In parallel, the visuals associated with the compositions, in particular cosmetic compositions, using macroscopic particles, in particular bubbles or beads as described above, are limited.

Thus, the particles are generally used in the presence of a more or less transparent suspensive aqueous gel ensuring in particular a good pumpability of these particles and their preservation over time. Alternatively, these particles are provided in the form of extemporaneous product, in which case the consumer, before the first use, performs a preliminary step of contacting and mixing said particles with a composition capable of depolymerizing the membrane of said particles, as described in WO2013 / 132082.

A growing craze is observed in the field of cosmetics for compositions with visuals, or even gestures, unpublished while remaining satisfactory in terms, in particular, of sensoriality and stability.

Thus, in general, the present invention aims to meet a continuous demand of consumers in this sense.

More particularly, an object of the invention is to provide a composition with a novel visual, derived from the implementation of macroscopic particles, which is inexpensive, while being adapted to multiple uses, including the cosmetic field, even pharmaceutical or agri-food.

Furthermore, an object of the invention is to provide a composition with a novel visual and improved properties in terms of particle stability over time and transport.

Another object of the invention is to provide particles that can be used alone, that is to say without resorting to the use of a wet medium comprising said particles in free form, where appropriate in suspension, and easy grip.

Finally, an object of the invention is to provide an asset encapsulation system with a novel visual and ensuring a release / diffusion of encapsulated assets controlled in such a way as to maintain an extended release level over the duration of life of the product under consideration.

Thus, the present invention relates to a set of particles, identical or different, wherein at least two particles are fixed to one another by means of a layer of solid adhesion solution at room temperature and atmospheric pressure.

These particles are fixed together and can be considered to be mechanically interconnected.

According to the invention, among these particles, certain particles are fixed to each other without intermediate layer but by physical contact (presence of a contact zone), others are fixed by means of the aforementioned adhesion solution.

The present invention is based on the manufacture of buildings (or complexes) by association of macroscopic particles with each other. More particularly, the particles are "glued" to each other by means of a solid adhesion solution at room temperature and atmospheric pressure. The set of particles according to the present invention can therefore be likened to a complex of at least two macroscopic particles, which are identical or different, in particular each particle having a mean diameter greater than 200 μm, characterized in that the particles are "glued" >> between them thanks to a solution of adhesion.

By "complex" is meant a polyparticular building consisting of at least two particles, identical or different. The set of particles according to the invention is particularly advantageous in that it consists of an unprecedented visual alternative in terms of composition, especially cosmetic. It is also an original alternative to preserve the integrity of the particles as such and therefore also assets likely to be encapsulated therein, the encapsulation of assets to reduce or prevent their subsequent aging, including oxidation, enzymatic and / or ionic degradation, etc .... A set therefore improves the stability of the particles in time and transport.

An assembly according to the invention can also be used alone, that is to say without resorting to the implementation of a wet medium comprising said particles and is easy to grip.

particles

According to one embodiment, the particles of the assembly according to the invention have a mean diameter greater than 200 μm, and preferably between 200 μm and 7,000 μm. Thus, these particles are macroscopic particles, that is to say, visible to the naked eye.

Preferably, the particles of the assembly according to the invention have an average diameter of between 200 .mu.m and 5000 .mu.m, preferably between 300 .mu.m and 3000 .mu.m, especially between 400 .mu.m and 2500 .mu.m, and in particular between 500 .mu.m and 500 .mu.m. and 2000 pm.

Preferably, the particles according to the invention have a substantially spherical shape.

According to one embodiment, the particles according to the invention are monodisperse. In the context of the present description, the term "monodisperse particles" means that the population of particles according to the invention has a uniform size distribution, especially as defined in FR3041251.

According to one embodiment, the particles according to the invention are transparent or at least translucent (at the level of the bark and / or the heart in the case of particles of the heart / bark type).

According to one embodiment, the particles are colored (at the level of the bark and / or the heart in the case of particles of the core / bark type).

According to one embodiment, the particles are of identical or different size and / or composition of active (s) and / or of color.

According to one embodiment, an assembly according to the invention comprises at least two populations of different particles which differ by at least the size and / or the composition and / or the content of the active agent (s) and / or the color.

Preferably, the particles according to the invention are chosen from solid or matrix particles and / or particles of the core / shell type, in particular capsules with a liquid core. According to one embodiment, the set of particles may comprise identical or different particles, and therefore for example may comprise solid or matrix particles, particles of the core / shell type and mixtures of these.

According to one embodiment, the set of particles according to the invention comprises identical particles.

The particles according to the invention can be monophasic or multiphasic. For example, they comprise a heart (which comprises at least one phase) and a shell (or envelope or membrane) (which constitutes another phase) completely encapsulating the heart. The core is preferably liquid at 25 ° C. The heart can itself include one or more phases. The bark completely encapsulating the core is typically based on at least one gelled polyelectrolyte (P1) as defined below.

Solid particles

According to one embodiment, the particles according to the invention are solid (or monophasic) particles.

According to a particular embodiment, the particles are spheres (S1) which are solid at ambient temperature and at atmospheric pressure, comprising at least one gelling agent, preferably heat-sensitive,

The spheres (S1) are preferably soft solids. According to the invention, the term "flexible solid" is understood to mean in particular that the spheres (S1) according to the invention do not flow under their own weight, but may be deformed by pressure, for example with a finger.

According to one embodiment, the gelling agent, preferably heat-sensitive, and therefore the spheres (S1), is / are hydrophilic (s) and thus formed (es) of at least one aqueous phase.

According to another embodiment, the gelling agent, preferably heat-sensitive, and therefore the spheres (S1), is / are lipophilic (s) and therefore formed (s) of at least one oily phase.

Preferably, the spheres (S1) are hydrophilic and are in particular agar beads.

According to one embodiment, the spheres (S1) according to the invention are prepared by using a "non-microfluidic" process, namely by simple emulsification, or a "microfluidic" process, in particular such as described in FR1752208.

Preferably, the spheres (S1) are translucent, or even transparent.

Particles of the heart / bark type

According to another embodiment, the particles according to the invention are particles of the heart / shell (or core / shell) type, also referred to as "capsules" or "beads".

According to one embodiment, the particles comprise a liquid core or at least partially gelled or at least partially thixotropic and a bark completely encapsulating said core, said core being monophasic or having an intermediate drop of an intermediate phase, the intermediate phase being placed in contact with the bark, and at least one, preferably a single, internal drop of an internal phase disposed in the intermediate drop.

According to one embodiment, the particles according to the invention are capsules which comprise a liquid core or at least partially gelled or at least partially thixotropic and a bark, in particular a gelled envelope, totally encapsulating said liquid core, said core liquid being monophasic, and in particular based on a predominantly aqueous phase or on the contrary a predominantly oily phase.

Such a type of particles then corresponds to simple capsules comprising two distinct phases, an internal liquid phase or at least partially gelled or at least partially thixotropic and an external phase, in particular in the gelled state, surrounding the internal phase.

According to a particular embodiment, the particles according to the invention are capsules which comprise a liquid heart or at least partially gelled or at least partially thixotropic and a bark, in particular a gelled envelope, totally encapsulating said heart, said heart comprising an intermediate drop of an intermediate phase, the intermediate phase being placed in contact with the bark, and at least one, preferably a single, internal drop of an inner phase disposed in the intermediate drop. Advantageously, the ratio of the volume of the core to the volume of the shell, in particular of the gelled shell, is greater than 2, advantageously less than 50, and preferably is between 5 and 10. The intermediate phase is for example made from an aqueous or oily solution. When the intermediate phase is aqueous, the internal phase is oily, and conversely when the intermediate phase is oily, the internal phase is aqueous.

Such a type of particle then corresponds to complex capsules meaning that the liquid heart, viscous or thixotropic, has a single intermediate drop of an intermediate phase, the intermediate phase being placed in contact with the bark, in particular the envelope gelled, and at least one, preferably a single, internal drop of an inner phase disposed in the intermediate drop.

According to one variant, the core comprises a continuous intermediate phase within which a plurality of internal phase drops (s) are located.

Advantageously, the intermediate phase further comprises at least one gelling agent, especially as defined below. In particular, the gelling agent contributes to improving the suspension of the internal drop (s) disposed in the intermediate drop of the particles of the invention according to this embodiment. In other words, the gelling agent makes it possible to prevent / avoid the phenomena of creaming or sedimentation of the internal drop (s) arranged in the intermediate drop of the particles of the invention according to this method. embodiment.

According to a particular embodiment, the bark of the heart / shell type particles according to the invention is a gelled envelope. In the context of the present description, the term "gelled envelope" means an external phase at least partially surrounding an internal phase, and comprising at least one compound in the gelled state or in gel form. Preferably, the gelled envelope is an aqueous phase, and typically a hydrogel of at least one polyelectrolyte (P1) in the gelled state. The gelled envelope may also be referred to as "membrane" or "bark".

Preferably, the gelled envelope has a thickness of less than 500 μm, advantageously greater than 10 μm. The gelled envelope is generally formed by a monolayer of a homogeneous material. The gelled envelope preferably comprises a gel containing water and a polyelectrolyte advantageously chosen from proteins, natural polysaccharides, polyelectrolytes reactive with multivalent ions, and mixtures thereof.

For the purposes of the present invention, the term "polyelectrolyte reactive with polyvalent ions" means a polyelectrolyte capable of passing from a liquid state in an aqueous solution to a gelled state under the effect of contact with a gelling solution containing multivalent ions such as alkaline earth metal ions selected for example from calcium ions, barium ions, magnesium ions, and mixtures thereof.

In the liquid state, the individual polyelectrolyte chains are substantially free to flow relative to one another. An aqueous solution of 2% by weight of polyelectrolyte then exhibits a purely viscous behavior at the shear gradients characteristic of the forming process. The viscosity of this zero shear solution is between 50 mPa.s and 10,000 mPa.s, advantageously between 3000 mPa.s and 7000 mPa.s. This viscosity at the shear gradients characteristic of the flows involved during the manufacture of the capsules is for example measured using a stress-strain rheometer, or deformation, imposed at the manufacturing temperature, for example 25 ° C. For measurements, use a cone-plane geometry with a diameter of 10 to 50 mm, and a cone angle of 2 ° maximum.

The individual polyelectrolyte chains in the liquid state advantageously have a molar mass greater than 65,000 g / mol.

In the gelled state, the individual polyelectrolyte chains together with the multivalent ions form a coherent three-dimensional network which holds the liquid core and prevents its flow. The individual chains are held together and can not flow freely relative to each other. In this state, the viscosity of the formed gel is infinite. In addition, the gel has a threshold of stress to the flow. This stress threshold is greater than 0.05 Pa. The gel also has a modulus of elasticity that is non-zero and greater than 35 kPa.

The three-dimensional gel of polyelectrolyte (P1) contained in the envelope traps water and the surfactant when it is present. The mass content of the polyelectrolyte (P1) in the envelope is, for example, from 0.5% to 5% relative to the total mass of the envelope.

The polyelectrolyte (P1) is preferably a biocompatible polymer that is harmless to the human body. It is for example produced biologically.

Advantageously, it is chosen from polysaccharides, synthetic polyelectrolytes based on acrylates (sodium, lithium, potassium or ammonium polyacrylate, or polyacrylamide), synthetic polyelectrolytes based on sulfonates (polystyrene sulfonate), sodium, for example), and mixtures thereof.

More particularly, the polyelectrolyte is chosen from alkaline earth alginates, such as sodium alginate or potassium alginate, gellan or pectin, and mixtures thereof.

According to one embodiment of the invention, the polyelectrolyte (P1) is a sodium alginate.

Alginates are produced from brown algae called "laminaria", referred to as "sea weed".

Such alginates advantageously have a content of α-L-guluronate greater than about 50%, preferably greater than 55%, or even greater than 60%.

According to this embodiment, the ratio "weight of the membrane / weight of the core", especially when one has an alginate membrane (especially at 2%), is between 0.02 and 3, preferably between 0, 2 and 2, and more preferably between 0.5 and 1.5, in particular is equal to 1. This embodiment is advantageous in that it ensures an improved resistance of the capsule over time. The gelled envelope may further contain at least one surfactant. The surfactant is preferably an anionic surfactant, a nonionic surfactant, a cationic surfactant or a mixture thereof. The molecular weight of the surfactant is between 150 g / mol and 10,000 g / mol, advantageously between 250 g / mol and 1500 g / mol.

In the case where the surfactant is an anionic surfactant, it is, for example, chosen from alkyl sulphates, alkyl sulphonates, alkyl aryl sulphonates, alkaline alkyl phosphates, dialkyl sulphosuccinates and alkaline earth salts of saturated or unsaturated fatty acids. These surfactants advantageously have at least one hydrophobic hydrocarbon chain having a number of carbons greater than 5 or even 10 and at least one hydrophilic anionic group, such as a sulphate, a sulphonate or a carboxylate linked to one end of the hydrophobic chain.

In the case where the surfactant is a cationic surfactant, it is for example chosen from alkylpyridium or alkylammonium halide salts such as N-ethyldodecylammonium chloride or bromide, cetylammonium chloride or bromide (CTAB) . These surfactants advantageously have at least one hydrophobic hydrocarbon chain having a number of carbon atoms greater than 5 or even 10 and at least one hydrophilic cationic group, such as a quaternary ammonium cation.

In the case where the surfactant is a nonionic surfactant, it is for example chosen from polyoxyethylenated and / or polyoxypropylenated derivatives of fatty alcohols, fatty acids, or alkylphenols, arylphenols, or from alkylglucosides, polysorbates, cocamides.

According to one embodiment of the invention, the surfactant is sodium lauryl sulphate (SLS or SDS).

The mass content of surfactant in the shell is greater than 0.001% and is advantageously greater than 0.1%.

According to another particular embodiment, the bark of the core / bark type particles results from a coacervation reaction between at least one anionic polymer and at least one cationic polymer. These particles can also be called "bubbles" or "drops"

According to one embodiment, these particles are prepared by implementing a "non-microfluidic" method, namely by simple emulsification, or a "microfluidic" method, like the processes described in WO2012120043.

These particles may have a very thin bark, in particular of thickness less than 1% of the diameter of the particles. The thickness of the bark is thus preferably less than 1 μm and is too small to be measured by optical methods.

According to one embodiment, the thickness of the bark of the particles is less than 1000 nm, in particular between 1 and 500 nm, preferably less than 100 nm, advantageously less than 50 nm, and preferably less than 10 nm.

A method of measuring the thickness of the bark of the drops according to this embodiment is described in WO2012120043.

As noted above, the bark is formed by coacervation, i.e. by precipitation of charged polymers of opposite charges. Within a coacervate, the bonds binding the charged polymers to each other are of ionic type, and are generally stronger than bonds present within a surfactant-type membrane. The bark is formed by coacervation of at least two charged polymers of opposite polarity (or polyelectrolyte) in the presence of a first polymer, cationic type, and a second polymer, different from the first polymer, anionic type. These two polymers act as stiffening agents for the membrane.

The formation of the coacervate between these two polymers can be caused by a modification of the conditions of the reaction medium (temperature, pH, concentration of reagents, etc.). The coacervation reaction results from the neutralization of these two charged polymers of opposite polarities and allows the formation of a membrane structure by electrostatic interactions between the anionic polymer and the cationic polymer. The membrane thus formed around each particle typically forms a bark which completely encapsulates the core of the particle and thereby isolates the core of the particle from the continuous aqueous phase.

In the context of the present description, the term "anionic polymer" (or "anionic type polymer") a polymer having chemical functions of anionic type. We can also speak of anionic polyelectrolyte.

By "chemical function of anionic type" is meant a chemical function AH capable of giving a proton to give a function A. According to the conditions of the medium in which it is located, the anionic polymer thus comprises chemical functions in the form of AH, or in the form of its conjugate base A ".

As an example of chemical functions of the anionic type, mention may be made of the carboxylic acid functions -COOH, optionally present in the form of a carboxylate anion -COO-.

As an example of anionic type polymer, there may be mentioned any polymer formed by the polymerization of monomers at least a part of which carries anionic type chemical functions, such as carboxylic acid functions. Such monomers are, for example, acrylic acid, maleic acid, or any ethylenically unsaturated monomer containing at least one carboxylic acid function. It may for example be anionic polymer comprising monomeric units comprising at least one chemical function of carboxylic acid type.

Preferably, the anionic polymer is hydrophilic, i.e., soluble or dispersible in water.

Examples of anionic polymer suitable for carrying out the invention include copolymers of acrylic acid or maleic acid and other monomers, such as acrylamide, alkyl acrylates, C5-C8 alkyl acrylates, C10-C30 alkyl acrylates, C12-C22 alkyl methacrylates, methoxypolyethylene glycol methacrylates, hydroxyester acrylates, crosspolymer acrylates, and mixtures thereof.

According to one embodiment, the anionic polymer according to the invention is a crosslinked carbomer or copolymer acrylates / C10-30 alkyl acrylate. Preferably, the anionic polymer according to the invention is a carbomer.

According to one embodiment, the bark of the particles comprises at least one anionic polymer, such as for example a carbomer.

In the context of the invention, and unless otherwise stated, the term "carbomer" means an optionally crosslinked homopolymer resulting from the polymerization of acrylic acid. It is therefore a poly (acrylic acid) optionally crosslinked.

Among the carbomers of the invention, mention may be made of those sold under the names Tego®Carbomer 340FD from Evonik, Carbopol® 981 from Lubrizol, Carbopol ETD 2050 from Lubrizol or Carbopol Ultrez 10 from Lubrizol.

According to one embodiment, the term "carbomer" or "carbomer" or "Carbopol®" means a high molecular weight acrylic acid polymer crosslinked with allyl sucrose or pentaerythritol allyl ethers (handbook of Pharmaceutical Excipients, 5th Edition , plll). Examples include Carbopol®10, Carbopol®934, Carbopol®934P, Carbopol®940, Carbopol®941, Carbopol®71G, Carbopol®980, Carbopol®971P or Carbopol® 974P. According to one embodiment, the viscosity of said carbomer is between 4,000 and 60,000 cP at 0.5% w / w.

The carbomers have other names: polyacrylic acids, carboxyvinyl polymers or carboxy polyethylenes.

According to the invention, the anionic polymer may also be a crosslinked copolymer acrylates / C10-30 alkyl acrylate (INCI name: acrylates / Cw-30 alkyl acrylate Crosspolymer) as defined above.

According to the invention, the compositions according to the invention may comprise a carbomer and a crosslinked acrylates / C 10-30 alkyl acrylate copolymer.

In the context of the present application, and unless otherwise stated, the term "cationic polymer" (or "cationic type polymer") a polymer having chemical functions of cationic type. We can also speak of cationic polyelectrolyte.

Preferably, the cationic polymer is lipophilic or fat-soluble.

In the context of the present application, and unless otherwise stated, "chemical function of cationic type" means a chemical function B capable of capturing a proton to give a BIT function. Depending on the conditions of the medium in which it is located, the cationic type polymer therefore has chemical functions in form B, or in BIT form, its conjugated acid.

As an example of chemical functions of cationic type, mention may be made of the primary, secondary and tertiary amine functions, optionally present in the form of ammonium cations.

As an example of a cationic polymer, mention may be made of any polymer formed by the polymerization of monomers of which at least a part carries chemical functions of cationic type, such as primary, secondary or tertiary amine functions.

Such monomers are, for example, aziridine, or any ethylenically unsaturated monomer containing at least one primary, secondary or tertiary amine function.

Among the examples of cationic polymers suitable for the implementation of the invention, there may be mentioned amodimethicone, derived from a silicone polymer (polydimethylsiloxane, also called dimethicone), modified with primary amine and secondary amine functions.

Mention may also be made of amodimethicone derivatives, for example copolymers of amodimethicone, aminopropyl dimethicone, and more generally linear or branched silicone polymers containing amine functions.

Mention may be made of PEG-14 / amodimethicone bis-isobutyl copolymer, Bis (C13-15 Alkoxy) PG-Amodimethicone, Bis-Cetearyl Amodimethicone and bis-hydroxy / methoxy amodimethicone.

Mention may also be made of polysaccharide polymers comprising amine functions, such as chitosan or guar gum derivatives (hydroxypropyltrimonium guar chloride).

Mention may also be made of polypeptide-type polymers comprising amine functions, such as polylysine.

Mention may also be made of polyethyleneimine polymers comprising amine functions, such as linear or branched polyethyleneimine.

According to one embodiment, the particles, and in particular the shell of said particles, comprise a cationic polymer which is a silicone polymer modified with a primary, secondary or tertiary amine function, such as amodimethicone.

According to one embodiment, the particles, and in particular the bark of said particles, comprise amodimethicone.

According to a particularly preferred embodiment, the cationic polymer has the following formula:

/ çn3 m X / çhA R - Si-O-H-Si-O-H-Si-FR

\ ch3 ZvL NH? in which: R15 R2 and R3, independently of each other, represent OH or CH3; - R4 represents a group -CH2- or a group -X-NH- in which X is a divalent alkylene radical C3 or C4; x is an integer between 10 and 5000, preferably between 30 and 1000, and more preferably between 80 and 300; y is an integer between 2 and 1000, preferably between 4 and 100, and more preferably between 5 and 20; and - z is an integer between 0 and 10, preferably between 0 and 1, and better is equal to 1.

In the aforementioned formula, when R4 is -X-NH-, X is attached to the silicon atom.

In the aforementioned formula, R 1, R 2 and R 3 are preferably CH 3.

In the aforementioned formula, R4 is preferably - (CH2) 3 -NH-,

According to one embodiment, in the set of particles according to the invention, at least one particle comprises at least one active agent chosen from cosmetic, dermo-pharmaceutical, pharmaceutical or food agents.

Membership solution

The adhesion solution makes it possible to freeze / stabilize the complex formed by the association or set of particles according to the invention.

Any system and / or type of reaction ensuring the stabilization of the complex formed by the set of particles can be envisaged.

The reactivity of the adhesion solution may be of the thermoreactive, luminoreactive, ionoreactive, electroreactive, and preferably ionoreactive type.

Thus, preferably, the adhesion solution is a thermoreactive, luminoreactive, ionoreactive or electroreactive, preferably ionoreactive solution.

Depending on the type of reactivity, the adhesion solution may require coupling with a gel solution, as illustrated in more detail below.

Depending on the type of reactivity considered and in the light of the teaching of the present description, a person skilled in the art will be able to adjust the nature and / or quantity of the first material (s) required to satisfy the technical effect expected, namely, essentially, freeze / stabilize the arrangement of particles in the desired shape to form a set of particles according to the invention. In the light of the teaching of the present description, those skilled in the art will also be able to adjust the nature and / or quantity of the first material (s) at the level of the adhesion solution according to the minimum force required for detaching at least one particle from an assembly according to the invention.

Finally, those skilled in the art will also be able to adjust the type of reactivity to be preferred, given the nature of the particles used, so as to preserve the integrity of said particles.

According to the invention, the separation of the particles of an assembly according to the invention can be done by hand, and advantageously without altering the particle (s) of the assembly, in particular the membrane of said particles, which one seeks to dissociate. As an illustration, a method for qualifying this minimum force when the adhesion solution is represented by a gelled alginate solution (or alginate gel) is described below.

The method consists of making tensile measurements on macroscopic alginate gel cylinders of the spaghetti type. These wires (Lo length of about 0.2 m, diameter Cd of about 1 mm) were formed with a simple 1-channel extrusion device with a tip of about 1 mm in size, in immersing the tip in the calcium bath to suppress instability of the capillary. Controlled stress σ was applied with a set of calibrated weights m suspended from the alginate cylinders. The AL / L0 elongation of the alginate sample was measured with a rule. Assuming that v = 0.5, the Young's modulus was derived from

4ms AL of σ = -, - 2- · -t = L.-. The inventors have observed E = 71 ± 12 kPa (± SD, λ 2 O (i-al / 10) 10 N = 9).

When the minimum force is greater than E, the elongation is too great and the gel breaks. In an assembly according to the invention, this rupture is materialized by the separation of the particles of an assembly according to the invention.

The present invention is advantageous in that it allows the stabilization of a set (complex) of particles via an adhesion solution having a very thin thickness, almost imperceptible to the naked eye, which contributes to reinforce the novel visual of the invention.

To fix the particles together, the adhesion solution is solid at room temperature and atmospheric pressure.

According to the invention, the ambient temperature corresponds to a temperature of 25 ° C ± 2 ° C, and the atmospheric pressure to a pressure equal to 1 013 mbar.

The adhesion solution is preferably transparent, or at least translucent.

The adhesion solution is aqueous or oily, preferably aqueous.

According to a preferred embodiment, the reactivity of the adhesion solution is based on a reactivity of the thermoreactive type and advantageously rests on the use of at least one heat-sensitive gelling agent.

According to the invention, the expression "thermosensitive gelling agent" designates a gelling agent making it possible to increase the viscosity of the phase comprising it without said gelling agent, this viscosity evolving reversibly as a function of their temperature.

Thus, a thermosensitive gelling agent is a compound having a melting point above which it is in a liquid form, but below which it is in a solid form and thus contributes to increasing the viscosity of the phase comprising it.

Hydrophilic, ie water-soluble or water-dispersible, heat-sensitive gelling agents include, for example, gelatin, pectin, agar-agar, and mixtures thereof. Mention may in particular be made of natural gelling agents, in particular extracts of algae and, better, agar-agar.

Preferentially, the agar-agar is used as a heat-sensitive hydrophilic gelling agent. The agar-agar is particularly advantageous in that it has a good cold transparency and a good "gelling rate / crushing application" ratio.

Lipophilic, that is to say soluble or dispersible in an oil, lipophilic heat-sensitive gelling agents that may be mentioned include organic or inorganic, polymeric or molecular lipophilic gelling agents; solid fatty substances at room temperature and pressure; and mixtures thereof, especially chosen from waxes, pasty fatty substances, butters, and mixtures thereof. Those skilled in the art will be able to adjust the amount of gelling agent (s) to meet the criterion of strength of the adhesion solution at ambient temperature and atmospheric pressure.

Advantageously, a thermoreactive adhesion solution comprises between 0.1% and 15%, preferably between 0.3% and 10%, preferably between 0.5% and 5%, especially between 0.6% and 3%, particularly between 0.78% and 2%, by weight of gelling agent (s) thermosensitive (s) relative to the total weight of said adhesion solution.

According to another preferred embodiment, the reactivity of the adhesion solution is based on an ionoreactive type reactivity and is advantageously a polyvalent ion reactive polyelectrolyte / gelling solution system containing a reagent suitable for reacting with the polyelectrolyte (s) ( s), in particular an "alginate / calcium" system.

According to this preferred embodiment, the adhesion solution comprises at least one gelled polyelectrolyte (P2).

Thus, according to this preferred embodiment, the adhesion solution is derived from the gelling of at least one polyelectrolyte (P2) reactive with polyvalent ions (in particular a solution of sodium alginate) under the effect of a gelling solution containing a reagent capable of reacting with the polyelectrolyte (s) (P2).

In other words, according to one embodiment, the adhesion solution is derived from the gelling of at least one polyelectrolyte (P2) in the presence of a gelling solution containing a reagent capable of reacting with the polyelectrolyte (s). (s) (P2).

Thus, the adhesion solution is a gelled solution comprising at least one polyelectrolyte (P2) reactive with polyvalent ions; in other words, the adhesion solution is preferably a solution comprising at least one gelled polyelectrolyte.

The polyelectrolyte (P2) is as defined above for the polyelectrolyte (P1), these polyelectrolytes being identical or different.

The polyelectrolyte (P2) is advantageously chosen from polysaccharides, synthetic polyelectrolytes based on acrylates (sodium, lithium, potassium or ammonium polyacrylate, or polyacrylamide), synthetic polyelectrolytes based on sulfonates (polystyrene sulfonate), for example).

More particularly, the polyelectrolyte (P2) is chosen from an alkaline earth alginate, such as sodium alginate or potassium alginate, gellan or pectin, in particular sodium alginate. The skilled person will adjust the amount of polyelectrolyte (s) (P2) to meet the criterion of strength of the adhesion solution at room temperature and atmospheric pressure.

Preferably, the mass content of polyelectrolyte (s) (P2) reactive with polyvalent ions is less than 5%, preferably between 0.5% and 3%, and better still between 1% and 2%, by weight. relative to the total weight of the adhesion solution.

As defined above, the gelling solution comprises at least one reagent capable of reacting with the polyelectrolyte (s) (P2). In particular, the gelling solution contains at least multivalent ions, and is in particular a calcium solution.

A gelling solution according to the invention may advantageously comprise from 1% to 11%, preferably from 2% to 5%, by weight of calcium chloride relative to the total weight of said solution.

Additional compound (s)

According to the invention, the particles and / or the adhesion solution and / or, when present (s), the gelling solution and / or the depolymerizing composition defined later may / may further comprise at least one additional compound other than polyelectrolytes , anionic and cationic polymers and gelling agent mentioned above, and may furthermore include powders; Glitter, ; coloring agents, especially chosen from water-soluble or non-fat-soluble, liposoluble or non-organic or inorganic dyes, optical effect materials, liquid crystals, and mixtures thereof; particulate agents insoluble in the fatty phase; conservatives; texture agents; humectants; stabilizers; perfuming agents, especially as defined in WO2016096995; chelators; emollients; modifying agents selected from texturizing agents, viscosity agents (e.g., gelling agents / aqueous phase texture agents different from the abovementioned base), pH, osmotic strength and / or refractive index modifiers etc. or any usual cosmetic additive; and their mixtures.

According to one embodiment, the particulate agents insoluble in the fatty phase of the drops are chosen from the group consisting of pigments, ceramics, polymers, especially acrylic polymers, and mixtures thereof.

The particles and / or the adhesion solution and / or, when present (s), the gelling solution and / or the depolymerizing composition defined later may / may furthermore comprise at least one biological, cosmetic and / or food active agent, especially chosen from hydrating agents, healing agents, depigmenting agents, UV filters, desquamating agents, antioxidants, active agents stimulating the synthesis of dermal and / or epidermal macromoleculars, dermodecontracting agents, antiperspirants, soothing agents and / or anti-aging agents, and mixtures thereof.

Furthermore, the adhesion solution, or even the solution comprising at least one polyelectrolyte (P2) and / or the gelling solution, may additionally comprise any type of additional compounds such as those mentioned above, in particular humectants ( ie glycerin, propane diol, butylene glycol) and in high levels. This embodiment is advantageous in that it allows the implementation of such compounds in levels higher than those acceptable for the manufacture of the particles as such. In fact, the milli-microfluidic processes for manufacturing the particles described above can impose limits in terms of the contents of humectants, otherwise the formation of the corresponding particles may occur, because these particles can pierce the membrane. during the formation of said particles.

The present invention also relates to a kit comprising: at least two particles, chosen in particular from the solid or matrix particles and / or the core / shell type particles as defined above, at least one reactive liquid polyelectrolyte (P2) to the polyvalent ions, preferably in the form of a composition, and - at least one gelling solution containing a reagent capable of reacting with the polyelectrolyte (s) (P2) in order to make them pass from a liquid state to a gelled state.

By "liquid" polyelectrolyte (P2) is meant a polyelectrolyte (P2) in a liquid form, for example in solution, at room temperature and atmospheric pressure.

This kit is used in particular for the implementation of the methods described below, and to obtain a set of particles as defined above.

Preparation processes

The present invention relates to a process for preparing a set of particles as defined above comprising at least one step of applying an adhesion solution to at least two particles, which are identical or different, followed by the application a solution and / or conditions capable of ensuring the solidification of the adhesion solution.

The present invention also relates to a process for preparing a set of particles as defined above comprising the following steps: i) the application of an adhesion solution on at least a first particle, and ii) the addition at the level of the first particle obtained in step i), and therefore in direct contact or not with this first particle, of at least one second particle, the first and second particles being identical or different, these steps being followed by the application of a solution and / or conditions capable of ensuring the solidification of the adhesion solution, as described above.

Conditions suitable for ensuring the solidification of the adhesion solution may for example be represented by a heating or cooling step. These conditions are general knowledge of the skilled person.

The solution capable of ensuring the solidification of the adhesion solution is for example a gelling solution as described above.

For obvious reasons, the steps of applying an adhesion solution to at least one particle necessarily imply that said adhesion solution is in a liquid form. The viscosity of the adhesion solution may be adjusted to facilitate handling thereof and / or to hold the particles together for a time sufficient to solidify said adhesion solution and thus freeze the assembly according to the shape (the arrangement) wish. This adjustment is a matter of general knowledge of the person skilled in the art.

If the adhesion solution is solid at ambient temperature and atmospheric pressure before the step of applying a solution and / or conditions capable of ensuring its solidification, then the process comprises, prior to step d applying the adhesion solution to at least one particle, a step of liquefying said adhesion solution, i.e. passing said adhesion solution from a solid state to a liquid state. When the adhesion solution comprises at least one heat-sensitive gelling agent, this liquefaction step consists in heating the adhesion solution to a temperature higher than the melting point of said heat-sensitive gelling agent. In this particular embodiment, the conditions capable of ensuring the solidification of the adhesion solution may be represented by a cooling step at ambient temperature, or even at a temperature below room temperature, for example below 15 ° C. even below 10 ° C.

According to one embodiment, the method of the invention comprises the following steps: a) the application on at least two particles, identical or different, of at least one solution comprising at least one liquid polyelectrolyte (P2) suitable for gelation and b) the application, on the particles obtained at the end of step a), in particular by spraying, of at least one gelling solution, in particular containing a reagent capable of reacting with the polyelectrolyte (P2) for the change from a liquid state to a gelled state.

According to one embodiment, the method of the invention comprises the following steps: a ') the application on at least a first particle of at least one solution comprising at least one liquid polyelectrolyte (P2) capable of gelling, b' ) the addition, in contact with at least the solution comprising at least one polyelectrolyte (P2) applied to the first particle, of at least one second particle, the first and second particles being identical or different, and c ') the application, on the particles obtained at the end of step b '), in particular by spraying, of at least one gelling solution, in particular containing a reagent capable of reacting with the polyelectrolyte (P2) to make it pass from a liquid state in a gelled state.

According to one embodiment, the method of the invention further comprises at least one step of arranging the particles according to the desired shape, this step being able to be carried out before and / or after step a) or b ').

According to the invention, the various steps of the process can be repeated several times. For example, the process of the invention may comprise several steps of applying an adhesion solution, in particular a solution of sodium alginate, to at least one particle, before bringing this particle into contact with a second particle.

When the adhesion solution is an ionoreactive solution, the set of particles according to the invention is prepared according to a process consisting in: a1) having at least two particles, identical or different, in particular each particle having an average diameter greater than 200 μm, b1) applying to said particles at least one solution comprising at least one polyelectrolyte (P2), then arranging the particles into the desired shape, or vice versa, and c1) applying, in particular spraying, on the particle arrangement obtained in step (b1), at least one gelling solution, in particular containing at least one reagent capable of reacting with the (s) polyelectrolyte (s) (P2).

According to a particular embodiment, especially when it is desired to form sets of large shapes and / or volumes, the method of the invention may consist in repeating at least twice or even three times, four times, five times, six times, ..., steps (a1) to (c1) above until the desired final shape / architecture is obtained.

When the adhesion solution is a thermally reactive solution, the set of particles according to the invention is prepared according to a process consisting in: a2) having at least two particles, identical or different, in particular each particle having an average diameter greater than 200 μm, b2) applying to said particles at least one adhesion solution having a temperature sufficient to make it fluid, then arranging the particles into the desired shape, or vice versa, and c2) placing the arrangement obtained in step b2 ) at room temperature, or even at a temperature below room temperature, for example below 15 ° C, or even below 10 ° C, for a period sufficient to ensure solidification of the adhesive solution and thus freeze / stabilize the set of particles according to the invention.

These conditions of temperature and duration fall within the general knowledge of those skilled in the art.

According to a particular embodiment, especially when it is desired to form sets of large shapes and / or volumes, the method of the invention may consist in repeating at least twice or even three times, four times, five times, six times, ..., steps (a2) to (c2) above until the desired final shape / architecture is obtained.

uses

The present invention also relates to a composition, in particular a cosmetic composition, comprising at least one set of particles as defined above, in particular in association with a physiologically acceptable medium.

By "physiologically acceptable medium" is meant a medium which is particularly suitable for the application of a composition of the invention to keratin materials, in particular the skin, the lips, the nails, the eyelashes or the eyebrows, and preferably the skin.

The physiologically acceptable medium is generally adapted to the nature of the medium to which the composition is to be applied, as well as to the appearance under which the composition is to be packaged.

According to one embodiment, the physiologically acceptable medium in a composition according to the invention is devoid of agent capable of weakening and / or breaking the adhesion solution, or even the particles (in particular the membrane).

According to the invention, it is sought to preserve as much as possible the integrity of the set of particles (or complex) and particles.

Preferably, the composition according to the invention is devoid of depolymerizing agent as described below.

According to another embodiment, the physiologically acceptable medium in a composition according to the invention further comprises at least one agent capable of weakening and / or breaking the adhesion solution, or even the particles (in particular the membrane).

Advantageously, the physiologically acceptable medium comprises a low concentration of such an agent (ie less than 1% by weight) adapted to ensure embrittlement and / or slow destruction (especially over a period of time greater than 1 month) of the adhesion solution, or even the particles (in particular the membrane).

This embodiment is to be considered especially in the case where at least a portion of the particles is represented by particles employing at least one polyelectrolyte as described above.

In particular, in the context of core / shell particles comprising a gelled envelope (in particular of alginate), the agent is a depolymerizing agent as defined below.

According to the invention, the term "depolymerizing agent" means a compound capable of causing the rupture / the alteration of the particles, in particular the membranes of the particles if they are hollow particles.

This depolymerizing agent is preferably in the form of a composition or solution, which may also be referred to as "depolymerizing solution" or "depolymerizing composition".

Preferably, the depolymerizing agent is chosen from calcium chelating agents, calcium exchangeable salts, enzymes capable of degrading proteins or polysaccharides, and mixtures thereof.

This depolymerizing agent may also be a surfactant; preferably a nonionic surfactant; in particular, chosen especially from poly (ethylene oxide) alkyl and polyalkyl esters, poly (ethylene oxide) alkyl and polyalkyl ethers, polyoxyethylenated or non-polyoxyethylenated alkyl and polyalkyl esters of sorbitan polyoxyethylenated or unsaturated polyoxyethylenated alkyl- and polyalkyl ethers, alkyl- and polyalkylglucosides or polyglucosides, alkyl- and polyalkyl-sucrose esters, polyoxyethylenated or unsubstituted alkyl- and polyalkyl esters of glycerol, glycerol alkyl- and polyalkylether ethers, whether polyoxyethylenated or not, and mixtures thereof; better a PEG-7 Glyceryl Cocoate, PEG-6 Caprylic / Capric Glycerides surfactant, and mixtures thereof; for example TEGOSOFT® GC, TEGOSOFT® GMC 6 marketed by Evonik, and mixtures thereof.

The nature and / or content of the depolymerizing agent (s) which are suitable for causing the rupture / the alteration of the particles, in particular the membranes of the particles, in the case of hollow particles, is a matter of general knowledge. of the skilled person.

According to one embodiment, the cosmetic compositions are used for the makeup and / or care of keratin materials, especially the skin.

The cosmetic compositions according to the invention may be skincare, sun protection, cleaning (makeup removal), hygiene or make-up products for the skin.

Preferably, the cosmetic composition according to the invention is a make-up composition, in particular a foundation. The set of particles according to the invention allows new cosmetic gestures and the cosmetic composition according to the invention can therefore be in various forms as described below: (1) a receptacle (or conventional cosmetic pack) comprising a plurality of sets according to the invention, identical or different (a set may then correspond to a daily dose); (2) a cushion: the set of particles according to the invention is tapped with a means of application on a keratin material (ie brush, tassel, puff, mousse, brush); this causes a rupture of at least a part of the particles of said set; (3) a stick: there is a receptacle comprising at least one assembly according to the invention, the receptacle further comprising, at its upper part (ie near the outlet orifice of the composition), a means capable of causing a rupture of at least a part of the particles of said assembly (for example a grid provided with elements projecting towards the inside of the receptacle to facilitate the breaking of the particles); (4) a cosmetic kit with: - on the one hand, a plurality of identical or different sets according to the invention (a set which may correspond to a daily dose), and - on the other hand, a depolymerizing composition (ie capable of causing the separation or the rupture / alteration of at least a part of the particles forming an assembly according to the invention (each day the consumer mixes a complex with at least a part of the depolymerizing composition for "Manufacture" a custom cosmetic composition); or (5) a face mask ("sheet mask" in English): - the mask is affixed to an assembly according to the invention and then applied to the area of the body to be treated or the mask is formed by a set of particles according to the invention In this case, the solution comprising at least one polyelectrolyte, or even the adhesion solution, may further comprise at least one retarder to allow time for the asque formed by the association of particles to marry the shape of the area of the body to be treated; the set freezes once the mask manufactured and in position on the area to be treated. Thus, in the case where the adhesion solution comprises at least one polyelectrolyte, in particular an alkaline earth alginate, such as sodium alginate, a retarder may be tetrasodium pyrophosphate. Those skilled in the art will be able to adjust the concentration of the retarder to obtain the desired effect.

These compositions are therefore intended to be applied especially to the skin.

Thus, the present invention also relates to the non-therapeutic cosmetic use of a cosmetic composition mentioned above, as a makeup, hygiene, cleaning and / or care product for keratinous substances, in particular the skin.

According to one embodiment, the compositions of the invention are in the form of a foundation, a makeup remover, a facial and / or body and / or hair care, anti age, a sunscreen, a oily skin care, a whitening care, a moisturizer, a BB cream, tinted cream or foundation, a face and / or body cleanser , a shower gel or a shampoo.

A care composition according to the invention can be in particular a solar composition, a care cream, a serum or a deodorant.

The compositions according to the invention may be in various forms, in particular in the form of cream, balm, lotion, serum, gel, gel-cream or mist.

The present invention also relates to a non-therapeutic method for the cosmetic treatment of a keratinous material, in particular a make-up and / or a care product, preferably a make-up product, in particular a skin, a lips or a hair, comprising at least one step of application on said keratinous material of at least one set of particles as defined above, or of at least one composition as defined above.

In particular, the present invention relates to a non-therapeutic method for cosmetic treatment of the skin, comprising a step of applying to the skin at least one layer of a cosmetic composition as defined above.

The present invention also relates to a kit comprising: at least one set of particles as defined above, or a composition as defined above, and a composition comprising at least one depolymerizing agent as mentioned above.

According to the invention, the kit allows the consumer, every day, to mix a set of particles (or complex) according to the invention with at least a portion of the depolymerizing composition to prepare a custom cosmetic composition.

The present invention also relates to the use of a solid adhesion solution at ambient temperature and atmospheric pressure for forming and stabilizing a set of particles comprising at least two particles, which are identical or different, the said particles being chosen especially from solid particles or matrix and / or heart / bark type particles, in particular liquid heart capsules, as defined above.

The present invention also relates to a kit comprising: a set of particles or a composition according to the invention, and a second composition, in particular a cosmetic composition, different from the set of particles or from the composition according to the invention, comprising at least an agent capable of weakening and / or breaking the adhesion solution, or even the particles (in particular the membrane when the particles are of the core / shell type). The set of particles according to the invention can be used in other areas than the cosmetic field as described above. This set can be used for example in the food or pharmaceutical field.

According to one embodiment, the set of particles according to the invention comprises food additives, for example dyes and / or flavors, and is placed in a receptacle containing a solution, for example an alcoholic solution. The encapsulated food actives may diffuse more or less slowly in said solution for coloring and / or perfuming.

According to one embodiment, the set of particles according to the invention can be used to ensure a controlled and prolonged release of an encapsulated pharmaceutical active.

Throughout the description, the phrase "comprising a" should be understood as being synonymous with "including at least one", unless the opposite is specified.

The expressions "between ... and ...", "from ... to ..." and "from ... to ..." must be understood as inclusive, unless otherwise is specified.

The amounts of the ingredients in the examples are expressed as percentage by weight relative to the total weight of the composition, unless otherwise indicated.

The following examples illustrate the present invention without limiting its scope.

EXAMPLES

Example 1: Set of particles according to the invention with solid particles (spheres (S1)) and ionoreactive adhesion solution

Spheres (S1):

The spheres (S1) are obtained by a microfluidic method in dripping mode.

The phases used to prepare these spheres (S1) are the following: - aqueous phase (IF)

* Sufficient quantity for. - Oily phase (OF)

Preparation of the aqueous phase (IF) a) Blend the B1 together with stirring until a homogeneous mixture, b) B2 is added to the mixture a) without stirring and allowed to stand for 15 minutes until hydration of B2; then, stirring until a homogeneous mixture is obtained,

c) in parallel, a mixture is prepared with the B3 at 90 ° C until a homogeneous mixture is obtained in liquid form (melted), d) the mixture c) is added to the mixture b), with stirring at 90 ° C, until a homogeneous mixture is obtained so as to obtain the aqueous IF, and e) when present, add the B4 to the mixture d).

Preparation of the oily phase (OF) a) The A1 are mixed together with stirring until a homogeneous mixture is obtained, and b) A2 is added to the mixture a) with stirring and stirred until a mixture is obtained. homogeneous.

Process for preparing spheres (S1)

The spheres (S1) are obtained according to a microfluidic process, namely a double-shell microfluidic nozzle as described in WO2012 / 120043.

At the level of the microfluidic device, the parameters are as follows:

* Ambient temperature

Then, the spheres (S1) are recovered by filtration with a sieve mesh smaller than the mean diameter of the spheres (S1) and then rinsed with osmosis water.

Adhesion solution: This solution contains water, 0.5% alginate and preservatives (Microcare PE 0.8% and Microcare PTG 2%). This solution is liquid at room temperature and atmospheric pressure.

This adhesion solution, not yet gelled, is liquid at room temperature and atmospheric pressure.

Gelling solution: this solution contains water, calcium chloride (11%) and preservatives (Microcare PE 0.8% and Microcare PTG 2%).

The preparation of the adhesion and gelling solutions is a general knowledge of the person skilled in the art.

Process for preparing the set of particles according to the invention in the form of a cube: 1) 9 spheres (S1) are arranged in a horizontal plane so as to form a subset A, 2) a layer of liquid adhesion solution on the upper part of this subset A, 3) the gelling solution is sprayed on the adhesion solution to change it from a liquid state to a gelled state, and therefore solid, and thus freeze (solidify) the subassembly A, 4) 9 other spheres (S1) are arranged on the upper part of the subassembly A, so as to form a subset B identical to the subset A, 5) the steps 2 , 3 and 4 are repeated until a stack of subsets forming a cube (designated "cubic set").

Optionally, the method may further comprise a step of covering said cubic assembly with an adhesion solution and then spraying the gelling solution to provide said cubic assembly with superior strength.

Alternatively, the process for preparing the set of particles according to the invention in the form of a cube may be devoid of step 3) above in favor of a single step of spraying the gelling solution after formation of the cubic assembly, so as to gel all the layers of adhesion solution at once and freeze the assembly. This alternative may require the use of a mold or frame to facilitate the maintenance of the arrangement of spheres (S1) before gelation.

Subsequently, the consumer can destructurise the assembly by detaching said assembly from a sphere (S1) or a sphere block (S1) according to the quantity of sphere (s) (S1) that it wishes to apply to the skin.

Example 2: set of particles according to the invention with particles (P) of heart / bark type and thermoactive adhesion solution

Particles (P) of the heart / bark type:

These particles (P) consist of a gelled external phase envelope (OF), an intermediate drop of an aqueous intermediate phase (MF) and an internal drop of an oily internal phase (IF), said internal drop being completely surrounded by the intermediate drop. The particles (P) are obtained from these phases IF, MF, OF and a calcium bath (dedicated to gel the OF phase) and thus allow the formation of the gelled envelope of the particles) described below. after using a millifluidic device as described in WO2010063937 and WO2012089820. 2.1. Preparation of the oily internal phase (IF):

* Sufficient quantity for.

In a beaker, Tinogard® TT and apricot kernel oil were incorporated and then heated to 60 ° C with stirring until the Tinogard® TT was completely dissolved. 2.2. Preparation of the aqueous intermediate phase (MF):

In a beaker, the osmosis water, the microcollomer PTG, the microcare PE and the beaker were placed in mechanical agitation with a deflocculating blade.

While stirring, phylcare sodium hyaluronate CPS and protanal LF 200 were added. The engine speed was then gradually increased and agitation maintained until the powders were completely dispersed. 2.3. Preparation of the external phase (OF):

In a beaker, the osmosis water, the PTG softening microcare, the microcare PE were incorporated. The beaker was then placed under mechanical agitation with a deflocculating blade.

While stirring, sodium dodecyl sulfate and protanal LF 200 were added.

The engine speed was gradually increased and stirring continued until the powder was completely dispersed.

Finally, the Econa N-58881S and Timiron Splendid Green pigments were added, and the whole was stirred until the flakes were completely dispersed.

2.4 Composition of the calcium bath

The flows considered at the level of the millifluidic device are:

Adhesion Solution: This solution contains water, 1% agar-agar and preservatives (Microcare PE 0.8% and Microcare PTG 2%). This solution is solid at room temperature and atmospheric pressure.

Process for preparing the set of particles according to the invention in the form of a cube:

For the steps below, and unless otherwise indicated, a solution of liquid adhesion is applied by applying 80 ° C heating with stirring, 1) 9 particles (P) are arranged in a horizontal plane, 2) the liquid adhesion solution is added to these particles (P) so as to form a subset A, 3) before solidification of the adhesion solution applied in step 2), 9 other particles (P) are arranged on the adhesion solution so as to form a subset B identical to the subset A; these 9 particles (P) of the subset B are immobilized on the subset A upon solidification of the adhesion solution at room temperature, 4) Steps 2 and 3 are repeated until a stack of sub -Sets forming a cube (referred to as "cubic set").

Optionally, the method may further comprise a step of covering the cubic assembly with an adhesion solution to impart even greater strength to said cubic assembly.

Subsequently, the consumer can destructurise the assembly by dissociating said set of particles (P) or a block of particles (P) according to the amount of sphere (s) (S1) that it wishes to apply to the skin.

Example 3 Kit according to the invention

Particles (P) of the core / bark type: identical to those of Example 2.

Adhesion solution: identical to that of Example 1.

Gelling solution: identical to that of Example 1.

Depolymerizing composition:

The salts (citric acid and sodium citrate dihydrate) and water were weighed separately. The salts were then added to the water and the solution was stirred until all the salts were completely dissolved. Any active ingredients, preservatives, perfumes and / or dyes are added at this stage.

The xanthan gum is then added and the whole is stirred with a paddle stirrer for 50 minutes.

The kit comprises: a plurality of assemblies as described above; and a depolymerizing composition (see above) capable of causing the rupture / alteration of the gelled envelope of the particles (P).

Every day, the consumer makes an extemporaneous mixture between a set and a hazelnut of depolymerizing composition.

The depolymerization kinetics are approximately 2 to 10 min.

Claims (19)

1. A set of particles, identical or different, wherein at least two particles are attached to each other by means of a layer of solid adhesion solution at room temperature and atmospheric pressure. The particle assembly according to claim 1, wherein the particles have an average diameter greater than 200 μm, and preferably between 200 μm and 7,000 μm. 3. A set of particles according to claim 1 or 2, wherein the particles are selected from solid or matrix particles and / or core / shell particles. 4. A set of particles according to any one of claims 1 to 3, wherein the adhesion solution is a thermally active solution, luminous, ionoreactive or electroreactive, preferably ionoreactive. The particle assembly of any one of claims 1 to 3, wherein the adhesion solution comprises at least one heat-sensitive gelling agent. 6. A set of particles according to any one of claims 1 to 4, wherein the adhesion solution comprises at least one gelled polyelectrolyte (P2). 7. Set of particles according to any one of claims 1 to 3, wherein the adhesion solution is derived from the gelling of at least one polyelectrolyte (P2) in the presence of a gelling solution containing at least one clean reagent to react with the polyelectrolyte (s) (P2). 8. Set of particles according to any one of claims 1 to 7, wherein the particles are capsules comprising a liquid core or at least partially gelled or at least partially thixotropic and a casing completely encapsulating said core at its periphery, said core being monophasic or having an intermediate drop of an intermediate phase, the intermediate phase being placed in contact with the envelope, and at least one, preferably a single, internal drop of an internal phase disposed in the intermediate drop. 9. A set of particles according to claim 8, wherein the envelope is a gelled envelope comprising at least one polyelectrolyte (P2) in the gelled state. 10. A set of particles according to any one of claims 1 to 8, wherein the particles comprise a bark resulting from a coacervation reaction between at least one anionic polymer and at least one cationic polymer. 11. Set of particles according to any one of claims 1 to 10, wherein at least one particle comprises at least one active agent selected from cosmetics, dermopharmaceutical, pharmaceutical or food. 12. Composition, especially cosmetic, comprising at least one set of particles according to any one of claims 1 to 11, in particular in combination with a physiologically acceptable medium. 13. A method of preparing a set of particles according to any one of claims 1 to 11, comprising: - either at least one step of applying an adhesion solution on at least two particles, identical or different, followed by the application of a solution and / or conditions suitable (s) to ensure the solidification of the adhesion solution; at least the following steps: i) the application of an adhesion solution on at least a first particle, and ii) the addition at the level of the first particle obtained in step i) of at least a second particle. particle, the first and second particles being identical or different, these steps being followed by the application of a solution and / or conditions suitable (s) to ensure the solidification of the adhesion solution. 14. Preparation process according to claim 13, comprising: either the following steps: a) the application to at least two particles, identical or different, of at least one solution comprising at least one liquid polyelectrolyte (P2) specific to gel, and b) the application, on the particles obtained at the end of step a), in particular by spraying, with at least one gelling solution, in particular containing a reagent capable of reacting with the polyelectrolyte (P2) to to change it from a liquid state to a gelled state; or the following steps: a ') the application on at least a first particle of at least one solution comprising at least one liquid polyelectrolyte (P2) capable of gelling, b') adding, in contact with at least the solution comprising at least one polyelectrolyte (P2) applied to the first particle, at least one second particle, the first and second particles being identical or different, and c ') the application, on the particles obtained at the end of step b '), in particular by spraying, with at least one gelling solution, in particular containing a reagent capable of reacting with the polyelectrolyte (P2) to change it from a liquid state to a gelled state. 15. Preparation process according to claim 14, further comprising at least one step of arranging the particles according to the desired shape, this step being able to be carried out before and / or after step a) or b '). 16. Non-therapeutic method of makeup and / or care of a keratinous material, in particular the skin, comprising at least one step of applying to said keratinous material at least one set of particles according to any one of the claims. 1 to 11, or a composition according to claim 13. 17. Kit comprising: at least two particles, in particular chosen from solid or matrix particles and / or core / shell particles, at least one polyelectrolyte (P2) reactive with polyvalent ions, preferably in the form of a composition, and - at least one gelling solution containing a reagent capable of reacting with the (s) polyelectrolyte (s) (P2) for (s) passing from a liquid state to a gelled state. 18. Use of a solid adhesion solution at room temperature and atmospheric pressure to form and stabilize a set of particles comprising at least two particles, identical or different, said particles being chosen in particular from the solid particles or matrix and / or the heart / bark type particles. 19. Kit comprising: at least one set of particles according to any one of claims 1 to 11, or a composition according to claim 12, and a composition comprising at least one depolymerizing agent.