FR3064189A1 - ENCAPSULATION OF REAGENTS FOR THE PREPARATION OF A BIOMATERIAL - Google Patents

Abstract

The present invention relates to a composition comprising: at least one solid microcapsule comprising a core and a solid envelope completely encapsulating at its periphery the core, and a continuous phase containing the solid microcapsule (s), in which the core comprises at least one crosslinking composition and the solid shell is made of crosslinked polymer, and wherein the continuous phase further comprises at least one reactive composition and at least one reinforcing composition.

Description

064 189

52321 ® FRENCH REPUBLIC

NATIONAL INSTITUTE OF INDUSTRIAL PROPERTY © Publication number:

(to be used only for reproduction orders) (© National registration number

COURBEVOIE © Int Cl ⁸ : B 01 J 13/14 (2017.01), B 01 J 13/02, 31/00, B 01 F 3/08, C 08 F 2/22, 2/48, A 61 K 8 / 11, A 61 Q 19/00

A1 PATENT APPLICATION

(© Date of filing: 21.03.17. (© Applicant (s): CAPSUM Société par actions simpli- (30) Priority: trusted - FR. @ Inventor (s): GOUTAYER MATHIEU and BARDON SEBASTIAN. (43) Date of public availability of the request: 28.09.18 Bulletin 18/39. ©) List of documents cited in the report preliminary research: Refer to end of present booklet (© References to other national documents ©) Holder (s): CAPSUM Simplified joint-stock company. related: ©) Extension request (s): (© Agent (s): LAVOIX.

ENCAPSULATION OF REAGENTS FOR THE PREPARATION OF A BIOMATERIAL.

FR 3 064 189 - A1 including:

at least one solid microcapsule comprising a core and a solid envelope totally encapsulating the core at its periphery, and

a continuous phase containing the solid microcapsule (s), in which the core comprises at least one crosslinking composition and the solid envelope consists of crosslinked polymer, and in which the continuous phase further comprises at least one reactive composition and at least one reinforcing composition.

ENCAPSULATION OF REAGENTS FOR THE PREPARATION OF A BIOMATERIAL

The present invention relates to the encapsulation of reagents intended for the preparation of a biomaterial mimicking the properties of the skin, and more particularly of young and healthy skin. It also relates to the corresponding capsules as well as their uses and their preparation process.

In many industries, it is important to encapsulate and isolate an active material from the surrounding environment, in order to protect the active for example against hydrolysis, thermal degradation or oxidation which can reduce the performance of the active. In addition, many applications require that the capsules produced have a narrow size range typically in the micrometer range, in particular to have better control over their overall performance.

In recent years, a large number of encapsulation processes have been developed and reported in the literature, including spray drying, solvent evaporation, interfacial polymerization and centrifugal extrusion among many others. To date, the systems used produce emulsions and capsules which are polydisperse or too large in size.

In addition, these systems require the use of water and similar surfactants or emulsifiers to stabilize the emulsion, which have the disadvantage of being able to react with the encapsulant or provide contaminants in the different phases.

XPL technology is based on the in situ formation of an “elastic secondary skin” which consists of an intelligent biomaterial mimicking the properties of young and healthy skin, as described in particular in the article by Yu et al., An elastic second skin, Nature Materials, vol.15, August 2016, p.911-918, and in international applications WO 2012/030993, WO 2012/030984 and WO 2013/044098.

This technology is based on a 2-step process, which consists in applying a reactive reinforcement composition to the skin, then a crosslinking composition, and thus forming a transparent film having interesting properties in terms of elasticity, contractility, adhesion. , tensile strength and occlusiveness.

This process thus requires the implementation of two stages by the user and therefore the application of two separate compositions.

Thus, the present invention aims to facilitate the implementation of XPL technology by the user.

The object of the present invention is therefore to propose to the end user a process in a single application step in place of a two-step process, by using capsules containing the compositions necessary for the technology. XPL.

The present invention also aims to provide capsules containing the crosslinking and reactive compositions and for reinforcing the XPL technology, allowing their extemporaneous mixing during the application of these capsules to keratinous material, in particular the skin.

The present invention also aims to provide a simplified implementation process, making it possible to obtain a more attractive visual, while preserving the integrity of the raw materials used.

The present invention also aims to provide a simplified implementation process, making it possible to better control the quality of the film obtained on the skin after application of the capsules.

The present invention also aims to provide capsules advantageously devoid of surfactants.

The present invention also aims to provide a method of manufacturing capsules without resorting to the use of surfactants or emulsifiers which could weaken the envelope of the capsules and / or react with the components of the formulated product in which the capsules are intended to be incorporated.

Thus, the present invention relates to a composition comprising:

at least one solid microcapsule comprising a core and a solid envelope totally encapsulating the heart at its periphery, the diameter of said solid microcapsule preferably being between 1 μm and 30 μm, the thickness of the solid envelope being preferably included between 0.1 pm and 20 pm and the standard deviation of the distribution of the diameter of the microcapsules being preferably less than 50%, and in particular less than 25%, or less than 1 pm, and

a continuous phase containing the solid microcapsule (s), in which the core comprises at least one crosslinking composition and the solid envelope consists of crosslinked polymer, and in which the continuous phase further comprises at least one reactive composition and at least one reinforcing composition.

The compositions according to the invention therefore comprise a continuous phase containing at least one reactive composition and at least one reinforcing composition, in which solid microcapsules are dispersed.

These solid microcapsules, with an average diameter of between 1 μm and 30 μm, the size distribution of which is narrow, which have the following structure:

- a core composed of a crosslinking composition, and

- a solid envelope entirely composed of crosslinked polymer.

The capsules of the invention therefore make it possible to ensure the extemporaneous mixing of the reinforcement composition, of the reactive composition with the crosslinking composition to form the film of the “second elastic skin” type (or body correcting film) mentioned above, this mixture extemporaneous being produced during the application, and therefore the rupture, of the capsules on the keratin material.

In particular, as described below, these capsules are obtained by a double emulsion method.

The microcapsules preferably have a diameter of between 1 μm and 30 μm, and preferably less than 20 μm, or even less than 5 μm.

In the context of the present invention, the term size designates the diameter, in particular the average diameter, of the capsules.

The microcapsules of the invention, dispersed in the abovementioned continuous phase, are monodisperse capsules in size.

The size distribution of the solid microcapsules can be measured by light scattering technique using a Mastersizer 3000 (Malvern Instruments) equipped with a Hydro SV dying cell.

Crosslinking composition

The core of the capsules of the invention comprises at least one crosslinking composition.

According to the invention, the term “crosslinking composition” or “crosslinking composition” designates a composition (or an element), which, when it is applied and therefore brought into contact with the reinforcing composition and the reactive composition, catalyzes the in situ formation of the body correction film (of the “second elastic skin” type) as mentioned above.

The term "catalyzes the in situ formation of the body correction film" designates the implementation of a reaction between the reactive constituents of the reactive and reinforcing compositions, so that a body correction film is formed on the skin. Without being bound by any theory, preferably, the crosslinking composition induces a reaction between one or more organopolysiloxanes and the hydride-terminated polysiloxane of the reactive composition, causing the condensation of these constituents, so that a film is formed on the skin.

According to one embodiment, the crosslinking composition comprises at least one metallic catalyst, in particular a catalyst based on platinum, rhodium or tin.

Among the platinum-based catalysts which can be used according to the invention, mention may, for example, be made of platinum-carbonyl cyclovinylmethylsiloxane complexes, platinum-divinyltetramethyldisiloxane complexes, platinecyclovinylmethylsiloxane complexes, platinum-octanaldehyde / octanol complexes and combinations thereof. this.

Among the rhodium-based catalysts which can be used according to the invention, mention may, for example, be made of rhodium tris (dibutylsulfide) trichloride.

Among the tin catalysts which can be used according to the invention, there may be mentioned for example tin octoate (II), tin neodecanoate (II), dibutyltin diisooctylmaleate, di-N- butylbis (2,4-pentanedionate) tin, di-Nbutylbutoxychlorotine, dibutyltin dilaurate, dimethyltin dineodecanoate, dimethylhydroxy (oleate) tin and tin oleate (II).

According to one embodiment, the crosslinking composition further comprises at least one organopolysiloxane with vinyl terminal functions. Among these organopolysiloxane compounds, mention may, for example, be made of the compounds of formula (I), (II), (IIa), (IIb) or (Ile) described below.

In some embodiments, the amount of vinyl-terminated polysiloxane is a stabilizing amount of vinyl-terminated polysiloxane. The term "stabilizing amount" denotes an amount which prevents degradation of the catalyst and / or of the crosslinking composition and / or of the body correcting film. In some embodiments, the stabilizing amount of vinyl-terminated polysiloxane is less than about 50%, less than about 40%, less than about

30%, less than about 20%, less than about 10%, less than about 5% or less than about 2%. In certain embodiments, the stabilizing amount of polysiloxane with terminal vinyl functions is approximately 1%.

In some embodiments, the crosslinking composition has a viscosity of between about 1,000 mPa.s and about 50,000 mPa.s at 25 ° C.

In some embodiments, the catalyst is added as a solution and the solution comprises between about 1.0% and about 5.0% of the crosslinking composition, for example about 1.5%, about 2.0 %, approximately 2.5%, approximately 3.0%, approximately 3.5%, approximately 4.0% or approximately 4.5%. In one embodiment, the catalyst represents about 2.0% of the crosslinking composition.

In some embodiments, the catalyst comprises between about 0.005% and about 0.04% of the crosslinking composition, for example about 0.005%, about 0.010%, about 0.015%, about 0.020%, about 0.025%, about 0.030% or about 0.035% or about 0.040%. In one embodiment, the catalyst represents approximately 0.02% of the crosslinking composition.

In some embodiments, the catalyst is present in the crosslinking composition in an amount between about 100 ppm and about 500 ppm.

Reactive composition

According to the invention, the continuous phase of the compositions of the invention comprises a reactive composition.

The term "reactive composition" denotes a composition comprising one or more reactive constituents which provide the reactive film-forming elements of the formulation.

According to one embodiment, the reactive composition comprises at least one polymer chosen from polysiloxanes; poly (ethylene oxides); poly (propylene oxides); polyureas; polyurethanes; polyesters, in particular polylactic-co-glycolic acid, polycaprolactone, polylactic acid, polyglycolic acid and polyhydroxybutyrate; polyamides; polysulfones and their mixtures.

According to one embodiment, the reactive composition comprises at least one reactive component.

Among the reactive constituents, mention may be made, for example, of the compounds of formula (I) below:

- i X _1_ -v— - <

(D in which:

- W is R ¹ R ² R ³ SiO-, -OR ^4, -NR ⁵ R ^6, -CR ⁷ R ⁸ R ⁹ or (C _5-10) aryl;

- X is -R ¹¹ R ¹² Si-O-, -OCONR ¹³ -, -NR ¹⁴ CONR ¹⁵ -, -CO-, -NR ¹⁶ CO-, -SO ₂ -, -O-, -S- or -NR ¹⁷ -;

- V is absent or is a (C ₁ - ₂₀ ) alkyl, (C ₂ - ₂₀ ) alkenyl, (C ₅ - ₁₀ ) aryl, -O-, -NR ¹⁰ - or -S- group;

- Y is -R ¹⁸ R ¹⁹ Si-O-, -OCONR ²⁰ -, -NR ²¹ CONR ²² -, -CO-, -NR ²³ CO-, -SO ₂ -, -O-, -S- or -NR ²⁴ ;

Z is -SiR RR, -OR ^28, -NR R, -CR ³¹ R ³² R ³³ or a group (C _5-10) aryl;

R ¹ , R ² , R ^J , R, R ^B , R, R ¹¹ , R ¹² , R ^1B , R ^ia , R ^2S , R ^2b , R ^{2 /} , R ^J1 , R and R ³³ being independently of each other others chosen from H, or the groups (Ci- ₂₀ ) alkyl, (C ₂ - ₂₀ ) alkenyl, (C ₅ -i ₀ ) aryl, hydroxyl or (Ci- ₂₀ ) alkoxyl;

R ⁴ , R ⁵ , R ⁶ , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁸ , R ²⁹ and R ³⁰ being independently the one of the others chosen from H, or the groups (Ci- ₂₀ ) alkyl, (C ₂ - ₂₀ ) alkenyl and (C ₅ -io) aryl;

- s and t are independently of each other an integer between 0 and 6000.

The groups X and Y of formula (I) represent independent monomer units. The number of these monomer units is provided by the values of s and t respectively. Among these monomeric units, the following units may be mentioned, for example:

R

Si-O ·

R

H

If-o

R

H

If-o

H

OR '[X

R in which R is as defined above in particular for the groups R ¹ , R ² or R ³ .

When one or more monomer units X (or Y) are present (for example when s (or t) is greater than 1), the values for R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ ,

R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ are chosen independently for each individual monomer unit represented by - [X] s- (or - [Y] t- ). For example, if X represents a group -R ¹¹ R ¹² Si-O- and if s = 3, then - [X] s- is [R ¹¹ R ¹² Si-OR ¹¹ R ¹² Si-OR ¹¹ R ¹² Si- O] -. In this example, it is understood that the three R ¹¹ groups present may be the same or different, for example, one R ¹¹ may be H, and the other two R ¹¹ groups may be methyl.

W and Z of formula (I) represent terminal entities. For example, the following groups may be mentioned as terminal units:

R R H

the symbol ⁵ representing a bond to a monomeric unit and R being as defined above as R ¹ for example.

According to one embodiment, in formula (I):

- W is R ¹ R ² R ³ SiO-, -OR ⁴ , -NR ⁵ R ⁶ , -CR ⁷ R ⁸ R ⁹ or (C ₅ -i ₀ ) aryl;

- X is -R ¹¹ R ¹² Si-O- or -NR ¹⁴ CONR ¹⁵ -;

- V is absent or is a (C ^ ojalkyle, (C _2-2 o) alkenyl, (C _5-10) aryl, -O-, -NR ¹⁰ - or -S-;

- Y is -R ¹⁸ R ¹⁹ Si-O- or -NR ²¹ CONR ²² -;

- Z is -SiR ²⁵ R ²⁶ R ²⁷ , -OR ²⁸ , -NR ²⁹ R ³⁰ , -CR ³¹ R ³² R ³³ or a group (C ₅ -i ₀ ) aryl;

R ¹ , R ² , R ³ , R ⁷ , R ⁸ , R ⁹ , R ¹¹ , R ¹² , R ¹⁸ , R ¹⁹ , R ²⁵ , R ²⁶ , R ²⁷ , R ³¹ , R ³² and R ³³ being independently the one of the others chosen from H, or the groups (Ci- ₂₀ ) alkyl, (C ₂ - ₂₀ ) alkenyl, (C ₅ -i ₀ ) aryl, hydroxyl or (Ci- ₂₀ ) alkoxyl;

R ⁴ , R ⁵ , R ⁶ , R ¹⁴ , R ¹⁵ , R ²¹ , R ²² , R ²⁸ , R ²⁹ and R ³⁰ being independently of each other chosen from H, or (Ci- ₂₀ ) alkyl groups, ( C _2-20) alkenyl and (C ₅ -i ₀₎ aryl;

- s and t are independently of each other an integer between 0 and 6000, the sum s + t not being equal to 0.

According to one embodiment, in formula (I):

- W is R ¹ R ² R ³ SiO-, -CR ⁷ R ⁸ R ⁹ or (C _5-10) aryl;

- X is -R ¹¹ R ¹² Si-O- or -NR ¹⁴ CONR ¹⁵ -;

- V is absent or is a group (Cr ^ jalkyle, (C ₂ - ₂₀ ) alkenyl or (C ₅ - ₁₀ ) aryl;

- Y is -R ¹⁸ R ¹⁹ Si-O- or -NR ²¹ CONR ²² -;

- Z is -SiR RR, RR or -CR a (C _5-10) aryl;

R ¹ , R ² , R ³ , R ⁷ , R ⁸ , R ⁹ , R ¹¹ , R ¹² , R ¹⁸ , R ¹⁹ , R ²⁵ , R ²⁶ , R ²⁷ , R ³¹ , R ³² and R ³³ being independently the one of the others chosen from H, or the groups (Ci- ₂₀ ) alkyl, (C ₂ - ₂₀ ) alkenyl, (C ₅ -i ₀ ) aryl, hydroxyl or (Ci- ₂₀ ) alkoxyl;

R ¹⁴ , R ¹⁵ , R ²¹ and R ²² being independently of each other chosen from H, or the groups (Ci- ₂₀ ) alkyl, (C ₂ - ₂₀ ) alkenyl and (C ₅ -i ₀ ) aryl;

- s and t are independently of each other an integer between 0 and 6000, s + t being different from 0.

According to one embodiment, V is absent; W is R ¹ R ² R ³ SiO-; X is -R ¹¹ R ¹² Si-O-; Y is -R ¹⁸ R ¹⁹ Si-O-; Z is -SiR ²⁵ R ²⁶ R ²⁷ ; R ¹ , R ² , R ³ , R ¹¹ , R ¹² , R ¹⁸ , R ¹⁹ , R ²⁵ , R ²⁶ and R ²⁷ are each independently chosen from the groups (C ^ oalkyls (for example alkyl such as methyl), or (C2-20) alkenyl groups (for example C2 alkenyl, such as vinyl). According to one embodiment, at least one of the groups R ¹ , R ² , R ³ , R ¹¹ , R ¹² , R ^18, R ^19, R ^25, R ²⁶ and R ²⁷ represents a (C2 ₂₀₎ alkenyl, for example C ₂ alkenyl (e.g., vinyl). in another embodiment, at least two of R ¹ , R ² , R ³ , R ¹¹ , R ¹² , R ¹⁸ , R ¹⁹ , R ²⁵ , R ²⁶ and R ²⁷ represent a (C ₂ - ₂₀ ) alkenyl group, for example a C ₂ alkenyl (for example a vinyl In certain embodiments, at least one of the groups R ¹ , R ² , R ³ , R ²⁵ , R ²⁶ and R ²⁷ each represent a (C ₂ - ₂ o) alkenyl group, for example an alkenyl in C ₂ (such as a vinyl group).

In one embodiment, V is absent; W is R ¹ R ² R ³ SiO-; X is -R ¹¹ R ¹² Si-O-; Y is -R ¹⁸ R ¹⁹ Si-O-; Z is -SiR ²⁵ R ²⁶ R ²⁷ ; R ¹ , R ² , R ³ , R ²⁵ , R ²⁶ and R ²⁷ are each independently chosen from (Ci-20) alkyl groups (for example Ci alkyl such as methyl), or (C2-20) alkenyl groups ( for example C2 alkenyl, such as vinyl); R ¹¹ , R ¹² , R ¹⁸ and R ¹⁹ are each independently chosen from (Ch-2o) alkyl groups (for example Ch alkyl such as methyl). According to one embodiment, at least one of R ^1, R ² and R ³ and at least one of R ^25, R ²⁶ and R ²⁷ represents a (C2 ₂₀₎ alkenyl, alkenyl e.g. in C ₂ (for example, vinyl). According to one embodiment, one of the groups R ¹ , R ² and R ³ represents a C2 alkenyl group (for example, vinyl) and the others are (Ch-2o) alkyl groups (for example Ch alkyl such as methyl) and at least one of R ^25, R ²⁶ and R ²⁷ represents a (C2 ₂₀₎ alkenyl, for example C ₂ alkenyl (eg vinyl) and other groups are ₍₂ Ch- o) alkyls (for example Ch alkyl such as methyl). According to one embodiment, at least one of the groups R ¹¹ and R ¹² and at least one of the groups R ¹⁸ and R ¹⁹ is a (C2-20) alkenyl group, for example C2 alkenyl (for example, vinyl) for at least one monomeric unit. According to one embodiment, one of the groups R ¹¹ and R ¹² represents a C2 alkenyl group (for example vinyl) and the others are (Ci- ₂₀ ) alkyl groups (for example Ch alkyl such as methyl), and one of the groups R ¹⁸ and R ¹⁹ represents a (C ₂ - ₂₀ ) alkenyl group, for example C ₂ alkenyl (for example, vinyl) and the others are (Ci- ₂₀ ) alkyl groups (for example Ch alkyl such as methyl), for at least one monomeric unit.

In certain embodiments, the organopolysiloxane includes vinyl groups only at the terminal ends of the polymer. In some embodiments, the organopolysiloxane includes vinyl groups only in the monomer units, but not at the terminal ends of the polymer. In other embodiments, the organopolysiloxane includes vinyl groups both in the terminal ends and in the monomer units of the polymer. In one embodiment, the polymer comprises two vinyl groups located either at the terminal ends, or in the monomer unit, or a combination of these. In one embodiment, on average at least two vinyl groups are present in the polymer. In a specific embodiment, at least two vinyl groups are present in the polymer and at least two vinyl groups are present on the two terminal ends of the polymer. In a specific embodiment, only two vinyl groups are present in the polymer. In a specific embodiment, only two vinyl groups are present in the polymer and are located on each of the terminal ends. In a specific embodiment, on average at least two vinyl groups are present in the polymer and at least two vinyl groups are present in one or more monomer units of the polymer.

In a particular embodiment, at least two vinyl groups are present anywhere in the polymer, but separated from another vinyl group by approximately 2,000 monomer units, for example 1,500, 1,600, 1,700, 1,800 , 1,900, 2,000, 2,100, 2,200, 2,300, 2,400 or 2,500 monomer units. In a specific embodiment, on average at least two vinyl groups are present anywhere in the polymer, but separated from another vinyl group by approximately 850 monomer units, for example 350, 450, 550, 650, 750, 850, 950, 1,050, 1,150, 1,250 or 1,350 monomer units. In a specific embodiment, on average, two vinyl groups are present anywhere in the polymer, but separated from another vinyl group by about 40 monomer units, for example 5, 10, 15, 20, 25, 30 , 35, 45, 50, 55, 60, 65, 70, 75 or 80 monomer units. In a specific embodiment, one or more Si-H units are present in addition to the vinyl fragment. Alternatively, in one embodiment, if a vinyl group is present, then an Si-H is not present.

According to one embodiment, V is absent; W is R ¹ R ² R ³ SiO-; X is -R ¹¹ R ¹² Si-O-; Y is -R ¹⁸ R ¹⁹ Si-O-; Z is -SiR ²⁵ R ²⁶ R ²⁷ ; R ¹ , R ² , R ³ , R ¹¹ , R ¹² , R ¹⁸ , R ¹⁹ , R ²⁵ , R ²⁶ and R ²⁷ are each independently chosen from H or (C1-20) alkyl groups (for example Cb alkyl such than methyl). According to one embodiment, R ^1, R ^2, R ^3, R ^25, R ²⁶ and R ²⁷ are each independently selected from (C1- ₂₀₎ alkyl (e.g. Cb alkyl such as methyl); and the groups R ¹¹ , R ¹² , R ¹⁸ and R ¹⁹ are each independently chosen from H or the groups (C ₁ - ₂₀ ) alkyls (for example Cb alkyl such as methyl), at least one of the groups R ¹¹ , R ¹² , R ¹⁸ and R ¹⁹ being H for at least one monomeric unit. According to one embodiment, on average more than two Si-H units (for example one or more among R ¹¹ , R ¹² , R ¹⁸ and R ¹⁹ is H) are present in the polymer, for example from 3 to 15 units can to be present. In a specific mode, 8 Si-H units are present. In one embodiment, one or more Si-H units (for example one or more of R ¹¹ , R ¹² , R ¹⁸ and R ¹⁹ is H) are present in the polymer. In one embodiment, at least two monomeric units include an Si-H unit (for example one or more of R ¹¹ , R ¹² , R ¹⁸ and R ¹⁹ is H). In one embodiment, at least three monomeric units include an Si-H unit (for example one or more of R ¹¹ , R ¹² , R ¹⁸ and R ¹⁹ is H). In one embodiment, at least four monomeric units include an Si-H unit (for example one or more of R ¹¹ , R ¹² , R ¹⁸ and R ¹⁹ is H). In one embodiment, at least five monomeric units include an Si-H unit (for example one or more of R ¹¹ , R ¹² , R ¹⁸ and R ¹⁹ is H). In one embodiment, at least six monomeric units include a Si-H unit (for example one or more of R ¹¹ , R ¹² , R ¹⁸ and R ¹⁹ is H). In one embodiment, at least seven monomeric units include an Si-H unit (for example one or more of R ¹¹ , R ¹² , R ¹⁸ and R ¹⁹ is H). In one embodiment, at least eight monomeric units include an Si-H unit (for example one or more of R ¹¹ , R ¹² , R ¹⁸ and R ¹⁹ is H). According to one embodiment, an Si-H unit can be present in one or both of the terminal ends in addition to being present in a monomeric unit as described above. In a specific embodiment, Si- (alkyl) or Si- (vinyl) units may also be present in the polymer. In a specific embodiment, only Si-CH ₃ and Si-H units are present. In a specific embodiment, the monomeric units or terminal ends include groups (-C ₂ o) alkyl, specifically methyl groups, for positions not Si-H polymer.

In a specific embodiment, at least two Si-H units are present on average in the polymer. In a specific embodiment, on average at least two Si-H fragments are present anywhere in the polymer, but separated from another Si-H fragment by approximately 2,000 monomer units, for example 1,500, 1,600 , 1,700, 1,800, 1,900, 2,000, 2,100, 2,200, 2,300, 2,400 or 2,500 monomer units. In a specific embodiment, on average at least two Si-H units are present anywhere in the polymer, but separated from another Si-H fragment by approximately 850 monomer units, for example 350, 450, 550, 650, 750, 800, 850, 950, 1,050, 1,150, 1,250 or 1,350 monomer units. In a specific embodiment, on average more than two Si-H units are present anywhere in the polymer, but separated from another Si-H fragment by approximately 40 monomer units, for example 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75 or 80 monomer units.

In one aspect of any of the above embodiments, the sum of s and t is an integer from about 1,000 to about 8,000; about

300 to about 2,700; from about 1,500 to about 2,700; from about 1,600 to about

600; from about 1,600 to about 2,500; from about 1,700 to about 2,500; about

800 to about 2,400; from about 1,800 to about 2,300; from about 1,900 to about

300; from about 2,000 to about 2,200; from about 2,050 to about 2,150; or about 2,100.

In one aspect of any of the above embodiments, the sum of s and t is an integer from about 200 to about 1,100; from about 600 to about 1,100; from about 700 to about 1,000; from about 800 to about 900; from about 825 to about 875; about 850; from about 200 to about 800; from about 225 to about 700; from about 250 to about 600; from about 275 to about 500; from about 300 to about 400; from about 350 to about 400; of about 375. In a specific embodiment, the sum of s and t is an integer of about 850.

In one aspect of any of the above embodiments, the sum of s and t is an integer from about 5 to about 1,300; from about 10 to about 1,100; from about 10 to about 600; from about 15 to about 500; from about 15 to about 400; from about 20 to about 300; from about 20 to about 200; from about 25 to about 100; from about 25 to about 75; from about 30 to about 50; about 40.

According to one embodiment, the reactive composition comprises at least one organopolysiloxane, optionally with vinyl terminal functions.

In certain embodiments, the reactive component comprises at least one organopolysiloxane. The term "organopolysiloxane" includes the compounds of formula (II) below:

I p10a rss R8a R ^2a -Si-0 -If-0 -If-O- -Si-R ^7a R ^3a R4a R5a R6a at

wherein R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a , R ^8a , R ^9a and R ^10a are each independently selected from H, or the groups (C ^ ojalkyle, (C ₂ - ₂ o) alkenyl, (C _5-10) aryl, or hydroxyl (-C ₂₀₎ alkoxy, and p and q each independently represents an integer number between 10 and about 6000.

In certain embodiments, the organopolysiloxane is a compound of the following formula (IIa):

in which R

1a ’

R

1a ’

Q, _ ₀ p3a '

p10a ' r \ -If-0 R ^4a '

R® ^a (Ha)

R ^3a , R ^4a , R ^5a , R ^6a , R ^8a , R ^9a and R ^10a 'are each independently chosen from H, or the groups (C ^ oalkyl, (C ₂ - ₂ o) alkenyl, (C ₅ - ₁₀ ) aryl, hydroxyl or (Cj- ^ alkoxyl, and p and q each independently represent an integer between 10 and about 6000. In one embodiment, R ^1a ,

58a ’D9a’> 10a ’

R ^3a , R ^4a , R ^5a , R ^ea , R ^Ba , R ^aa and R ^lua are alkyl groups (in particular methyl).

According to the invention, the term "alkyl" encompasses both branched and linear saturated aliphatic hydrocarbon groups having the specified number of carbon atoms. The term "(Ci- ₂₀ ) alkyl" includes branched and straight chain aliphatic groups having from 1 to 20 carbon atoms. Examples of alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, sec-butyl, tert- butyl, isopentyl, and s-pentyl. In addition, the term "alkyl" includes both unsubstituted and substituted alkyls, corresponding to alkyl groups comprising at least one substituent (for example, F, Cl, Br, I, NO ₂ , CN, alkyl , aryl, hydroxyl, alkoxyl, COCH ₃ and the like) replacing a hydrogen on one or more carbon atoms of the hydrocarbon backbone.

The term "alkenyl" embraces hydrocarbon groups with the specified number of carbon atoms, either linear or branched, with one or more unsaturated carbon-carbon bonds which can occur at any point along the chain, such as groups ethenyl and propenyl. The term (C ₂ - ₂₀ ) alkenyl denotes linear or branched hydrocarbon groups having between 2 and 20 carbon atoms and with one or more carbon-carbon double bonds. In addition, the term "alkenyl" includes both unsubstituted alkenyls and substituted alkenyls, corresponding to alkenyl groups comprising at least one substituent (for example, F, Cl, Br, I, NO ₂ , CN, alkyl, aryl, hydroxyl, alkoxyl, COCH ₃ and the like) replacing a hydrogen on one or more carbon atoms of the hydrocarbon backbone.

The term "aryl" embraces 5-10 membered monocyclic, bicyclic or tricyclic rings, in which at least one ring, if more than one is present, is aromatic. The term aryl also embraces heteroaryl groups in which a heteroatom (e.g. N, O or S) replaces one or more carbon atoms in the monocyclic, bicyclic or tricyclic ring. The term aryl encompasses both unsubstituted and substituted aryls, the latter referring to aryl groups comprising at least one substituent (for example, F, Cl, Br, I, NO ₂ , CN, alkyl, aryl, hydroxyl , alkoxyl, COCH ₃ and the like) replacing a hydrogen on one or more carbon atoms of the aromatic ring.

The term hydroxyl designates -OH.

The term alkoxyl designates groups in which an oxygen atom is covalently linked to a group (CrC ^ alkyl, as defined above.

In certain embodiments, the organopolysiloxane comprises vinyl terminal functions. The term “vinyl-terminated organopolysiloxane” includes organopolysiloxanes of the above-mentioned formula (II) in which one or both R ^2a and R ^7a are substituted by a C2 alkyl group, for example a vinyl group (for example -CH = CH2). In a particular embodiment, an organopolysiloxane with vinyl terminal functions comprises organopolysiloxanes of the above-mentioned formula (II) in which one or both R ^2a and R ^7a are substituted by a C2 alkyl group, for example a vinyl group , and R ^1a , R ^3a , R ^4a , R ^5a , R ^6a , R ^8a , R ^9a and R ^10a are independently chosen from (Ci-20) alkyl groups, for example methyl.

In other embodiments, the organopolysiloxane is chosen from: vinyl terminated polydimethylsiloxane; vinyl-terminated diphenylsiloxanedimethylsiloxane copolymers; vinyl-terminated polyphenylmethylsiloxane, vinylphenylsiloxane-phenylmethylsiloxane-vinylphenylmethyl copolymer; the vinyl-terminated trifluoropropylmethylsiloxane-dimethylsiloxane copolymer; the vinyl terminated diethylsiloxane-dimethylsiloxane copolymer; the vinylmethylsiloxane-dimethylsiloxane copolymer, with trimethylsiloxy ending; vinyl-terminated vinylmethylsiloxane-dimethylsiloxane copolymers; vinyl gums; vinyl methylsiloxane homopolymers; vinyl T-polymers; monovinyl-terminated polydimethylsiloxanes; vinylmethylsiloxane terpolymers; vinyl methoxysilane homopolymers and combinations thereof.

According to one embodiment, the organopolysiloxane is a high viscosity organopolysiloxane, a low viscosity organopolysiloxane or a combination thereof.

When the organopolysiloxane is a combination of high and low viscosity organopolysiloxanes, the combination of a high viscosity and low viscosity vinyl organosiloxane provides a bimodal molecular weight distribution of organosiloxane. In at least one embodiment, the organopolysiloxane is a combination of high and low viscosity vinyl-terminated organopolysiloxanes providing bimodal distribution of the vinyl-terminated organopolysiloxane. In one embodiment, the organopolysiloxane is a combination of formulas (I), (II), (lia), (llb) and (Ile), specifically of formula (lia), (llb) and / or (Ile) , and more specifically, of formula (IIb) and (Ile), providing a bimodal distribution of vinyl-terminated organopolysiloxanes. In one embodiment, the bimodal distribution of the molecular weight of the polymer is represented by a ratio between the molecular weights (for example the sum of s and t) of the high viscosity organopolysiloxanes and of the low viscosity organopolysiloxane. In one embodiment, this ratio is from 2 to 3. In a specific embodiment, this ratio is 2.5.

The term viscosity refers to the measurement of the resistance of a fluid which is deformed by a shear stress or a tensile stress. Those skilled in the art without undue experimentation could determine how to measure the viscosity of a fluid, for example using a viscometer or a rheometer. Representative methods include the use of a capillary viscometer, a rotary viscometer or a rheometer to measure viscosity at a specific strain of the instrument. By way of illustration, mention may be made of the method described in Example 8 of application WO2012 / 030984.

The term "high viscosity organopolysiloxane" includes organopolysiloxanes having a viscosity between about 100,000 and about 500,000 mPa.s at 25 ° C, for example between about 110,000 and about 450,000 mPa.s at 25 ° C, between approximately 120,000 and approximately 400,000 mPa.s at 25 ° C, between approximately 125,000 and approximately 350,000 mPa.s at 25 ° C, between approximately 130,000 and approximately 300,000 mPa.s at 25 ° C, between approximately 135,000 and around 250,000 mPa.s at 25 ° C, between approximately 140,000 and approximately 200,000 mPa.s at 25 ° C, between approximately 145,000 and approximately 190,000 mPa.s at 25 ° C, between approximately 150,000 and approximately 185 000 mPa.s to

25 ° C, between approximately 155,000 and approximately 175,000 mPas at 25 ° C, or between approximately 160,000 and approximately 170,000 mPa.s at 25 ° C. In some embodiments, the viscosity of the high viscosity organopolysiloxane is between about 140,000 and about 200,000 mPa.s at 25 ° C. In one embodiment, the high viscosity organopolysiloxane has a viscosity of about 165,000 mPa.s at 25 ° C.

In one embodiment, the average molecular weight of the high viscosity organopolysiloxane is between approximately 100,000 and approximately 200,000 Da, for example between approximately 115,000 and approximately 195,000 Da, between approximately 120,000 and approximately 190,000 Da , between approximately 125,000 and approximately 185,000 Da, between approximately 130,000 and approximately 180,000 Da, between approximately 135,000 and approximately 175,000 Da, between approximately 140,000 and approximately 170,000 Da, between approximately 145,000 and approximately 165,000 Da , or between approximately 150,000 and approximately 160,000 Da. In one embodiment, the average molecular weight of the high viscosity organopolysiloxane is about 155,000 Da.

In certain embodiments, the high viscosity organopolysiloxane is of formula (II), in which R ^2a and R ^7a are (C2-2o) alkenyl groups, for example a C2 alkenyl (for example a vinyl) and R ^1a , R ^3a , R ^4a , R ^5a , R ^6a , R ^8a , R ^9a and R ^10a each represent an (C1-20) alkyl group, for example methyl. In some embodiments, the high viscosity organopolysiloxane is terminated with vinyl. In other embodiments, the high viscosity organopolysiloxane is vinyl terminated polydimethylsiloxane.

In some embodiments, the vinyl-terminated high viscosity organopolysiloxane has a vinyl weight percentage of between about 0.010 and about 0.100, for example between about 0.015 and about 0.080, between about 0.020 and about 0.075, between about 0.025 and about 0.060, or between about 0.030 and about 0.050. In one embodiment, the high viscosity organopolysiloxane has a vinyl weight percentage of between about 0.030 and about 0.040.

In other embodiments, the high viscosity organopolysiloxane has a vinyl equivalent per kilogram of between about 0.0100 and about 0.0200, for example between about 0.0110 and about 0.0190, between about 0.0115 and about 0.0180, between about 0.0120 and about 0.0170, between about 0.0125 and about 0.0165 or between about 0.013 and about 0.016.

In one embodiment, the high viscosity organopolysiloxane has on average at least two vinyl units per high viscosity organopolysiloxane. In one embodiment, the monomer units comprising a vinyl moiety are spaced throughout the polymer. In one embodiment, the vinyl-containing monomer unit is spaced about 2,000 monomer units away from another vinyl-containing monomer unit or from a vinyl-containing terminal end. For example, the vinyl units in organopolysiloxanes of high viscosity are separated by 1,500, 1,600, 1,700,

800, 1,900, 2,000, 2,100, 2,200, 2,300, 2,400 or 2,500 monomer units.

In certain embodiments, the high viscosity organopolysiloxane is chosen from: vinyl-terminated polydimethylsiloxane; vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymers; vinyl-terminated polyphenylmethylsiloxane, vinylphenylsiloxanephenylmethylsiloxane copolymer with vinylphenylmethyl termination; the vinyl-terminated trifluoropropylmethylsiloxane-dimethylsiloxane copolymer; the vinyl terminated diethylsiloxane-dimethylsiloxane copolymer; the vinylmethylsiloxane-dimethylsiloxane copolymer, with trimethylsiloxy ending; vinyl-terminated vinylmethylsiloxane-dimethylsiloxane copolymers; vinyl gums; vinyl methylsiloxane homopolymers; vinyl T-polymers; monovinyl-terminated polydimethylsiloxanes; vinylmethylsiloxane terpolymers; vinyl methoxysilane homopolymers and combinations thereof.

The term "low viscosity organopolysiloxane" includes organopolysiloxanes having a viscosity between about 500 and about 50,000 mPa.s at 25 ° C, for example between about 1,000 and about 45,000 mPa.s at 25 ° C, between approximately 1,500 and approximately 40,000 mPa.s at 25 ° C, between approximately 2,000 and approximately 35,000 mPa.s at 25 ° C, between approximately 2,500 and approximately 30,000 mPa.s at 25 ° C, between approximately 3,000 and approximately 25,000 mPa.s at 25 ° C, between approximately 3,500 and approximately 20,000 mPa.s at 25 ° C, between approximately 4,000 and approximately 15,000 mPa.s at 25 ° C, or between approximately 4,000 and around 12,000 mPa.s at 25 ° C. In some embodiments, the low viscosity organopolysiloxane comprises organopolysiloxanes having a viscosity between about 100 and about 5,000 mPa.s at 25 ° C, for example between about 200 and about 4,000 mPa.s at 25 ° C , between approximately 300 and approximately 3000 mPa.s at 25 ° C, ertre approximately 400 and approximately

000 mPa.s at 25 ° C or between around 750 and around 1500 mPa.s at 25 ° C. In one embodiment, the low viscosity organopolysiloxane has a viscosity of about 10,000 mPa.s at 25 ° C. In some embodiments, the low viscosity organopolysiloxane has a viscosity of about 1000 mPa.s at 25 ° C.

In certain embodiments, the low viscosity organopolysiloxane has an average molecular mass of between approximately 20,000 and approximately 80,000 Da, for example between approximately 50,000 and approximately 75,000 Da, between approximately 55,000 and approximately 70,000 Da between around 60,000 and around 65,000 Da or between 62,000 and around 63,000 Da. In one embodiment, the low viscosity organopolysiloxane has an average molecular weight of about 62,700 Da. In one embodiment, the low viscosity organopolysiloxane has an average molecular weight of about 28,000 Da.

In certain embodiments, the low viscosity organopolysiloxane is of formula (II), in which R ^2a and R ^7a are (C ₂ - ₂₀ ) alkenyl groups, for example a C ₂ alkenyl (for example vinyl) and R ^1a , R ^3a , R ^4a , R ^5a , R ^6a , R ^8a , R ^9a and R ^10a each represent a group (C ^ alkyl, for example methyl. In certain embodiments, the low viscosity organopolysiloxane is vinyl terminated In other embodiments, the low viscosity organopolysiloxane is vinyl terminated polydimethylsiloxane.

In certain embodiments, the low viscosity organopolysiloxane has a percentage by weight of vinyl of between about 0.010 and about 0.30, for example between about 0.020 and about 0.29, between about 0.030 and about 0.28, between approximately 0.040 and approximately 0.27, between approximately 0.050 and approximately 0.26, between approximately 0.060 between approximately 0.25, between approximately 0.070 and approximately 0.24, between approximately 0.080 and approximately 0.23, or between approximately 0.090 and approximately 0.22. In some embodiments, the low viscosity organopolysiloxane has a vinyl weight percentage of between about 0.18 and about 0.26.

In other embodiments, the low viscosity organopolysiloxane has a vinyl equivalent per kilogram of between about 0.010 and about 0.100, for example between about 0.015 and about 0.090, between about 0.020 and about 0.080, between about 0.025 and about 0.070 , between about 0.030 and about 0.060 or between about 0.040 and about 0.050. In some embodiments, the low viscosity organopolysiloxane has a vinyl equivalent per kilogram of between about 0.030 and about 0.040.

In other embodiments, the low viscosity organopolysiloxane has on average at least two vinyl units per low viscosity organopolysiloxane. In one embodiment, the monomer units comprising a vinyl moiety are spaced throughout the polymer. In one embodiment, the vinyl-containing monomer unit is spaced about 850 monomer units away from another vinyl-containing monomer unit or from a vinyl-containing terminal end. For example, the vinyl units in low viscosity organopolysiloxanes are separated by 450, 550, 650, 750, 800, 850, 950, 1,050, 1,150, 1,250 or 1,350 monomer units.

In certain embodiments, the low viscosity organopolysiloxane is chosen from: vinyl-terminated polydimethylsiloxane; vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymers; vinyl-terminated polyphenylmethylsiloxane, vinylphenylsiloxanephenylmethylsiloxane copolymer with vinylphenylmethyl termination; the vinyl-terminated trifluoropropylmethylsiloxane-dimethylsiloxane copolymer; the vinyl terminated diethylsiloxane-dimethylsiloxane copolymer; the vinylmethylsiloxane-dimethylsiloxane copolymer, with trimethylsiloxy ending; vinyl-terminated vinylmethylsiloxane-dimethylsiloxane copolymers; vinyl gums; vinyl methylsiloxane homopolymers; vinyl T-polymers; monovinyl-terminated polydimethylsiloxanes; vinylmethylsiloxane terpolymers; vinyl methoxysilane homopolymers and combinations thereof

In certain embodiments, the organopolysiloxane is a compound of the following formula (llb):

(llb) in which R ^1c , R ^3c , R ^4c , R ^5c , R ^6c , R ^8c , R ^9c and R ^10c are each independently chosen from H, or (Ci- ₂ o) alkyl, (C ₂ - ₂ o) alkenyl, (C ₅ -i ₀ ) aryl, hydroxyl or (Ci- ₂₀ ) alkoxyl, and e and f each independently represent an integer between 10 and about 6000. In one embodiment, R ^1c , R ^3c , R ^4c , R ^5c , R ^6c , R ^8c , R ^9c and R ^10c are alkyl groups, in particular methyl. In some embodiments, the sum of e and f is an integer from about 1,000 to about 8,000; from about 1,300 to about 2,700;

from about 1,500 to about 2,700; from about 1,600 to about 2,600; from about 1,600 to about 2,500; from about 1,700 to about 2,500; from about 1,800 to about 2,400;

from about 1,800 to about 2,300; from about 1,900 to about 2,300; from about 2,000 to about 2,200; from about 2,050 to about 2,150; approximately 2,100.

In certain embodiments, the organopolysiloxane is a compound of the following formula (Ile):

ë J (Ile) in which R ^1d , R ^3d , R ^4d , R ^5d , R ^6d , R ^8d , R ^9d and R ^10d are each independently chosen from H, or the groups (C ^ ojalkyle, (C ₂ - ₂₀ ) alkenyl, (C _5-10) aryl, or hydroxy (Cr ^ jalcoxyle, and g and j each independently represents an integer number between 10 and about 6 000. in one embodiment, R ^1d, R ^3d, R ^4d , R ^5d , R ^6d , R ^8d , R ^9d and R ^10d are alkyl groups, especially methyl groups. In some embodiments, the sum of g and j is an integer from about 200 to about 1,100; approximately 600 to approximately 1,100; approximately 700 to approximately 1,000; approximately 800 to approximately 900; approximately 825 to approximately 875; approximately 850; approximately 200 to approximately 800; approximately 225 to approximately 700; approximately 250 to approximately 600; approximately 275 to approximately 500; approximately 300 to approximately 400; approximately 350 to approximately 400; approximately 375. In some embodiments, the sum of g and j is an integer of about 850.

According to one embodiment, the organopolysiloxane is chosen from organopolysiloxanes with a viscosity between 100,000 mPa.s and 500,000 mPa.s at 25 ° C, organopolysiloxanes with a viscosity between 500 mPa.s and 50,000 mPa.s at 25 ° C, and mixtures thereof.

According to one embodiment, the reactive composition comprises at least one polysiloxane with hydride termination (or polysiloxane with hydride functionalization or polysiloxane functionalized with at least one hydride function).

According to the invention, the term "hydride-terminated polysiloxane" includes compounds of formula (III) below:

R ^1b I R ^10b R ^9b R ^8b _R 2b_si_0 -If-0 -If ^- O ^- -Si- _R 7t> s P> 3b _R 4b _R 5b _R 6b rr 1 ⁿ (III)

wherein R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b , R ^8b , R ^9b and R ^10b are each independently selected from H, or the groups (C ^ ojalkyle, (C2-20 ) alkenyl, (C5-10) aryl, hydroxyl or (C1-20) alkoxyl, and m and n each independently represent an integer between 10 and about 6000, provided that at least one of R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b , R ^8b , R ^9b and R ^10b represents H. In certain embodiments, at least one of R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b , R ^8b , R ^9b and R ^10b represents a hydrogen atom and the remainder represents a (Ci-20) alkyl group. In some embodiments, at least two of the groups R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b , R ^8b , R ^9b and R ^10b are H (for example two Si-H units per molecule of functionalized hydride polysiloxane). other embodiments, at least three of the groups R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b , R ^8b , R ^9b and R ^10b are H (for example three Si-H units per molecule of functionalized hydride polysiloxane). In certain embodiments, at least two of the groups R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b , R ^8b , R ^9b and R ^10b are H (for example two Si-H units per hydride functionalized polysiloxane molecule) and the other groups are alkyl (CV 2 O) groups. In other embodiments, at least three of the groups R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b , R ^8b , R ^9b and R ^10b are H (e.g. three Si units -H per molecule of functionalized hydride polysiloxane) and the other groups are alkyl (CV 2 O) groups. In certain embodiments, at least two of the groups R ^4b , R ^5b , R ^9b and R ^10b are H (for example two SiH units per molecule of functionalized hydride polysiloxane) and the remainder are (CV2o) alkyl groups. In other embodiments, at least three of the groups R ^4b , R ^5b , R ^9b and R ^10b are H (for example three Si-H units per molecule of functionalized hydride polysiloxane) and the rest are groups (CV2o) alkyls.

In one embodiment, at least more than two monomer units of formula III comprise a -Si-H unit (for example one or more of R ¹¹ , R ¹² , R ¹⁸ and R ¹⁹ is H). For example, on average 2 to 15 monomer units of formula (III) comprise an Si-H unit. In one embodiment, at least two monomer units of formula (III) comprise a -Si-H unit (for example one or more of R ¹¹ , R ¹² , R ¹⁸ and R ¹⁹ is H). In one embodiment, at least three monomer units of formula (III) comprise a -Si-H unit (for example one or more of R ¹¹ , R ¹² , R ¹⁸ and R ¹⁹ is H). In one embodiment, at least four monomer units of formula (III) comprise a -Si-H unit (for example one or more of R ¹¹ , R ¹² , R ¹⁸ and R ¹⁹ is H). In one embodiment, at least five monomer units of formula (III) comprise a -Si-H unit (for example one or more of R ¹¹ , R ¹² , R ¹⁸ and R ¹⁹ is H). In one embodiment, at least six monomer units of formula (III) comprise a -Si-H unit (for example one or more of R ¹¹ , R ¹² , R ¹⁸ and R ¹⁹ is H). In one embodiment, at least seven monomer units of formula (III) comprise a -Si-H unit (for example one or more of R ¹¹ , R ¹² , R ¹⁸ and R ¹⁹ is H). In one embodiment, at least eight monomer units of formula (III) comprise a -Si-H unit (for example one or more of R ¹¹ , R ¹² , R ¹⁸ and R ¹⁹ is H). In a specific embodiment, the non-Si-H positions can comprise a Si- (alkyl) or Si (vinyl) unit. In a specific embodiment, the non-Si-H positions are Si-CH ₃ . In one embodiment, the Si-H units in the polysiloxanes functionalized with at least one hydride are separated by 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 65, 70, 75 , 80, 85, 90, 100, 125, 150 or 200 monomer units.

In one aspect of any of the above embodiments, the sum of m and n is an integer from about 10 to about 1,300; from about 10 to about 1,100; from about 10 to about 600; from about 15 to about 500; from about 15 to about 400; from about 20 to about 300; from about 20 to about 200; from about 25 to about 100; from about 25 to about 75; from about 30 to about 50; about 40. In some embodiments, the hydride-functionalized polysiloxane includes Si-H units only at the terminal ends of the polymer. In some embodiments, the polysiloxane includes Si-H units only in the monomer units, but not at the terminal ends of the polymer. In other embodiments, the polysiloxane includes Si-H units both in the terminal ends or in the monomer units of the polymer. In one embodiment, the polysiloxane comprises two to twelve Si-H units located either at the terminal end, or inside the monomer unit, or a combination thereof. In one embodiment, the polysiloxane comprises four to fifteen Si-H units located either at the terminal end, or inside the monomer unit, or a combination thereof.

In one embodiment, the polysiloxane comprises eight Si-H units located either at the terminal end, or inside the monomer unit, or a combination thereof.

In certain embodiments, the polysiloxane functionalized with at least one hydride has a viscosity of between approximately 5 and approximately 11,000 mPa.s at 25 ° C, for example between approximately 10 and approximately 10,000 mPa.s at 25 ° C, between around 15 and around 5,000 mPa.s at 25 ° C, between around 20 and around 1,000 mPa.s at 25 ° C, between around 25 and around 500 mPa.s at 25Ό, between around 30 and around 100 mPa.s at 25 ° C, and between about 40 and about 50mPa.s at 25 ° C. In one embodiment, the hydride terminated polysiloxane has a viscosity of about 45 mPa.s at 25 ° C.

In some embodiments, the hydride terminated polysiloxane has an average molecular weight of between about 900 and about 60,000 Da, for example between about 1,000 and about 50,000 Da, between about 1,200 and about 25,000 Da, between 1,400 and approximately 20,000 Da, between approximately 1,600 and approximately 15,000 Da, between approximately 1,800 and approximately 10,000 Da, between approximately 2,000 and approximately 5,000 Da, between approximately 2,200 and approximately 4,000 Da and between 2 300 and around 2,500 Da. In one embodiment, the average molecular weight of the polysiloxane functionalized by a hydride is approximately 2400 Da.

In certain embodiments, the hydride-functionalized polysiloxane has a percentage SiH content of between approximately 3 and approximately 45%, for example between approximately 5 and approximately 40%, between approximately 10 and approximately 35%, between approximately 20 and about 30%, or between about 26 and 27%. In some embodiments, the hydride-functionalized polysiloxane has a percentage SiH content of about 26%.

In certain embodiments, the polysiloxane functionalized by a hydride has an SiH content of between approximately 0.500 mmol / g and approximately 10.00 mmol / g, for example between approximately 1.00 mmol / g and approximately 9.00 mmol / g, between about 2.00 and about 8.00 mmol / g, between about 3.00 mmol / g and about 7.00 mmol / g, and about 4.00 mmol / g and about 6.00 mmol / g. In one embodiment, the hydride-functionalized polysiloxane has an SiH content of between about 4.00 and about 5.00 mmol / g, for example, 4.35 mmol / g.

In other embodiments, the polysiloxane functionalized by a hydride is terminated by an alkyl group (therefore has an alkyl termination). The term alkyl termination includes polysiloxanes functionalized by hydrides of formula (III) in which one or both R ^2b and R ^7b represent a (Ci- ₂₀ ) alkyl group. In certain embodiments, the term alkyl termination includes polysiloxanes functionalized by a hydride of formula (III) in which one, two, three, four, five or six of the groups R ^1b , R ^2b , R ^3b , R ^6b , R ^7b and R ^8b are (Ci-2o) alkyl groups. In one embodiment, the groups R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b , R ^8b and R ^10b are each alkyl (Ci-20) groups, for example methyl, and R ^9b is H. In one embodiment, the groups R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b , R ^8b and R ^9b are each groups (Ci- ₂₀ ) alkyl, for example methyl, and R ^10b is H.

In certain embodiments, the polysiloxane functionalized with a hydride is chosen from: polydimethylsiloxane with hydride termination; hydride-terminated polyphenyl- (dimethylhydrosiloxy) siloxane; hydride-terminated methylhydrosiloxane-phenylmethylsiloxane; trimethylsiloxy temrinaison methylhydrosiloxane-dimethylsiloxane copolymers; trimethylsiloxy-terminated polymethylhydrogensiloxanes; polyethylhydrogenosiloxane, triethylsiloxane, methylhydrosiloxanephenyloctylmethylsiloxane copolymer; the methyl hydrosiloxanephenyloctylmethylsiloxane terpolymer and combinations thereof.

In certain embodiments, the reactive component comprises combinations of polymers of formulas (I), (II), (lla), (llb), (Ile), (Ild) and / or (III). In a specific embodiment, the reactive component comprises a combination of polymers of formulas (11a), (11b), (Ile) and / or (III). In a specific embodiment, the reactive component comprises a combination of polymers of formulas (llb), (Ile) and (III).

According to one embodiment, the reactive composition comprises at least one organopolysiloxane and at least one polysiloxane with hydride termination.

In certain embodiments, the reactive component includes combinations of high molecular weight vinyl organopolysiloxanes, low molecular weight vinyl organopolysiloxanes and / or hydride functionalized organopolysiloxanes. In one embodiment, each of the organopolysiloxanes of high and low molecular weight comprises on average at least two vinyl groups per polymer. In a specific embodiment, each vinyl organopolysiloxane comprises exactly two vinyl groups. In one embodiment, the ratio between the high molecular weight organopolysiloxane and the low molecular weight organopolysiloxane is between 2 and 3, and is for example 2, 2.5 or 3. The ratio can be chosen to adjust the chemical and physical properties of the film to suit a specific method or part of the body. In one embodiment, the hydride-terminated organopolysiloxane (or functionalized by hydrides) includes on average more than two Si-H units in the polymer. In a specific embodiment, there are 8 Si-H units per organopolysiloxane with hydride termination.

In certain embodiments, the reactive component comprises combinations of high molecular weight hydride functionality organopolysiloxanes, low molecular weight hydride functionality organopolysiloxanes and / or vinyl organopolysiloxanes. In one embodiment, each of the organopolysiloxanes of high and low molecular weight comprises on average at least two Si-H units per polymer. In a specific embodiment, each organopolysiloxane with hydride functionality comprises exactly two Si-H functions. In one embodiment, the ratio between the high molecular weight organopolysiloxane and the low molecular weight organopolysiloxane is 2 to 3, for example 2, 2.5 or 3. The ratio can be chosen to adjust the chemical properties and physical aspects of the film to suit a specific method or part of the body. In one embodiment, the vinyl organopolymer comprises on average more than at least two vinyl units in the polymer. In a specific embodiment, there are 8 vinyl units per vinyl organopolysiloxane.

Reinforcement composition

According to the invention, the continuous phase of the compositions of the invention comprises a reinforcing composition.

The term "reinforcing constituent" denotes one or more constituents of the reinforcing composition which provide the required physical properties of the film which result from the in situ reaction between the reactive and reinforcing compositions and the crosslinking composition. Such physical properties include, for example, mechanical elements (e.g. elasticity, durability, breaking strain, tensile strength, etc.), biocompatibility (e.g. selective breathability, adhesion, etc ...), optical effects (eg reflectance, color, etc ...) and surface modulation (eg texture, chemistry, etc.).

According to one embodiment, the reinforcing composition comprises at least one reinforcing constituent chosen from the group consisting of clays (for example AI ₂ O ₃ , SiO ₂ ), chalk, talc, calcites (for example CaCO ₃ ), mica, barium sulfate, zirconium dioxide, zinc sulfide, zinc oxide, titanium dioxide, aluminum oxide, silica aluminates, calcium silicates, silicas, and their mixtures, said reinforcing constituent being optionally surface treated.

The reinforcing constituent may be silica, preferably surface-treated silica, in particular silica treated with hexamethyldisilazane, or alternatively fumed silica, hydrated silica or anhydrous silica.

In certain embodiments, the reinforcing constituent has a specific surface of between approximately 100 and approximately 300 m ² / g, for example between approximately 110 and approximately 250 m ² / g, between approximately 120 and approximately 225 m ² / g, between approximately 130 and approximately 200 m ² / g, between approximately 135 and approximately 185 m ² / g, between approximately 160 and approximately 170 m ² / g, and between approximately 164 and approximately 166 m ² / g. In one embodiment, the reinforcing constituent has a specific surface of approximately 160 ± 25 m ² / g.

In some embodiments, the reinforcing component has an average particle size of from about 1 to about 20 µm.

In certain embodiments, the reinforcing constituent is composed with the organopolysiloxane of low viscosity and / or of high viscosity.

In certain embodiments, the reactive component and the reinforcing component constitute between approximately 20% and approximately 90%, for example between approximately 40% and approximately 60%, of the assembly formed by the reactive and reinforcing compositions. In certain embodiments, the reactive component and the reinforcing component constitute between approximately 45.0% and approximately 61.0% of the assembly formed by the reactive and reinforcing compositions, for example approximately 45.0%, approximately 45 , 5%, approximately 46.0%, approximately 46.5%, approximately 47.0%, approximately 47.5%, approximately 49.5%, approximately 49.0%, approximately 49.5%, approximately 50.0 %, approximately 50.5%, approximately 51.0%, approximately 51.5%, approximately 52.0%, approximately 52.5%, approximately 53.0%, approximately 53.5%, approximately 54.0%, approximately 54.5%, approximately 55.0%, approximately 55.5%, approximately 56.0%, approximately 56.5%, approximately 57.0%, approximately 58.0%, approximately 58.5%, approximately 59 , 0%, approximately 59.5%, approximately 60.0% or approximately 60.5%. In certain embodiments, the reactive constituent and the reinforcing constituent constitute approximately 45% of the whole formed by the reactive and reinforcing compositions. In one embodiment, the reactive component and the reinforcing component constitute approximately 48.0% of the whole formed by the reactive and reinforcing compositions.

In certain embodiments, the reactive component and the reinforcing component constitute approximately 50.0% of the whole formed by the reactive and reinforcing compositions. In another embodiment, the reactive constituent and the reinforcing constituent constitute approximately 51.0% of the whole formed by the reactive and reinforcing compositions. In certain embodiments, the reactive constituent and the reinforcing constituent constitute approximately 51.5% of the whole formed by the reactive and reinforcing compositions. In another embodiment, the reactive constituent and the reinforcing constituent constitute approximately 54.5% of the whole formed by the reactive and reinforcing compositions. In another embodiment, the reactive constituent and the reinforcing constituent constitute approximately 55.0% of the whole formed by the reactive and reinforcing compositions. In certain embodiments, the reactive constituent and the reinforcing constituent constitute approximately 59.5% of the whole formed by the reactive and reinforcing compositions. In another embodiment, the reactive constituent and the reinforcing constituent constitute approximately 60.5% of the whole formed by the reactive and reinforcing compositions. In certain embodiments, the reactive component and the reinforcing component constitute between approximately 30.0 and approximately 40.0% of the assembly formed by the reactive and reinforcing compositions, for example approximately 30.0%, approximately 30, 5%, approximately 31.0%, approximately 31.5%, approximately 32.0%, approximately 32.5%, approximately 33.0, approximately 33.5%, approximately 34.0%, approximately 34.5%, approximately 35.0%, approximately 35.5%, approximately 36.0%, approximately 36.5%, approximately 37.0%, approximately 37.5%, approximately 38.0%, approximately 38.5%, approximately 39 , 0%, about 39.5%, about 40.0%.

In certain embodiments, the reactive component and the reinforcing component constitute between approximately 33.0% and approximately 40.0% of the assembly formed by the reactive and reinforcing compositions.

In one embodiment, the reinforcing constituent comprises between approximately 8.0% and approximately 13.0% of the assembly formed by the reactive and reinforcing compositions, for example approximately 8.5%, approximately 9.0%, approximately 9.5%, approximately 10.0%, approximately 10.5%, approximately 11.0%, approximately 11.5%, approximately 12.0% or approximately 12.5%. In certain embodiments, the reinforcing constituent comprises approximately 8.5% of the whole formed by the reactive and reinforcing compositions. In one embodiment, the reinforcing constituent comprises approximately 9.0% of the whole formed by the reactive and reinforcing compositions. In another embodiment, the reinforcing constituent comprises approximately 9.5% of the whole formed by the reactive and reinforcing compositions. In certain embodiments, the reinforcing constituent comprises approximately 10.0% of the whole formed by the reactive and reinforcing compositions. In certain embodiments, the reinforcing constituent comprises approximately 10.5% of the whole formed by the reactive and reinforcing compositions. In another embodiment, the reinforcing constituent comprises approximately 11.0% of the whole formed by the reactive and reinforcing compositions. In another embodiment, the reinforcing constituent comprises approximately 12.0% of the whole formed by the reactive and reinforcing compositions.

In another embodiment, the reinforcing constituent comprises approximately 13.0% of the whole formed by the reactive and reinforcing compositions.

In another embodiment, the reactive component comprises between approximately 30.0% and approximately 60.0% of the assembly formed by the reactive and reinforcing compositions, for example approximately 30.5%, approximately 31.0%, approximately 32.0%, approximately 33.0%, approximately 34%, approximately 35.0%, approximately 36.0, approximately 37.0%, approximately 38.0%, approximately 39.0%, approximately 40.0% , approximately 41.0%, approximately 42.0%, approximately

43.0%, approximately 44.0%, approximately 45.0%, approximately 46.0%, approximately 47.0%, approximately

48.0%, approximately 49.0%, approximately 50.0%, approximately 51.0%, approximately 52.0%, approximately

53.0%, approximately 54.0%, approximately 55.0%, approximately 56.0%, approximately 57.0%, approximately

58.0% or about 59.0%.

In certain embodiments, the assembly formed by the reactive and reinforcing compositions has a viscosity of between approximately 5,000 and 1,000,000 mPa.s at 25 ° C. In certain embodiments, the assembly formed by the reactive and reinforcing compositions has a viscosity of between approximately 10,000 and 10,000,000 mPa.s at 25 ° C., for example around 10,000,000, approximately 9,000,000, approximately 8,000,000, approximately 7,000,000, approximately 6,000,000, approximately 5,000,000, approximately 4,000,000, 3,000,000, approximately 2,000,000, approximately 1,000,000, approximately 900,000, approximately 800,000, approximately 700,000, approximately 600,000, approximately 500,000, approximately 400,000, approximately 300,000, approximately 200,000, approximately 100,000, approximately 90,000, approximately 80,000, approximately 70,000, approximately 60,000, approximately 50,000, approximately 40,000, approximately 30 000, around 20,000, around 10,000 mPa.s at 25 ° C.

In one embodiment, the assembly formed by the reactive and reinforcing compositions has a viscosity of approximately 1,000,000 mPa.s at 25 ° C.

In certain embodiments, the assembly formed by the reactive and reinforcing compositions has a relationship between the vinyl radical and the hydride function (for example, between the -CH = CH _{2 groups} of the organopolysiloxane (s) and the Si-H groups hydride-functional polysiloxane) between about 1:10 and about 1: 100, between about 1:15 and about 1:90, between about 1:20 and about 1:80, between about 1:25 and about 1:70 , between approximately 1:30 and approximately 1:60, between approximately 1:35 and approximately 1:50. In one embodiment, the assembly formed by the reactive and reinforcing compositions has a functional vinyl / hydride ratio of approximately 1:40. In another embodiment, the assembly formed by the reactive and reinforcing compositions has a functional vinyl / hydride ratio of approximately 1:20. In certain embodiments, the assembly formed by the reactive and reinforcing compositions has a functional vinyl / hydride ratio of approximately 1:15.

According to the invention, as described above, the solid microcapsules of the invention comprise a solid envelope made of crosslinked polymer. This crosslinked polymer is obtained by crosslinking from a monomer as described below.

Preferably, the microcapsules according to the invention are devoid of surfactant.

According to one embodiment, the above-mentioned compositions comprise two populations of capsules, the first population of capsules containing in their heart at least one crosslinking composition, these capsules corresponding to those mentioned above, and the second population of capsules containing in their heart at least one reactive composition and at least one reinforcing composition, these compositions being as defined above.

According to another embodiment, the compositions of the invention comprise two populations of capsules according to the invention, the first population of capsules containing in their heart a crosslinking composition as defined above PC1 and a mixture of a reactive composition and reinforcing RRC1 as a continuous phase containing them, and the second population of capsules containing in their heart a crosslinking composition as defined above PC2 and a mixture of a reactive composition and reinforcing RRC2 as a continuous phase containing,

PC1 and PC2 being identical or different and / or RRC1 and RRC2 being identical or different.

This embodiment is advantageous in that it makes it possible to obtain a film which combines the advantageous properties of 2 films according to the invention having at the base different properties in terms of elasticity, contractility, adhesion, tensile strength and occlusiveness.

According to one embodiment, a composition according to the invention is devoid of surfactant, in particular at the interface between the solid envelope and the external medium (or continuous phase) notably represented by the composition C3 and / or C4.

According to a particular embodiment, the composition C3 and / or C4 can itself be a single or multiple emulsion, in which the dispersed phase can be stabilized by any means known to those skilled in the art, in particular by means of surfactant (s ) or by the formation of a membrane, in particular resulting from a reaction of interfacial complex coacervation between a first anionic polymer (in particular a carbomer) and a second cationic polymer (in particular an amodimethicone).

Uses

The compositions according to the invention can in particular be used in the cosmetic field, but also in the dermatological or therapeutic field.

They can comprise, in addition to the abovementioned ingredients, at least one physiologically acceptable medium.

The present invention also relates to a cosmetic composition comprising a composition as defined above and further comprising at least one physiologically acceptable medium.

The term “physiologically acceptable medium” is intended to denote 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 support on 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 cosmetic compositions are used for making up and / or caring for keratin materials, in particular the skin.

The cosmetic compositions according to the invention can be care, sun protection, cleansing (make-up removing), hygiene or make-up products for the skin.

îo These compositions are therefore intended to be applied in particular to the skin.

Thus, the present invention also relates to the non-therapeutic cosmetic use of a cosmetic composition mentioned above, as a make-up, hygiene, cleaning and / or care product for keratin materials, especially 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 treatment, an anti-treatment -age, a sunscreen, an oily skin treatment, a whitening treatment, a hydrating treatment, a BB cream, tinted cream or foundation, a face and / or body cleanser , shower gel or shampoo.

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

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

The present invention also relates to a non-therapeutic method of cosmetic treatment of a keratin material, comprising a step of applying to the keratin material of at least one layer of a cosmetic composition as defined above.

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

The present invention also relates to a composition as defined above for its use as a medicament.

The present invention also relates to a composition as defined above for its use for the treatment of wounds.

The present invention also relates to a composition as defined above for its use for the treatment of headaches.

Thus, the compositions of the invention can be used as a cosmetic, dermatological or therapeutic composition, in particular:

- for make-up and / or skin care;

- to improve the appearance of the skin, in particular hide / blur / reduce skin imperfections such as wrinkles and fine lines and dark circles, crow's feet, vitiligo, ephelides (or freckles), or ichthyosis, scabs, psoriasis or pruritus;

- to prevent and / or treat dry skin (or xerosis);

- to hydrate the skin; to prevent / limit water loss from the skin; or to prevent and / or treat dry skin;

- to restore the elasticity of the skin; or prevent sagging of the tissue;

- to protect the skin following a laser or light treatment;

- to improve the skin barrier function;

- to prevent and / or treat dermatological disorders (or disorders) in the skin, such as eczema or dermatitis;

- to deliver cosmetic or therapeutic active ingredients (transdermally) (as an alternative to the current patch);

- for screening cosmetic and / or therapeutic active ingredients;

- to protect the skin, in particular from the effects of the sun, wind, rain, pollution; in particular as sun protection tools, which preferably involves the additional presence of sun filters;

- to treat skin wounds;

- to treat headaches; and or

- to protect the skin against extreme temperatures, toxins, microorganisms, radiation, potentially irritating products (cosmetics, etc.), especially for sensitive skin, and / or injuries.

These different uses can involve the necessary or optional use of additional compounds.

As additional compound, there may be mentioned preservatives, humectants, stabilizers, chelators, emollients, modifiers chosen from agents of pH, osmotic force and / or modifiers of refractive index, etc. or any usual cosmetic additive, and mixtures thereof.

Mention may also be made of active agents, in particular biological or cosmetic active agents, for example chosen from hydrating agents, healing agents, depigmenting agents, UV filters, desquamating agents, antioxidant agents, active agents stimulating the synthesis of dermal macromoleculars and / or epidermal, dermodecontracting agents, antiperspirant agents, soothing agents, anti-aging agents, perfuming agents and their mixtures. Such assets are described in particular in application FR 1 558 849.

Of course, the person skilled in the art will take care to choose any optional compound (s) and / or active agent (s) mentioned above and / or their respective amounts in such a way that the advantageous properties of a composition according to the invention are not or substantially not altered by the proposed addition. These adjustments fall within the competence of a person skilled in the art.

Preparation process

The present invention also relates to a process for manufacturing the abovementioned capsules making it possible to impart to them in a controlled manner the structure described above, as well as to obtain a narrow size distribution, the mean diameter of which can be fixed between 1 μm and 30 pm and the thickness of the envelope can be between 0.1 pm and 20 pm.

The present invention also relates to a process for manufacturing these capsules without resorting to the use of surfactants or emulsifiers which could weaken the envelope of the capsules and / or react with the components of the formulated product in which the capsules are intended to be incorporated.

The preparation of the capsules according to the process of the invention consists in producing a double, or even triple, emulsion composed of droplets containing the crosslinking composition enveloped in a crosslinkable liquid phase. These double drops are then made monodisperse in size before being transformed by crosslinking into rigid capsules and then placed in the presence of a composition comprising the reactive composition and the reinforcement composition. Preparation involves 5, even 6, steps described in more detail below.

Thus, the present invention also relates to a process for the preparation of a composition as defined above, comprising the following steps:

a) the preparation of a composition C1 comprising at least one crosslinking composition,

b) the addition, with stirring, of said composition C1 in a polymeric composition C2, the compositions C1 and C2 not being miscible with each other, the composition C2 comprising at least one monomer or polymer, at least one agent crosslinking agent, and optionally at least one (photo) initiator or crosslinking catalyst, the viscosity of the composition C2 being between 500 mPa.s and

100,000 mPa.s at 25 ° C, and preferably being greater than the viscosity of composition C1, whereby an emulsion (E1) is obtained comprising drops of composition C1 dispersed in composition C2;

c) the addition, with stirring, of the emulsion (E1) in a composition C3, the compositions C2 and C3 not being miscible with each other, the viscosity of the composition C3 being between 500 mPa.s and

100,000 mPa.s at 25 ° C, and preferably being greater than the viscosity of the emulsion (E1), the composition C3 optionally comprising at least one reactive composition and at least one reinforcing composition, whereby a double emulsion (E2) comprising drops dispersed in composition C3;

d) applying an emulsion shear (E2), whereby a double emulsion (E3) is obtained comprising drops of controlled size dispersed in composition C3;

e) polymerization of composition C2, whereby solid microcapsules are obtained dispersed in composition C3; and

f) when the composition C3 does not comprise the reactive composition and the reinforcing composition, the addition of the solid microcapsules, dispersed in the composition C3, in a composition C4, the composition C4 comprising at least one reactive composition and at least one composition reinforcement.

Step a)

Step a) of the process according to the invention consists in preparing a composition C1 comprising at least one crosslinking composition as defined above.

Composition C1

Composition C1 comprises at least one crosslinking composition as defined above, this crosslinking composition preferably being a catalyst, and in particular a platinum catalyst.

According to one embodiment, composition C1 comprises at least one catalyst, in particular a platinum catalyst, and at least one organopolysiloxane with vinyl terminal functions, as defined above.

Step b)

Step b) of the process according to the invention consists in preparing a first emulsion (E1).

The first emulsion consists of a dispersion of droplets of a composition C1 as defined above in a polymeric composition C2, immiscible with C1, created by dropwise addition of C1 to C2 with stirring.

Composition C2 is stirred so as to form an emulsion comprising drops of composition C1 dispersed in composition C2. This emulsion is also called "simple emulsion" or C1-in-C2 emulsion.

To implement step b), one can use any type of agitator usually used to form emulsions, such as for example a mechanical paddle stirrer, a static foam concentrate, an ultrasonic homogenizer, a membrane homogenizer, a homogenizer at high pressure, a colloid mill, a high shear disperser or a high speed homogenizer.

Composition C2

Composition C2 is intended to form the future rigid envelope of the microcapsules.

The volume fraction of C1 in C2 can vary from 0.1 to 0.7 in order to control the thickness of the capsule shell obtained at the end of the process.

Preferably, the viscosity of composition C2 at 25 ° C is between 1,000 mPa.s and 50,000 mPa.s, preferably between 2,000 mPa.s and 25,000 mPa.s, and for example between 3,000 mPa. s and 15,000 mPa.s.

Preferably, the viscosity of composition C2 is greater than the viscosity of composition C1.

The viscosity is measured using a Haake Rheostress ™ 600 rheometer equipped with a cone with a diameter of 60 mm and an angle of 2 degrees, and with a temperature regulation cell set at 25 ° C. The viscosity value is read for a shear speed equal to 10 s ¹ .

Preferably, the interfacial tension between the compositions C1 and C2 is low. Typically, these interfacial tensions vary between 0 mN / m and 50 mN / m, preferably between 0 mN / m and 20 mN / m.

The low interfacial tension between the compositions C1 and C2 also advantageously makes it possible to ensure the stability of the emulsion (E1) obtained at the end of step b).

According to one embodiment, the ratio between the volume of composition C1 and the volume of composition C2 varies between 1:10 and 10: 1. Preferably, this ratio is between 1: 3 and 5: 1, preferably between 1: 3 and 3: 1. This ratio can be adapted to control the thickness of the envelope of the polymerized microcapsules.

Composition C2 contains at least one monomer or polymer, at least one crosslinking agent, and optionally at least one (photo) initiator or crosslinking catalyst, thus making it crosslinkable.

According to one embodiment, the composition C2 comprises from 50% to 99% by weight of monomer or polymer, or a mixture of monomers or polymers, relative to the total weight of the composition C2.

According to one embodiment, the composition C2 comprises from 1% to 20% by weight of crosslinking agent or of a mixture of crosslinking agents, relative to the total weight of the composition C2.

According to one embodiment, the composition C2 comprises from 0.1% to 5% by weight of photoinitiator or of a mixture of photoinitiators, relative to the total weight of the composition C2.

According to one embodiment, composition C2 comprises from 0.001% to 70% by weight of crosslinking agent (s) relative to the weight of said composition C2.

According to the invention, the term “monomer” or “polymer” designates any base unit suitable for the formation of a solid material by polymerization, either alone or in combination with other monomers or polymers.

These monomers can be chosen from monomers comprising at least one reactive function chosen from the group consisting of acrylate, methacrylate, vinyl ether, N-vinyl ether, mercaptoester, thiolene, siloxane, epoxy, oxetane, urethane, isocyanate and peroxide functions.

In particular, the monomers can be chosen from the monomers carrying at least one of the reactive functions mentioned above and carrying in addition at least one function chosen from the group consisting of primary, secondary and tertiary alkylamine functions, quaternary amine functions, sulfate functions, sulfonate, phophate, phosphonate, carboxylate, hydroxyl, halogen, and mixtures thereof.

The polymers used in composition C2 can be chosen from polyethers, polyesters, polyurethanes, polyureas, polyethylene glycols, polypropylene glycols, polyamides, polyacetals, polyimides, polyolefins, polysulphides and polydimethylsiloxanes, said polymers additionally carrying at least one reactive function chosen in the group consisting of the acrylate, methacrylate, vinyl ether, N-vinyl ether, mercaptoester, thiolene, siloxane, epoxy, oxetane, urethane, isocyanate and peroxide functions.

Among the examples of such polymers, there may be mentioned, but not limited to, the following polymers: poly (2- (1-naphthyloxy) -ethyl acrylate), poly (2- (2naphthyloxy) -ethyl acrylate), poly (2 - (2-naphthyloxy) -ethyl methacrylate), polysorbitol dimethacrylate, polyacrylamide, poly ((2- (1-naphthyloxy) ethanol), poly (2- (2naphthyloxy) ethanol), poly (1-chloro-2,3-epoxypropane ), poly (n-butyl isocyanate), poly (N-vinyl carbazole), poly (N-vinyl pyrrolidone), poly (p-benzamide), poly (pchlorostyrene), poly (p-methyl styrene), poly (p- phenylene oxide), poly (p-phenylene sulfide), poly (N- (methacryloxyethyl) succinimide), polybenzimidazol, polybutadiene, polybutylene terephthalate, polychloral, polychloro trifluoro ethylene, polyether imide, polyether ketone, polyether sulfone, polyhydridosilides ), poly (methyl 2-acrylamido-2-methoxyaceate), poly (2acrylamido-2-methylpropanesulfonic acid), poly-mono-butyl maleate, polybutylmeth acrylate, poly (N-tert-butylmethacrylamide), poly (N-nbutylmethacrylamide), polycyclohexylmethacrylamide, poly (m-xylenebisacrylamide 2,3-dimethyl-1,3-butadiene, N, N-dimethylmethacrylamide), poly (n-butyl methacrylate ), poly (cyclohexyl methacrylate), polyisobutyl methacrylate, poly (4cyclohexylstyrene), polycyclol acrylate, polycyclol methacrylate, polydiethyl ethoxymethylenemalonate, poly (2,2,2-trifluoroethyl methacrylate), poly (1,1,1trimethylolpropyl) (N, N-dimethylaniline, dihydrazide), poly (isophthalic dihydrazine), isophthalic polyacid, polydimethyl benzilketal, epichlorohydrin, poly (3,3-ethyl-diethoxyacrylate), poly (3,3-dimethylacrylate), poly (ethyl vinyl ketone), poly (vinyl ethyl ketone), poly (penten-3one), polyformaldehyde poly (diallyl acetal), polyfumaronitrile, polyglyceryl propoxy triacrylate, polyglyceryl trimethacrylate, polyglycidoxypropyltrimethoxysilane, polyglycidyl acrylate, poly (n-heptyl acrylate), poly (n-heptyl ester of acrylic acid), poly (n-heptyl methacrylate), poly (3-hydroxypropionitrile), poly (2-hydroxypropyl acrylate), poly (2-hydroxypropyl methacrylate), poly (N ( methacryloxyethyl) phthalimide), poly (1,9-nonanediol diacrylate), poly (1,9nonanediol dimethacrylate), poly (N- (n-propyl) acrylamide), poly (orthophthalic acid), poly (isophthalic acid), poly (1,4-benzenedicarboxylic acid), poly (1,3-benzenedicarboxylic acid), poly (phthalic acid), poly (mono-2acryloxyethyl ester), poly terephthalic acid, phthalic polyanhydride, polyethylene glycol diacrylate, polyethylene glycol methacrylate, polyethylene glycol dimethacr , poly (isopropyl acrylate), polysorbitol pentaacrylate, polyvinyl bromoacetate, polychloroprene, poly (di-n-hexyl silylene), poly (di-n-propyl siloxane), polydimethyl silylene, polydiphenyl siloxane, polyvinyl propionate, polyvinyl triacetoxys tert-butoxysilane, polyvinyl butyral, polyalcohol v inylic, polyvinyl acetate, polyethylene co-vinyl acetate, poly (bisphenol-A polysulfone), poly (1,3-dioxepane), poly (1,3-dioxolane), poly (1,4-phenylene vinylene), poly ( 2,6-dimethyl-1A-phenylene oxide), poly (4-hydroxybenzoic acid), poly (4-methyl pentene-1), poly (4-vinyl pyridine), polymethylacrylonitrile, polymethylphenylsiloxane, polymethylsilmethylene, polymethylsilsesquioxane, poly (phenylsilsesquioxane) , poly (pyromellitimide-1,4-diphenyl ether), polytetrahydrofuran, polythiophene, poly (trimethylene oxide), polyacrylonitrile, polyether sulfone, polyethylene-co-vinyl acetate, poly (perfluoroethylene propylene), poly (perfluoralkoxyl alkane), or poly ( styrene-acrylonitrile).

By “crosslinking agent” is meant a compound carrying at least two reactive functions capable of crosslinking a monomer or a polymer, or a mixture of monomers or polymers, during its polymerization.

The crosslinking agent can be chosen from molecules carrying at least two functions chosen from the group consisting of acrylate, methacrylate, vinyl ether, N-vinyl ether, mercaptoester, thiolene, siloxane, epoxy, oxetane, urethane, isocyanate and peroxide functions.

As a crosslinking agent, we can notably mention:

- diacrylates, such as 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, polyethylene glycol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,4-butanediol dimethacrylate, 2,2-bis (4 -methacryloxyphenyl) propane, 1,3-butanediol dimethacrylate, 1,10-decanediol dimethacrylate, bis (2-methacryloxyethyl) N, N'-1,9-nonylene biscarbamate, 1,4-butanediol diacrylate, ethylene glycol diacrylate, 1,5-pentanediol dimethacrylate, 1,4Phenylene diacrylate, allyl methacrylate, Ν, Ν'-methylenebisacrylamide, 2,2bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane , tetraethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, polyethylene glycol diglycidyl ether, Ν, Ν-diallylacrylamide, 2,2-bis [ 2-acryloxyethoxy) phenyljpropane, glycidyl methacrylate;

- multifunctional acrylates such as dipentaerythritol pentaacrylate, 1,1,1-trimethylolpropane triacrylate, 1,1,1-trimethylolpropane trimethacrylate, ethylenediamine tetramethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate;

- acrylates also having another reactive function, such as propargyl methacrylate, 2-Cyanoethyl acrylate, tricyclodecane dimethanol diacrylate, hydroxypropyl methacrylate, N-acryloxysuccinimide, N- (2Hydroxypropyl) methacrylamide, N- (3- aminopropyl) methacrylamide hydrochloride, N- (t-BOC-aminopropyl) methacrylamide, 2-aminoethyl methacrylate hydrochloride, monoacryloxyethyl phosphate, o-nitrobenzyl methacrylate, acrylic anhydride, 2- (tert-butylamino) ethyl methacrylate, Ν, iallydiallylacrylamide, glycidyl methacrylate, 2-hydroxyethyl acrylate, 4- (23064189 acryloxyaéhoxy) -2-hydroxybenzophenone, N- (Phthalimidomethyl) acrylamide, cinnamyl methacrylate.

By "photoinitiator" is meant a compound capable of fragmenting under the effect of light radiation.

The photoinitiators which can be used according to the present invention are known in the art and are described, for example in Photoinitiators in the crosslinking of coatings, G. Li Bassi, Double Liaison - Chimie des Peintures, n ° 361, November 1985, p.34- 41; Industrial applications of photoinduced polymerization, Henri Strub, L'Actualité Chimique, February 2000, p.5-13; and Photopolymers: theoretical considerations and setting reaction, Marc, J.M. Abadie, Double Liaison - Chimie des Peintures, n ° 435-436, 1992, p.28-34.

These photoinitiators include:

α-hydroxyketones, such as 2-hydroxy-2-methyl-1-phenyl-1-propanone, sold for example under the names DAROCUR® 1173 and 4265, IRGACURE® 184, 2959, and 500 by the company BASF, and ADDITOL ® CPK by CYTEC;

α-aminoketones, in particular 2-benzyl-2-dimethylamino-1- (4morpholinophenyl) -butanone-1, sold for example under the names IRGACURE® 907 and 369 by the company BASF;

- the aromatic ketones sold for example under the name

ESACURE® TZT by LAMBERTI; or the thioxanthones sold for example under the name ESACURE® ITX by LAMBERTI, and the quinones. These aromatic ketones most often require the presence of a hydrogen donor compound such as tertiary amines and in particular alkanolamines. Mention may in particular be made of the tertiary amine ESACURE® EDB sold by the company LAMBERTI.

- the α-dicarbonyl derivatives, the most common representative of which is benzyldimethylketal marketed under the name IRGACURE® 651 by BASF. Other commercial products are marketed by LAMBERTI under the name ESACURE® KB1, and

- the acylphosphine oxides, such as for example the bisacylphosphine oxides (BAPO) marketed for example under the names IRGACURE® 819, 1700, and 1800, DAROCUR® 4265, LUCIRIN® TPO, and LUCIRIN® TPO-L by the company BASF.

Among the photoinitiators, mention may also be made of aromatic ketones such as benzophenone, phenylglyoxylates, such as the methyl ester of phenyl glyoxylic acid, oxime esters, such as [1- (4phenylsulfanylbenzoyl) heptylidenene benzoate, the salts sulfonium, iodonium salts and oxime sulfonates.

According to one embodiment, composition C2 can also comprise an additional monomer or polymer capable of improving the properties of the shell of the microcapsules and / or of giving new properties to the shell of the microcapsules.

Among these additional monomers or polymers, mention may be made of monomers or polymers carrying a group sensitive to pH, temperature, UV or IR.

These additional monomers or polymers can induce the rupture of the solid microcapsules and subsequently the release of their content, after stimulation via pH, temperature, UV or IR.

These additional monomers or polymers can be chosen from monomers or polymers carrying at least one reactive function chosen from the group consisting of the acrylate, methacrylate, vinyl ether, N-vinyl ether, mercaptoester, thiolene, siloxane, epoxy, oxetane, urethane functions, isocyanate and peroxide, and also bearing one of the following groups:

- a hydrophobic group such as a fluorinated group, for example trifluoroethyl methacrylate, trifluoroethyl acrylate, tetrafluoropropyl methacrylate, pentafluoropropyl acrylate, hexafluorobutyl acrylate, or fluorophenyl isocyanate;

- a pH sensitive group such as primary, secondary or tertiary amines, carboxylic acids, phosphate, sulfate, nitrate, or carbonate groups;

a group sensitive to UV or cleavable by UV (or photochromic group) such as the azobenzene, spiropyran, 2-diazo-1,2-naphthoquinone, onitrobenzylated, thiol, or 6-nitro-veratroyloxycarbonyl groups, for example poly (ethylene oxide) -block-poly (2-nitrobenzylmethacrylate), and other block copolymers, as described in particular in Liu et al., Polymer Chemistry 2013, 4, 3431-3443;

- A group sensitive to IR or cleavable by IR such as o-nitrobenzyl or 2-diazo-1,2-naphthoquinone, for example the polymers described in Liu et al., Polymer Chemistry 2013, 4, 3431-3443; and

- a temperature sensitive group such as poly (N-isopropylacrylamide).

Step c)

Step c) of the process according to the invention consists in preparing a second emulsion (E2).

The second emulsion consists of a dispersion of droplets of the first emulsion in a composition C3 immiscible with C2, created by dropwise addition of the emulsion (E1) in C3 with stirring.

During step c), the emulsion (E1) is at a temperature between 15 ° C and 60 ° C. During step c), the composition C3 is at a temperature between 15 ° C and 60 ° C.

Under the addition conditions of step c), the compositions C2 and C3 are not miscible with each other, which means that the quantity (by weight) of the composition C2 capable of being dissolved in composition C3 is less than or equal to 5%, preferably less than 1%, and preferably less than 0.5%, relative to the total weight of composition C3, and that the quantity (by weight) of composition C3 capable of 'to be dissolved in composition C2 is less than or equal to 5%, preferably less than 1%, and preferably less than 0.5%, relative to the total weight of composition C2.

Thus, when the emulsion (E1) comes into contact with the composition C3 with stirring, the latter is dispersed in the form of drops, called double drops, the dispersion of these drops of emulsion (E1) in the continuous phase C3 being called emulsion (E2).

Typically, a double drop formed during step c) corresponds to a single drop of composition C1 as described above, surrounded by an envelope of composition C2 which completely encapsulates said single drop.

The double drop formed during step c) may also comprise at least two single drops of composition C1, said single drops being surrounded by an envelope of composition C2 which completely encapsulates said single drops.

Thus, said double drops comprise a heart consisting of one or more single drops of composition C1, and a layer of composition C2 surrounding said heart.

The resulting emulsion (E2) is generally a double polydisperse emulsion (C1-in-C2-in-C3 emulsion or C1 / C2 / C3 emulsion), which means that the double drops do not have a clear size distribution in the emulsion (E2).

The immiscibility between the compositions C2 and C3 makes it possible to avoid mixing between the layer of composition C2 and the composition C3 and thus ensures the stability of the emulsion (E2).

The immiscibility between the compositions C2 and C3 also makes it possible to prevent the water-soluble substance of the composition C1 from migrating from the heart of the drops to the composition C3.

To implement step c), one can use any type of agitator usually used to form emulsions, such as for example a mechanical paddle stirrer, a static foam concentrate, an ultrasonic homogenizer, a membrane homogenizer, a homogenizer at high pressure, a colloid mill, a high shear disperser or a high speed homogenizer.

Composition C3

According to one embodiment, the viscosity of the composition C3 at 25 ° C is greater than the viscosity of the emulsion (E1) at 25 ° G

According to the invention, the viscosity of the composition C3 at 25 ° C is between 500 mPa.s and 100,000 mPa.s.

Preferably, the viscosity of the composition C3 at 25 ° C is between 3,000 mPa.s and 100,000 mPa.s, preferably between 5,000 mPa.s and 80,000 mPa.s, for example between 7,000 mPa.s and 70,000 mPa.s.

According to this embodiment, given the very high viscosity of the continuous phase formed by composition C3, the speed of destabilization of the double drops of the emulsion (E2) is significantly slow compared to the duration of the process of the invention , which then provides kinetic stabilization of the emulsions (E2) then (E3) until the polymerization of the capsule shell is completed. The capsules, once polymerized, are thermodynamically stable.

Thus, the very high viscosity of the composition C3 ensures the stability of the emulsion (E2) obtained at the end of step c).

A low surface tension between C3 and the first emulsion as well as a high viscosity of the system make it possible to advantageously ensure the kinetic stability of the double emulsion, preventing it from being out of phase during the duration of the manufacturing process.

Preferably, the interfacial tension between the compositions C2 and C3 is low. The low interfacial tension between the compositions C2 and C3 also advantageously makes it possible to ensure the stability of the emulsion (E2) obtained at the end of step c).

The volume fraction of the first emulsion in C3 can be varied from 0.05 to 0.5 in order on the one hand to improve the production yield and on the other hand to vary the average diameter of the capsules. At the end of this step, the size distribution of the second emulsion is relatively wide.

According to one embodiment, the ratio between the volume of emulsion (E1) and the volume of composition C3 varies between 1:10 and 10: 1. Preferably, this ratio is between 1: 9 and 3: 1, preferably between 1: 9 and 1: 1.

This ratio can be adapted in order to control the total amount of active material encapsulated among the resulting population of polymerized microcapsules.

According to one embodiment, composition C3 also comprises at least one branched polymer, preferably of molecular weight greater than 5,000 g.mol ¹ , and / or at least one polymer of molecular weight greater than 5,000 g.mol ' ¹ , and / or solid particles such as silicates.

According to one embodiment, composition C3 comprises at least one branched polymer, preferably of molecular weight greater than 5,000 g.mol ¹ , preferably between 10,000 g.mol ¹ and 500,000 g.mol ¹ , for example between 50 000 g.mol ¹ and 300 000 g.mol ¹ .

By “branched polymer” (or branched polymer) is meant a polymer having at least one branching point between its two end groups, a branching point (also called branching point) being a point of a chain on which is fixed a side chain also called branch or hanging chain.

Among the branched polymers, mention may, for example, be made of grafted or comb polymers, or even star polymers or dendrimers.

According to one embodiment, composition C3 comprises at least one polymer of molecular weight greater than 5,000 g.mol ¹ , preferably between 10,000 g.mol ' ¹ and 500,000 g.mol' ¹ , for example between 50,000 g .mol ¹ and 300,000 g.mol ¹ .

As the polymer which can be used in composition C3, mention may be made of the following compounds, used alone or else mixed together:

- cellulose derivatives, such as cellulose ethers: methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose or methyl hydroxypropyl cellulose;

- polyacrylates (also called carbomers), such as polyacrylic acid (PAA), polymethacrylic acid (PMAA), poly (hydroxyethyl methacrylate) (pHEMA), poly (N-2-hydroxypropyl methacrylate) (pHPMA) ;

- polyacrylamides such as poly (N-isopropylacrylamide) (PNIPAM); polyvinylpyrrolidone (PVP) and its derivatives;

- polyvinyl alcohol (PVA) and its derivatives;

- poly (ethylene glycol), poly (propylene glycol) and their derivatives, such as poly (ethylene glycol) acrylate / methacrylate, poly (ethylene glycol) diacrylate / dimethacrylate, polypropylene carbonate;

- polysaccharides such as carrageenans, carob gums or tara gums, dextran, xanthan gums, chitosan, agarose, hyaluronic acids, gellan gum, guar gum, gum arabic, gum tragacanth , diutane gum, oat gum, karaya gum, ghatti gum, curdlan gum, pectin, konjac gum, starch;

- protein derivatives such as gelatin, collagen, fibrin, polylysine, albumin, casein;

- silicone derivatives such as polydimethylsiloxane (also called dimethicone), alkyl silicones, aryl silicones, alkyl aryl silicones, polyethylene glycol dimethicones, polypropylene glycol dimethicone;

- waxes, such as diester waxes (alkanediol diesters, hydroxyl acid diesters), triester waxes (triacylglycerols, alkane-1,2-diol, ω-hydroxy acid and fatty acid triesters, esters hydroxymalonic acid, fatty acid and alcohol, triesters of hydroxyl acids, fatty acid and fatty alcohol, triesters of fatty acid, hydroxyl acid and diol) and polyester waxes (polyesters of Fatty acids). The fatty acid esters which can be used as waxes in the context of the invention are, for example, cetyl palmitate, cetyl octanoate, cetyl laurate, cetyl lactate, cetyl isononanoate, stearate cetyl, stearyl stearate, myristyl stearate, cetyl myristate, isocetyl stearate, glyceryl trimyristate, glyceryl tripalmitate, glyceryl monostearate or glyceryl and cetyl palmitate;

fatty acids which can be used as waxes such as cerotic acid, palmitic acid, stearic acid, dihydroxystearic acid, behenic acid, lignoceric acid, arachidic acid, myristic acid, l lauric acid, tridecyclic acid, pentadecyclic acid, margaric acid, nonadecyclic acid, heneicosylic acid, tricosylic acid, pentacosylic acid, heptacosylic acid, montanic acid or l nonacosylic acid;

- fatty acid salts, in particular aluminum fatty acid salts such as aluminum stearate, hydroxyl aluminum bis (2-ethylhexanoate);

- isomerized jojoba oil;

- hydrogenated sunflower oil;

- hydrogenated coconut oil; hydrogenated lanolin oil;

castor oil and its derivatives, in particular modified hydrogenated castor oil or the compounds obtained by esterification of castor oil with fatty alcohols;

- polyurethanes and their derivatives;

- styrenic polymers such as styrene butadiene;

- polyolefins such as polyisobutene.

According to one embodiment, composition C3 comprises solid particles such as clays, silicas and silicates.

As solid particles which can be used in composition C3, mention may be made of clays and silicates belonging in particular to the category of phyllosilicates (also called sheet silicas). As an example of a silicate which can be used in the context of the invention, mention may be made of Bentonite, Hectorite, Attapulgite, Sepiolite, Montmorillonite, Saponite, Sauconite, Nontronite, Kaolinite, Talc , Sepiolite, Chalk. Synthetic fumed silicas can also be used. The clays, silicates and silicas mentioned above can advantageously be modified by organic molecules such as polyethers, ethoxylated amides, quaternary ammonium salts, long chain diamines, long chain esters, polyethylene glycols, polypropylene glycols.

These particles can be used alone or mixed together.

According to one embodiment, composition C3 comprises at least one polymer of molecular weight greater than 5,000 g.mol ¹ and solid particles. Any mixture of the compounds mentioned above can be used.

Step d)

Step d) of the method according to the invention consists in refining the size of the drops of the second emulsion (E2).

This step may consist in applying a homogeneous controlled shear to the emulsion (E2), said shear speed applied being between 10 s ′ ¹ and 100,000 s ¹ .

According to one embodiment, the double polydisperse drops obtained in step c) are subjected to size refinement consisting in subjecting them to a shear capable of fragmenting them into new double drops of homogeneous and controlled diameters. Preferably, this fragmentation step is carried out using a high shear cell of the Couette type according to a method described in patent application EP 15 306 428.2.

According to one embodiment, in step d), the second emulsion (E2), obtained at the end of step c), consisting of double polydisperse drops dispersed in a continuous phase, is subjected to shearing in a mixer, which applies a homogeneous controlled shear.

Thus, according to this embodiment, step d) consists in applying a homogeneous controlled shear to the emulsion (E2), said applied shear speed being between 1000 s ′ ¹ and 100,000 s ′ ¹ .

According to this embodiment, in a mixer, the shear speed is said to be controlled and homogeneous, regardless of the duration, when it passes to an identical maximum value for all the parts of the emulsion, at a given instant which may vary. from one point of the emulsion to another. The exact configuration of the mixer is not essential according to the invention, as long as the entire emulsion has been subjected to the same maximum shear when leaving this device. The mixers suitable for performing step d) are described in particular in document US 5,938,581.

The second emulsion can undergo a homogeneous controlled shearing when it circulates through a cell formed by:

- two concentric rotary cylinders (also called a Couette type mixer);

- two parallel rotating discs; or

- two parallel oscillating plates.

According to this embodiment, the shearing speed applied to the second emulsion is between 1,000 s ¹ and 100,000 s ¹ , preferably between 1,000 s ¹ and 50,000 s ¹ , and preferably between 2,000 s ¹ and 20 000 s ¹ .

According to this embodiment, during step d), the second emulsion is introduced into the mixer and is then subjected to shearing which results in the formation of the third emulsion. The third emulsion (E3) is chemically identical to the second emulsion (E2) but consists of double monodisperse drops while the emulsion (E2) consists of double polydisperse drops. The third emulsion (E3) typically consists of a dispersion of double drops comprising a core consisting of one or more drops of composition C1 and a layer of composition C2 encapsulating said core, said double drops being dispersed in composition C3.

The difference between the second emulsion and the third emulsion is the variance in size of the double drops: the drops of the second emulsion are polydispersed in size while the drops of the third emulsion are monodispersed, thanks to the fragmentation mechanism described above.

Preferably, according to this embodiment, the second emulsion is introduced continuously into the mixer, which means that the amount of double emulsion (E2) introduced at the inlet of the mixer is the same as the amount of third emulsion ( E3) at the outlet of the mixer.

Since the size of the drops of the emulsion (E3) essentially corresponds to the size of the drops of the solid microcapsules after polymerization, it is possible to adjust the size of the microcapsules and the thickness of the envelope by adjusting the speed of shear during step d), with a strong correlation between the decrease in the size of the drops and the increase in the shear rate. This allows the resulting dimensions of the microcapsules to be adjusted by varying the shear rate applied during step d).

According to a preferred embodiment, the mixer used during step d) is a duvet type mixer, comprising two concentric cylinders, an external cylinder with internal radius R _o and an internal cylinder with external radius R ,, the cylinder external being fixed and the internal cylinder being in rotation with an angular speed ω.

A Duvet type mixer suitable for the process of the invention can be supplied by the company T.S.R. France.

According to one embodiment, the angular speed ω of the internal rotating cylinder of the Couette type mixer is greater than or equal to 30 rad.s' ¹ .

For example, the angular speed ω of the internal cylinder in rotation of the Duvet type mixer is around 70 rad.s ¹ .

The dimensions of the fixed external cylinder of the Duvet type mixer can be chosen to modulate the space (d = R _o - R,) between the internal rotating cylinder and the fixed external cylinder.

According to one embodiment, the space (d = R _o - R,) between the two concentric cylinders of the Couette type mixer is between 50 μm and 1000 μm, preferably between 100 μm and 500 μm, for example between 200 pm and 400 pm.

For example, the distance d between the two concentric cylinders is 100 µm.

According to this embodiment using a Duvet type mixer, during step d), the second emulsion is introduced at the inlet of the mixer, typically via a pump, and is directed towards the space between the two concentric cylinders , the outer cylinder being fixed and the inner cylinder being in rotation at an angular speed ω.

When the double emulsion is in the space between the two cylinders, the shear rate applied to said emulsion is given by the following equation:

fi j® (fl _o fij in which:

- ω is the angular speed of the internal cylinder in rotation,

- R _o is the internal radius of the fixed external cylinder, and

- R, is the external radius of the internal cylinder in rotation.

According to another embodiment, when the viscosity of the composition C3 is greater than 2000 mPa.s at 25 ° C, step d) consists in applying to the emulsion (E2) a shear rate less than 1000 s' ¹ .

According to this embodiment, the fragmentation step d) can be carried out using any type of mixer usually used to form emulsions with a shear rate of less than 1000 s ¹ , in which case the viscosity of the composition C3 is greater than 2,000 mPa.s, namely under conditions such as those described in patent application FR 16 61787.

The geometric characteristics of the double drops formed at the end of this stage will dictate those of future capsules.

According to this embodiment, in step d), the emulsion (E2), consisting of polydisperse drops dispersed in a continuous phase, is subjected to shearing, for example in a mixer, at a low shearing speed, know less than 1000 s ¹ .

According to this embodiment, the shear speed applied in step d) is for example between 10 s ¹ and 1000 s ¹ .

Preferably, the shear rate applied in step d) is strictly less than 1000 s ¹ .

According to this embodiment, the emulsion drops (E2) can only be effectively fragmented into fine, monodisperse emulsion drops (E3) if a high shear stress is applied to them.

The shear stress σ applied to a drop of emulsion (E2) is defined as the tangential force per unit of drop surface resulting from the macroscopic shear applied to the emulsion during its agitation during step d).

The shear stress σ (expressed in Pa), the viscosity of the composition C3 η (expressed in Pa s) and the shear rate γ (expressed in s ¹ ) applied to the emulsion (E2) during its stirring during from step d) are connected by the following equation:

σ = ηγ

Thus, according to this embodiment, the high viscosity of the composition C3 makes it possible to apply a very high shear stress to the drops of emulsion (E2) in the mixer, even if the shear speed is low and the shear inhomogeneous.

To implement step d) according to this embodiment, one can use any type of stirrer usually used to form emulsions, such as for example a mechanical paddle stirrer, a static foam concentrate, an ultrasonic homogenizer, a homogenizer with membrane, a high pressure homogenizer, a colloid mill, a high shear disperser or a high speed homogenizer.

According to a preferred embodiment, a simple foam concentrate is used such as a mechanical paddle stirrer or a static foam concentrate to implement step d). Indeed, this is possible because this embodiment requires neither a controlled shear nor a shear greater than 1000 s ¹ .

Step e)

Step e) of the process of the invention consists of crosslinking and therefore the formation of the envelope of the solid microcapsules according to the invention.

This stage makes it possible both to achieve the expected protection and retention performance of the capsules and to ensure their thermodynamic stability, by definitively preventing any destabilization mechanism such as coalescence or ripening.

According to one embodiment, when the composition C2 comprises a photoinitiator, step e) is a photopolymerization step consisting in exposing the emulsion (E3) to a light source capable of initiating the photopolymerization of the composition C2, in particular to a UV light source preferably emitting in the wavelength range between 100 nm and 400 nm, in particular for a period of less than 15 minutes.

According to this embodiment, step e) consists in subjecting the emulsion (E3) to a photopolymerization, which will allow the photopolymerization of the composition C2. This step will make it possible to obtain microcapsules encapsulating the water-soluble substance as defined above.

According to one embodiment, step e) consists in exposing the emulsion (E3) to a light source capable of initiating the photopolymerization of the composition C2.

Preferably, the light source is a UV light source.

According to one embodiment, the UV light source emits in the wavelength range between 100 nm and 400 nm.

According to one embodiment, the emulsion (E3) is exposed to a light source for a duration of less than 15 minutes, and preferably for 5 to 10 minutes.

During step e), the envelope of the above-mentioned double drops, consisting of photocrosslinkable composition C2, is crosslinked and thus converted into a viscoelastic polymeric envelope, encapsulating and protecting the water-soluble substance from its release in the absence of a mechanical trigger. .

By way of illustration, a composition C2 according to the invention can be a mixture of polymer CN981 (polyacrylate oligomer of the brand Sartomer, Arkema) (for example of 69% by weight), of hexanediol diacrylate (crosslinking agent) (for example 30 % by weight) and Darocure 1173 (photoinitiator) (for example 1% by weight).

According to another embodiment, when the composition C2 does not comprise a photoinitiator, step e) is a polymerization step, without exposure to a light source, the duration of this polymerization step e) preferably being between 8 hours and 100 hours and / or this step e) is carried out at a temperature between 20 ° C and 80 ° C.

According to this embodiment, the polymerization is initiated for example by exposure to heat (thermal initiation), or by simple contacting of the monomers, polymers and crosslinking agents together, or with a catalyst. The polymerization time is then generally greater than several hours.

Preferably, step e) of polymerization of the composition C2 is carried out for a period of between 8 hours and 100 hours, at a temperature between 20 ° C and 80 ° C.

By way of illustration, a composition C2 according to the invention can be a PDMS preparation capable of being polymerized, prepared with the two-component kit Sylgard 184 from Dow Corning. Composition C2 can then comprise 30% of component No. 1 and 70% of component No. 2.

Step f)

Step f) of the process of the invention is implemented when the composition C3 does not include the above-mentioned reactive and reinforcing compositions.

It consists in adding the solid microcapsules obtained in the previous step into a composition C4, the composition C4 comprising at least the above-mentioned reactive and reinforcing compositions. This is done to prevent / avoid any degradation of the reactive component and / or of the reinforcing component during step d) of size refining.

According to one embodiment, when composition C3 does not comprise a reactive composition and a reinforcing composition, said method according to the invention also comprises, after step e) and before step f), a step g) filtration, total or partial, preferably total, of the solid microcapsules in order to exclude partially or totally, preferably completely, the composition C3.

According to the invention, this filtration step f) can be carried out by any suitable means known to those skilled in the art, such as by centrifugation, mechanical filtration, strainer sieve, aspiration of the aqueous phase continuously or after creaming of the microcapsules. solids, preferably by centrifugation.

According to a first variant, C3 and C4 are miscible with each other.

According to another variant, C3 and C4 are not miscible with each other.

According to one embodiment, the composition C4 has properties in terms of viscosity and / or interfacial tension as defined above concerning the composition C3.

According to one embodiment, composition C4 further comprises at least one branched polymer, preferably of molecular weight greater than 5,000 g.mol ¹ , and / or at least one polymer of molecular weight greater than 5,000 g.mol ' ¹ , and / or solid particles such as silicates.

Said branched polymer, said polymer with a molecular weight greater than 5000 g.mol ¹ , and said solid particles are as defined above concerning composition C3.

According to one embodiment, the compositions C3 and C4 comprise at least one branched polymer, preferably of molecular weight greater than 5,000 g.mol ¹ , and / or at least one polymer of molecular weight greater than 5,000 g.mol ¹ , and / or solid particles such as silicates.

The present invention also relates to a mechanism for releasing the crosslinking composition contained in the capsules by mechanical stimulation such as shearing or compression.

The expressions "ranging between ... and ... >>," ranging from ... to ... >> and "ranging from ... to ... >> must be understood bounds included, except if the opposite is specified.

The examples which follow illustrate the present invention without limiting its scope.

EXAMPLES

Example 1: Preparation of solid microcapsules according to the invention with a polymeric composition C2 but not comprising a step of exposure to a UV light source

Composition of C1, C2, C3 and C4:

. C1 îo Composition C1, of direct emulsion type, comprises a crosslinking composition as described below:

Ingredients INCI Name Weight content (%) 1 Propylene glycol Propylene glycol 19.72 2 Glycerol Glycerin 3.94 3 Jeechem BUGL Butylene Glycol 9.86 4 Sodium chloride Sodium Chloride 0.99 5 Dow Elastomer Blend 9041 Dimethicone (and) Dimethicone Crosspolymer 9.86 6 Dow 245 Fluid Cyclopentasiloxane 7.89 7 Jeensile CPS-312 Cyclomethicone 1.97 8 Nylon 10-12 Nylon 12 (and) Isopropyl Titanium Triisostearate 4.64 9 Chronosphere Optical Brite Silica and polyurethane40 / silica and polyurethane-40 and green 5 0.18 10 Platinum divinyl complex PC 075.3 1,3-diethenyl-1,1,3,3tetramethyldisiloxane platinum (1: 1) 1.00 11 Water - Qsp * TOTAL 100.00

* Qsp: sufficient quantity for.

Ingredients 11 and 1 to 4 were combined and mixed at 750 rpm for two minutes with a 40 mm 4-blade propeller until homogeneous to create an aqueous phase. In a separate container, ingredients 5-7 were mixed at 750 rpm for two minutes with a 4-blade 40 mm propeller until homogeneous to create a silicone mixture A. In the aqueous phase, ingredients 8 and 9 were added and mixed at 750 rpm with a propeller of 4 40 mm blades. The mixing speed was increased to 1000 rpm and the mixture A was mixed with the aqueous phase until a homogeneous final mixture was obtained. Ingredient 10 was added and stirred at 1,000 rpm for 1 minute, then homogenized at 25,000 rpm for 5 minutes.

Alternatively, composition C1 comprises a crosslinking composition as described below:

Ingredients INCI Name Weight content (%) 1 Water - Osp 2 Carbopol ULTREZ 21 1.01 3 Denaturated Ethanol 190 Proof 29.35 4 Glycerol Glycerin 2.02 5 Sodium hydroxide (2%) Sodium Hydroxide (2%) 0.20 6 Platinum divinyl complex 3% PC 075.3 1,3-diethenyl-1,1,3,3tetramethyldisiloxane platinum (1: 1) 1.99 TOTAL 100.00

Ingredients 1 and 2 were mixed at 250 rpm until Carbopol was completely hydrated and the mixture was free of white particles. Ingredients 3 and 4 were mixed at 500 rpm with a 40 mm 4-blade propeller. Ingredient 5 was added dropwise with moderate stirring to

550 rpm with a propeller of 4 40 mm blades until the mixture is homogeneous and thickened. Ingredient 6 was added with moderate stirring at 550 rpm with a propeller of 4 40 mm blades, followed by mixing at 1000 rpm for 5 minutes until the mixture was homogeneous.

. C2

Composition C2 is a PDMS preparation capable of being polymerized, prepared with the two-component kit Sylgard 184 from Dow Corning. Composition C2 comprises 30% of component No. 1 and 70% of component No. 2.

C1 and C2 are therefore immiscible and have a non-zero surface tension.

Component 1 of the kit includes the following products (data provided by Dow Corning):

. between 55.0% and 75.0% of dimethyl, methylhydrogen siloxane,. between 15.0% and 35.0% of dimethyl siloxane, dimethylvinyl-terminated,. between 10.0% and 30.0% of dimethylvinylated and trimethylated silica,. between 1.0% and 5.0% of tetramethyl tetravinyl cyclotetrasiloxane,. less than 0.10% ethylbenzene.

Component 2 of the kit includes the following products (data supplied by Dow Corning):

. less than 200 ppm of a platinum complex,. between 55.0 and 75.0% dimethyl siloxane, dimethylvinyl-terminated,. between 30.0 and 50.0% dimethylvinylated and trimethylated silica,. less than 1.0% tetra (trimethylsiloxy) silane,. 0.5% xylene,. 0.2% ethylbenzene.

This kit can be considered as the mixture of several polymers, several crosslinking agents and a catalyst within the meaning of the invention.

. C3

Composition C3 is a Tego 340FD carbomer solution (Evonik, Essen, Germany) at 4% by mass in distilled water. The solution is stirred at 2000 rpm for 20 minutes using a propeller stirrer. The pH is then adjusted to 6 using a 2M sodium hydroxide solution. The viscosity of the composition C3 at 10 s ¹ is 52,000 mPa.

C2 and C3 are therefore immiscible and have a non-zero surface tension.

. C4

Composition C4 includes the reactive composition and the reinforcing composition and is as described in Tables 1 or 2 below: Table 1

Ingredients INCI Name Weight content (%) 1 DMS-V41 Poly (Dimethylsiloxane), Vinyl Terminated Qsp 2 Aerosil 8200 Fumed silica modified with hexamethyldisilazane 9.45 3 PS123-KG Hydrogen Dimethicone 12.00 4 UCT-PS448.5 Polydimethylsiloxane, Vinyldimethyl Terminated 8.55 5 Velvesil 125 Cyclopentasiloxane (and) C30-45 Alkyl Cetearyl Dimethicone Crosspolymer 3.60 6 Water - 27.00 7 Granhydrogel 0 Water (and) Glyceryl Polyacrylate (and) 1,3Butylene Glycol (and) PVM / MA (and) Propylparaben (and) Methylparaben 6.70 8 Granpowder Nylon Nylon-12 5.90 TOTAL 100.00

Ingredients 1-4 were mixed by hand in a 4 oz graduated blender until the mixture was free of white particles. Then ingredient 5 was added and the mixture was confirmed as homogeneous (mixture A). In a separate container, ingredients 6 and 7 were mixed by hand until homogeneous (mixture B). Mixture B was added to mixture A with vigorous stirring, supplied by a propeller of 4 blades and 40 mm, at 550 rpm, then ingredient 8 was added and the mixing speed was 1000 revolutions / min and the whole was mixed for 5 minutes. The mixture was confirmed as homogeneous.

Table 2

Ingredients INCI Name Weight content (%) 1 DMS-V41 Poly (Dimethylsiloxane), Vinyl Terminated Qsp 2 Aerosil 8200 Fumed silica modified with hexamethyldisilazane 10.87 3 PS123-KG Hydrogen Dimethicone 3.47 4 UCT-PS448.5 Polydimethylsiloxane, Vinyldimethyl Terminated 16.41 5 Velvesil 125 Cyclopentasiloxane (and) C30-45 Alkyl Cetearyl Dimethicone Crosspolymer 4.16 6 Water - 21.45 7 Granhydrogel O Water (and) Glyceryl Polyacrylate (and) 1,3Butylene Glycol (and) PVM / MA (and) Propylparaben (and) Methylparaben 5.38 8 Granpowder Nylon Nylon-12 6.82 TOTAL 100.00

Ingredients 1-4 were mixed by hand in an oz. Graduated mixer until the mixture was free of white particles. Then ingredient 5 was added and the mixture was confirmed as homogeneous (mixture A). In a separate container, ingredients 6 and 7 were mixed by hand until homogeneous (mixture B). Mixture B was added to mixture A with vigorous stirring, supplied by a propeller of 4 blades and 40 mm, at 550 rpm, then ingredient 8 was added and the mixing speed was 1000 revolutions / min and the whole was mixed for 5 minutes. The mixture was confirmed as homogeneous.

Manufacturing of microcapsules:

A mechanical agitator (Heidolph RZR 2021) equipped with a deflocculating stirring propeller with a diameter of 3 cm is used to carry out all of the emulsification steps.

Step a): composition C1 is added dropwise to composition C2 with stirring at 200 rpm until a ratio C1: C2 = 20:80 by weight is obtained. Stirring is then maintained at 200 rpm for 30 minutes.

Step b): the emulsion (E1) thus obtained is added dropwise to composition C3 with stirring at 500 rpm until an E1: C3 ratio = 10:90 by weight is obtained.

Step c): The emulsion (E2) thus obtained is stirred at 500 rpm for 30 minutes. Under these conditions, the shear applied to the emulsion (E2), although very little controlled, can be estimated at less than 500 s ¹ (for the calculation details, we will refer to: Metzner AB, Otto RE. Agitation of non-Newtonian fluids. AlChE J (1957) 3: 3-10; Wu, J et al., Estimation of agitatorflow shear rate. AlChE J (2006) 52: 23232332).

Step d): the emulsion (E3) thus obtained is left for 48 hours at rest without agitation to allow the capsules to polymerize.

Step e): the capsules are filtered so as to remove the composition C3. To do this, we make a 10-fold dilution in water and then add a 10% w / w NaCl solution (equivalent to 5% of the diluted solution). The mixture is allowed to settle and the mixture is filtered to recover the capsules.

Step f): the capsules are then added to composition C4 at a “Capsules: C4” ratio between 10:90 and 50:50 by weight with stirring.

Example 2: Preparation of solid microcapsules according to the invention with a photocrosslinkable polymeric composition C2

Composition of C1, C2, C3 and C4:

Composition C1 is identical to the formulas described in Example 1 above.

Composition C2 is a mixture of 69% by weight of polymer CN981 (polyacrylate oligomer from the brand Sartomer, Arkema), 30% by weight of hexanediol diacrylate (crosslinking agent) and 1% by weight of Darocure 1173 (photoinitiator).

Composition C3 is a composition of ExxonMobil PAO 100 or a 15% by mass alginate solution, with a viscosity of 63,000 s-1 at 25 ° C.

C2 and C3 are immiscible.

Composition C4 is identical to the formulas described in Example 1 above.

Manufacturing of microcapsules:

A mechanical agitator (Heidolph RZR 2021) equipped with a deflocculating stirring propeller with a diameter of 3 cm is used to carry out all of the emulsification steps.

Step a): composition C1 is added dropwise to composition C2 at a ratio C1: C2 = 30:70 by weight with stirring at 500 rpm.

Step b): the emulsion (E1) obtained in the previous step is added dropwise to composition C3 at a ratio E1: C3 = 10:90 by weight with stirring at 500 rpm.

Step c): the emulsion (E2) thus obtained is left under stirring at 500 rpm for 10 minutes. The shear applied by a stirring propeller is very little controlled. Under the conditions of step c), the shear applied to the emulsion (E2) can be estimated at less than 500 s ¹ (for the calculation details, reference is made to: Metzner AB, Otto RE. Agitation of no -Newtonian fluids. AlChE J (1957) 3: 3-10; Wu, J et al., Estimation of agitator flow shear rate. AlChE J (2006) 52: 2323-2332).

Step d): the monodisperse emulsion (E3) thus obtained is irradiated for 10 minutes using a UV light source (Dymax LightBox ECE 2000) having a maximum light intensity of 0.1 W / cm ² at a wavelength of 365 nm, to allow cross-linking of the capsules.

The size distribution of the capsules thus obtained is measured by light scattering technique using a Mastersizer 3000 (Malvern Instruments) equipped with a Hydro SV measuring cell. The average size of the capsules is measured at 26 µm. The width at mid-height of the size distribution (considered as a simple means of evaluating the monodispersity of the capsules) is measured at 31 μm.

Step e): the capsules are filtered so as to remove the composition C3. To do this, we make a 10-fold dilution in water and then add a 10% w / w NaCl solution (equivalent to 5% of the diluted solution). The mixture is allowed to settle and the mixture is filtered to recover the capsules.

Step f): the capsules are then added to composition C4 at a “Capsules: C4” ratio between 10:90 and 50:50 by weight with stirring.

In Examples 3 to 5 below, people applied a composition according to Example 1 or 2 to the skin so as to obtain an “elastic secondary skin” which is the subject of XPL technology and compared the ease of use. of this composition compared to conventional XPL technology, that is to say based on a 2-step application process as described above.

The cosmetic benefits, the treatment of skin wounds and dermatological conditions, in particular eczema associated with the application to the skin of this composition according to example 1 or 2, have also been appreciated.

EXAMPLE 3 Cosmetic Benefits on the Skin

Concerning the properties of the transparent film in terms of elasticity, contractility, adhesion, tensile strength and occlusiveness, the protocol described in example 6 of international application WO 2012/030984 was applied using the capsules of Example 1 or 2.

It was then found that the encapsulation does not alter the properties of the product (crosslinking composition / reinforcing composition / reactive composition) according to the invention and remains effective and satisfactory in terms of the cosmetic benefits sought in the treated area. , in particular in terms of the treatment of fine lines and wrinkles, the texture of the skin and how these effects last over time.

Example 4: Wound treatment

The protocol described in example 7B of international application WO 2012/030993 was applied, using the capsules of example 1 or 2.

It was then found that the encapsulation does not alter the properties of the product (crosslinking composition / reinforcement composition / reactive composition) according to the invention and remains effective and satisfactory in terms of the treatment of skin injuries in the area. processed.

EXAMPLE 5 Dermatological Conditions

The protocol described in example 8 of international application WO 2013/044098 was applied, using the capsules of example 1 or 2.

It was then found that the encapsulation does not alter the properties of the product (crosslinking composition / reinforcing composition / reactive composition) according to the invention and remains effective and satisfactory in the area treated in terms of the treatment of the affections. dermatological, especially eczema.

Finally, the test persons mentioned in examples 3 to 5 decided on better control of the thickness, and therefore better final quality, of the “second skin” film obtained on the skin after application of the microcapsules according to the invention compared with classic XPL technology (ie in 2 steps).

Claims (19)

1. Composition including: at least one solid microcapsule comprising a core and a solid envelope totally encapsulating the heart at its periphery, the diameter of said solid microcapsule preferably being between 1 μm and 30 μm, the thickness of the solid envelope being preferably included between 0.1 pm and 20 pm and the standard deviation of the distribution of the diameter of the microcapsules being preferably less than 50%, or even less than 25%, or less than 1 pm, and a continuous phase containing the solid microcapsule (s), in which the core comprises at least one crosslinking composition and the solid envelope consists of crosslinked polymer, and in which the continuous phase further comprises at least one reactive composition and at least one reinforcing composition. 2. Composition according to claim 1, in which the crosslinking composition comprises at least one metallic catalyst, in particular a catalyst based on platinum, rhodium or tin. 3. Composition according to claim 2, in which the crosslinking composition further comprises at least one organopolysiloxane with vinyl terminal functions. 4. Composition according to any one of claims 1 to 3, in which the reactive composition comprises at least one polymer chosen from polysiloxanes; poly (ethylene oxides); poly (propylene oxides); polyureas; polyurethanes; polyesters, in particular polylactic-coglycolic acid, polycaprolactone, polylactic acid, polyglycolic acid and polyhydroxybutyrate; polyamides; polysulfones and their mixtures. 5. Composition according to any one of claims 1 to 4, in which the reactive composition comprises at least one organopolysiloxane, optionally with vinyl terminal functions. 6. Composition according to claim 5, in which the organopolysiloxane is chosen from organopolysiloxanes with a viscosity between 100,000 mPa.s and 500,000 mPa.s at 25 ° C, organopolysiloxanes with a viscosity between 500 mPa.s and 50 000 mPa.s at 25 ° C, and mixtures thereof 7. Composition according to any one of claims 1 to 6, in which the reactive composition comprises at least one hydride-terminated polysiloxane. 8. Composition according to any one of claims 1 to 7, in which the reactive composition comprises at least one organopolysiloxane and at least one hydride-terminated polysiloxane. 9. Composition according to any one of claims 1 to 8, in which the reinforcing composition comprises at least one reinforcing constituent chosen from the group consisting of clays, chalk, talc, calcites, mica, sulphate barium, zirconium dioxide, zinc sulfide, zinc oxide, titanium dioxide, aluminum oxide, silica aluminates, calcium silicates, silicas, and mixtures thereof , said reinforcing constituent possibly being treated on the surface. 10. Composition according to claim 9, in which the reinforcing constituent is silica, preferably surface-treated silica, in particular silica treated with hexamethyldisilazane. 11. Cosmetic composition comprising a composition according to any one of claims 1 to 10 and further comprising at least one physiologically acceptable medium. 12. Process for the preparation of a composition according to any one of claims 1 to 10, comprising the following steps: a) the preparation of a composition C1 comprising at least one crosslinking composition, b) the addition, with stirring, of said composition C1 in a polymeric composition C2, the compositions C1 and C2 not being miscible with each other, the composition C2 comprising at least one monomer or polymer, at least one agent crosslinking agent, and optionally at least one (photo) initiator or crosslinking catalyst, the viscosity of the composition C2 being between 500 mPa.s and 100,000 mPa.s at 25 ° C, and preferably being greater than the viscosity of composition C1, whereby an emulsion (E1) is obtained comprising drops of composition C1 dispersed in composition C2; c) the addition, with stirring, of the emulsion (E1) in a composition C3, the compositions C2 and C3 not being miscible with each other, the viscosity of the composition C3 being between 500 mPa.s and 100,000 mPa.s at 25 ° C, and preferably being greater than the viscosity of the emulsion (E1), the composition C3 optionally comprising at least one reactive composition and at least one reinforcing composition, whereby a double emulsion (E2) comprising drops dispersed in composition C3; d) applying an emulsion shear (E2), whereby a double emulsion (E3) is obtained comprising drops of controlled size dispersed in composition C3; e) polymerization of composition C2, whereby solid microcapsules are obtained dispersed in composition C3; and f) when the composition C3 does not comprise the reactive composition and the reinforcing composition, the addition of the solid microcapsules, dispersed in the composition C3, in a composition C4, the composition C4 comprising at least one reactive composition and at least one composition reinforcement. 13. The preparation method according to claim 12, in which composition C3 does not comprise a reactive composition and a reinforcement composition, and further comprising, after step e) and before step f), a step g) filtration, total or partial, preferably total, of the solid microcapsules in order to exclude partially or totally, preferably completely, the composition C3. 14. The preparation method as claimed in claim 12 or 13, in which step d) consists in applying a homogeneous controlled shear to the emulsion (E2), said applied shear rate being between 1000 s ¹ and 100,000 s ¹ . 15. The preparation method according to claim 12 or 13, in which, when the viscosity of the composition C3 is greater than 2,000 mPa.s at 25 ° C, in particular between 1,000 mPa.s and 100,000 mPa.s at 25 ° C, step d) consists in applying to the emulsion (E2) a shear rate less than 1000 s ¹ , and preferably between 10 s ¹ and 1000 s' ¹ . 16. Preparation process according to any one of claims 12 to 15, in which, when the composition C2 comprises a photoinitiator, step e) is a photopolymerization step consisting in exposing the emulsion (E3) to a source of light capable of initiating the photopolymerization of composition C2, in particular to a source of UV light emitting preferably in the wavelength range between 100 nm and 400 nm, and this in particular for a duration of less than 15 minutes. 17. Preparation process according to any one of claims 12 to 15, in which, when the composition C2 does not comprise a photoinitiator, step e) is a polymerization step, without exposure to a light source, the duration of this polymerization step e) preferably being between 8 hours and 100 hours and / or this step e) is carried out at a temperature between 20 ° C. and 80 ° C. 18. Method according to any one of claims 12 to 17, in which the composition C3 and / or C4 further comprises at least one branched polymer, preferably of molecular weight greater than 5000 g.mol ¹ , and / or at minus a polymer with a molecular weight greater than 5,000 g.mol ' ¹ , and / or solid particles such as silicates. 19. A non-therapeutic cosmetic method for reducing skin imperfections, comprising at least one step of applying to the skin a composition according to any one of claims 1 to 11.