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    • 专利摘要:
    The present invention relates to a dispersion containing a dispersed phase comprising drops and a continuous aqueous phase, preferably in the form of a gel, in which the drops comprise a fatty phase containing at least one gelling agent, and in which the fatty phase comprises at least a non-volatile hydrocarbon oil H1 containing more than 90%, preferably more than 95%, of fatty acids having at least 18 carbon atoms, preferably at least 20 carbon atoms.
    公开号:FR3067930A1
    申请号:FR1755907
    申请日:2017-06-27
    公开日:2018-12-28
    发明作者:Amelie Pujol；Helene Balbusquier；Mathieu Goutayer
    申请人:Capsum SAS；
    IPC主号:
    专利说明:

    DISPERSIONS COMPRISING AT LEAST ONE NON-VOLATILE OIL
    HYDROCARBON
    The present invention relates to stable dispersions comprising macroscopic drops of a dispersed fatty phase comprising at least one gelling agent and at least one non-volatile hydrocarbon-based oil. It also relates to compositions, especially cosmetic, containing said dispersions and their uses in the cosmetic field.
    To date, there are dispersions of macroscopic drops of a fatty phase dispersed in an aqueous phase, in particular described in applications WO 2012/120043, FR 2 972 367 and FR 2 976 824. These dispersions are in particular obtained using of a microfluidic process.
    The macroscopic nature of the drops makes it possible to obtain compositions endowed with a differentiating and attractive visual and with an original sensoriality, which constitutes an alternative to the classic classically white emulsions and comprising drops of dispersed phase not visible to the naked eye .
    Dispersions of macroscopic drops of this type, however, exhibit low mechanical resistance, which can lead to shearing or fragmenting of the drops during transport. To overcome this drawback, it is known to implement these dispersions in packaging requiring a specific atmosphere devoid of air (so-called "airless" packaging), which restricts their uses.
    To overcome this problem, application WO 2017/046305 describes the addition in dispersed fatty phase of at least one gelling agent, which makes it possible to obtain stable dispersions having high mechanical strengths, allowing them to resist shearing or fragments of macroscopic drops during transport.
    Nevertheless, a drawback sometimes observed in macroscopic dispersions according to WO 2017/046305 is an opacification of the continuous aqueous phase and / or an adhesion of the drops to each other and / or to the walls of the packaging. This latter phenomenon is more or less exacerbated depending on the nature of the packaging.
    Without wishing to be linked to any theory, the Applicant assumes that the clouding is associated with a leakage of oil (s) and / or gelling agent (s) from the dispersed phase to the continuous aqueous phase.
    For obvious reasons, these drawbacks are not desirable for at least the reasons described below. On the aesthetic level, especially in the cosmetic field, the visual is a very important choice (and therefore purchasing) criterion. In addition, the aforementioned leaks can be accompanied by agglomeration of the drops of phase dispersed therebetween, again having a negative impact on the visual of the dispersion. This leak is likely to cause a leak of encapsulated asset (s), which is detrimental to the integrity of said asset, or even reinforces clouding, and can even lead to undesired reactions with others. active ingredients present in the continuous aqueous phase. Encapsulation has the specific objective of preserving the integrity of the encapsulated active ingredient, or even of using within the same composition active ingredients which are incompatible with each other while providing a differentiating and attractive visual for consumers. Finally, the modification of the drop size distribution and the presence of agglomerates can lead to variable drop densities, and therefore to an inhomogeneous dose distribution.
    There is therefore a need for new dispersions comprising macroscopic drops which do not have the abovementioned drawbacks.
    More generally, the development of dispersions, in particular in the cosmetic field, which are always more stable and aesthetic over time remains a constant objective.
    The present invention therefore aims to provide stable dispersions of macroscopic drops in which the phenomena of opacification of the continuous aqueous phase and / or adhesion of the drops to the walls of the packaging and / or aggregation of the drops therebetween are reduced or even overcome.
    Another object of the invention is to provide a stable dispersion of macroscopic drops making it possible to prevent / prevent the escape of oil (s) and / or gelling agent (s), or even of encapsulated active agent (s). (s), from the dispersed phase to the continuous aqueous phase, thus preserving the integrity of said active agents and / or said drops and therefore the stability over time of said dispersion.
    Thus, the present invention relates to a dispersion containing a dispersed phase comprising drops and a continuous aqueous phase, preferably in the form of a gel, in which the drops comprise a fatty phase containing at least one gelling agent, and in which the fatty phase comprises at least one non-volatile hydrocarbon H1 oil containing more than 90%, preferably more than 95%, of fatty acids having at least 18 carbon atoms, preferably at least 20 carbon atoms.
    The dispersion of the invention has the advantage of being stable, especially over time and during transport. By "stable" is meant, in the sense of the present invention, the absence of creaming or sedimentation of the drops of phase dispersed in the continuous phase, the absence of clouding of the aqueous continuous phase, the absence aggregation of the drops therebetween, and in particular the absence of coalescence or Oswald ripening of the drops between them, and the absence of leakage of materials from the dispersed phase to the continuous phase, or vice versa.
    As is apparent from the examples described below, the use of at least one non-volatile hydrocarbon-based oil as mentioned above in a dispersion according to the invention makes it possible to reduce, or even prevent, the phenomenon of clouding of the continuous aqueous phase, leaks of materials, in particular oil (s) and / or gelling agent (s), from the dispersed phase to the continuous aqueous phase, the adhesion of the drops to the walls of the packaging, and / or the aggregation of the drops together. This preserves, or even improves, the visual and the stability over time of a dispersion according to the invention.
    The drops of the dispersion of the invention are macroscopic drops. Thus, according to one embodiment, at least 60%, or even at least 70%, preferably at least 80%, and better still at least 90%, of the drops have an average diameter greater than or equal to 500 μm, or even greater than or equal at 1000 pm, and better still between 500 pm and 3000 pm, preferably between 1000 pm and 2000 pm, and in particular between 800 pm and 1500 pm.
    In the context of the present invention, the above-mentioned dispersions can be designated either by the term emulsions.
    In addition, the drops advantageously have an apparent monodispersity (ie they are perceived to the eye as identical spheres in diameter). The drops are advantageously substantially spherical.
    Viscosity
    The viscosity of the compositions according to the invention can vary significantly, which therefore makes it possible to obtain various textures.
    According to one embodiment, a dispersion according to the invention has a viscosity of from 1 mPa.s to 500,000 mPa.s, preferably from 10 mPa.s to 300,000 mPa.s, better still from 400 mPa.s to 100 000 mPa.s, and more particularly from 1000 mPa.s to 30 000 mPa.s, as measured at 25 ° C.
    The viscosity is measured at room temperature, for example T = 25 ° C ± 2 ° C and at room pressure, for example 1013 mbar, by the method described in WO2017046305.
    Continuous aqueous phase
    As indicated above, the dispersions according to the invention comprise an aqueous continuous phase, preferably in the form of a gel.
    According to one embodiment, the aqueous phase has a viscosity between 400 mPa.s and 100,000 mPa.s, preferably between 800 mPa.s and 30,000 mPa.s, as measured at 25 ° C.
    This viscosity is measured according to the method described above.
    The continuous phase of dispersions includes water.
    In addition to distilled or deionized water, water suitable for the invention can also be natural spring water or floral water.
    According to one embodiment, the mass percentage of water in the aqueous continuous phase is at least 30%, preferably at least 40%, in particular at least 50%, and better still at least 60 %, especially between 70% and 98%, and preferably between 75% and 95%, relative to the total mass of said continuous phase.
    The aqueous continuous phase of the dispersion according to the invention can also comprise at least one base. It can include a single base or a mixture of several different bases. The presence of at least one base in said aqueous continuous phase contributes in particular to raising the viscosity of the latter.
    According to one embodiment, the base present in the aqueous phase is an inorganic base.
    According to one embodiment, the mineral base is chosen from the group consisting of hydroxides of alkali metals and hydroxides of alkaline earth metals.
    Preferably, the mineral base is an alkali metal hydroxide, and in particular NaOH.
    According to one embodiment, the base present in the aqueous phase is an organic base. Among the organic bases, there may be mentioned, for example, ammonia, pyridine, triethanolamine, aminomethylpropanol, or even triethylamine.
    A dispersion according to the invention can comprise from 0.01% to 10% by weight, preferably from 0.01% to 5% by weight, and preferably from 0.02% to 1% by weight of base, preferably from mineral base, and in particular NaOH, relative to the total weight of said dispersion.
    According to one embodiment, the dispersions according to the invention do not comprise a surfactant.
    Bark of drops
    According to a first embodiment, the drops of a dispersion according to the invention are devoid of bark or of membrane, in particular of polymeric membrane or formed by interfacial polymerization. In particular, the drops of a dispersion according to the invention are not stabilized using a coacervate membrane (anionic polymer (carbomer) / cationic polymer (amodimethicone) type).
    In other words, the contact between the aqueous continuous phase and the dispersed fatty phase is direct.
    According to another embodiment, the drops of the dispersed phase also comprise a bark. Preferably, this shell comprises at least one anionic polymer and at least one cationic polymer.
    According to a preferred embodiment, the drops according to the invention are surrounded by a bark (or membrane) comprising at least one anionic polymer and at least one cationic polymer.
    According to the invention, the drops obtained can have a very thin bark, in particular of thickness less than 1% of the diameter of the drops.
    The thickness of the bark is thus preferably less than 1 μm and is therefore too small to be measured by optical methods.
    According to one embodiment, the thickness of the bark of the drops is less than 1000 nm, in particular between 1 and 500 nm, preferably less than 100 nm, advantageously less than 50 nm, preferably less than 10 nm.
    The measurement of the thickness of the bark of the drops of the invention can be carried out by the small-angle Xray Scattering method, as implemented in Sato et al. J. Chem. Phys. 111, 13931401 (2007).
    For this, the drops are produced using deuterated water, then are washed three times with a deuterated oil, such as for example a deuterated oil of the hydrocarbon type (octane, dodecane, hexadecane).
    After washing, the drops are then transferred to the Neutron cell in order to determine the spectrum l (q); q being the wave vector.
    From this spectrum, classical analytical treatments (REF) are applied in order to determine the thickness of the hydrogenated crust (not deuterated).
    According to one embodiment, the bark surrounding the drops of the dispersed phase is stiffened, which in particular gives good resistance to the drops and reduces, or even prevents, their coalescence.
    This bark is typically formed by coacervation, that is to say by precipitation of polymers charged with opposite charges. Within a coacervate, the bonds binding the charged polymers to each other are of the ionic type, and are generally stronger than the bonds present within a membrane of the surfactant type.
    The bark is formed by coacervation of at least two charged polymers of opposite polarity (or polyelectrolyte) and preferably in the presence of a first polymer, of cationic type, and of a second polymer, different from the first polymer, of type anionic. These two polymers act as stiffening agents for the membrane.
    The formation of the coacervate between these two polymers can be caused by a modification of the conditions of the reaction medium (temperature, pH, concentration of reagents, etc.).
    The coacervation reaction results from the neutralization of these two polymers charged with opposite polarities and allows the formation of a membrane structure by electrostatic interactions between the anionic polymer and the cationic polymer. The membrane thus formed around each drop typically forms a bark which completely encapsulates the heart of the drop, and thus isolates the heart of the drop from the continuous aqueous phase.
    In the presence of a coacervate-like bark, in particular deriving from the use of amodimethicone, the advantageous effects attached to the use of an H1 oil, in particular when the latter is a vegetable oil, are unexpected.
    Indeed, it is known that amodimethicone has a lack of compatibility with vegetable oils, which can lead to poor solubilization of amodimethicone, therefore to an imperfect coacervate membrane quality and therefore to an exacerbated coalescence of the drops. between them. In other words, the present invention goes against a technical prejudice according to which the use of a vegetable oil can be detrimental to the stability of a dispersion stabilized by a coacervate membrane derived from the use using, in particular, amodimethicone. These problems are further exacerbated when we consider a dispersion comprising drops of macroscopic size.
    On the contrary, and as is apparent from the examples below, it is observed that the presence of a coacervate membrane has advantageous effects in terms of reduction of the phenomenon of opacification of the continuous aqueous phase and adhesion of the drops to the packaging walls, or even aggregation of the drops together, despite the use of a vegetable H1 oil.
    Anionic polymer
    In the context of the present description, the term “anionic type polymer” or “anionic polymer” means a polymer comprising chemical functions of anionic type. We can also speak of an anionic polyelectrolyte.
    By anionic chemical function is meant a chemical function AH capable of yielding a proton to give a function A. Depending on the conditions of the medium in which it is found, the anionic type polymer therefore comprises chemical functions in AH form, or well in the form of its conjugate base A.
    As an example of chemical functions of anionic type, mention may be made of the carboxylic acid functions -COOH, optionally present in the form of a carboxylate anion -COO.
    As an example of anionic type polymer, mention may be made of any polymer formed by the polymerization of monomers at least part of which carries anionic type chemical functions, such as carboxylic acid functions. Such monomers are, for example, acrylic acid, maleic acid, or any ethylenically unsaturated monomer comprising at least one carboxylic acid function. It may for example be an anionic polymer comprising monomer units comprising at least one chemical function of the carboxylic acid type.
    Preferably, the anionic polymer is hydrophilic, that is to say soluble or dispersible in water.
    Among the examples of anionic-type polymers suitable for implementing the invention, mention may be made of copolymers of acrylic acid or of maleic acid and of other monomers, such as acrylamide, alkyl acrylates , C 5 -C 8 alkyl acrylates, C 1 -C 30 alkyl acrylates, C 2 -C 22 alkyl methacrylates, methoxypolyethylene glycol methacrylates, hydroxyester acrylates, crosspolymer acrylates , and mixtures thereof.
    According to the invention, a polymer of anionic type is preferably a carbomer as described below. This polymer can also be a crosslinked acrylate / C 10 - 30 alkyl acrylate copolymer (INCI name: acrylates / C 10 - 30 alkyl acrylate Crosspolymer).
    According to one embodiment, the bark of the drops comprises at least one anionic polymer, such as for example a carbomer.
    In the context of the invention, and unless otherwise stated, the term “carbomer” means an optionally crosslinked homopolymer resulting from the polymerization of acrylic acid. It is therefore a poly (acrylic acid) possibly crosslinked. Among the carbomers of the invention, mention may be made of those sold under the names Tego®Carbomer 340FD from Evonik, Carbopol® 981 from Lubrizol, Carbopol ETD 2050 from Lubrizol, or even Carbopol Ultrez 10 from Lubrizol.
    According to one embodiment, the term “carbomer or carbomer or Carbopol®” is understood to mean a polymer of high molecular weight acrylic acid crosslinked with allylic sucrose or allyl ethers of pentaerythritol (handbook of Pharmaceutical Excipients, 5 th Edition, plll). For example, it is Carbopol®910, Carbopol®934, Carbopol®934P, Carbopol®940, Carbopol®941, Carbopol®71G, Carbopol®980, Carbopol®971 P or Carbopol® 974P. According to one embodiment, the viscosity of said carbomer is between 4,000 and 60,000 cP at 0.5% w / w.
    Carbomers have other names: polyacrylic acids, carboxyvinyl polymers or carboxy polyethylenes.
    A dispersion according to the invention can comprise from 0.01% to 5% by weight, preferably from 0.05% to 2%, and preferably from 0.10% to 0.5%, of anionic polymer (s) ( s), in particular of carbomer (s), relative to the total weight of said dispersion.
    According to the invention, the dispersions according to the invention can comprise a carbomer and a crosslinked acrylate / C 10 - 30 alkyl acrylate copolymer.
    The aqueous phase according to the invention can also comprise at least one crosslinked polymer or at least one crosslinked copolymer, said crosslinked polymer or crosslinked copolymer comprising at least one unit derived from the polymerization of one of the following monomers: acrylic or methacrylic acid, acrylate or alkyl methacrylate comprising from 1 to 30 carbon atoms, or their salts.
    This is particularly the case when a dispersion according to the invention comprises at least one perfuming agent as defined below.
    The aqueous phase may also comprise a mixture of crosslinked polymers or a mixture of crosslinked copolymers or else a mixture of crosslinked polymer (s) and of crosslinked copolymer (s).
    According to the invention, the term unit derived from the polymerization of a monomer means that the polymer or copolymer is a polymer or copolymer obtained by polymerization or copolymer of said monomer.
    According to one embodiment, the crosslinked polymer or the crosslinked copolymer is a crosslinked polyacrylate.
    The crosslinked copolymers and polymers of the invention are anionic.
    According to one embodiment, the copolymer is a copolymer of unsaturated carboxylic acid and of unsaturated Cate o, preferably C o-Calk alkyl carboxylate. Such a copolymer comprises at least one hydrophilic unit of olefinic unsaturated carboxylic acid type and at least one hydrophobic unit of (C 1 -C 30 ) alkyl ester type of unsaturated carboxylic acid.
    Preferably, these copolymers are chosen from those in which the hydrophilic unit of olefinic unsaturated carboxylic acid type corresponds to the monomer of formula (I) below: H c = C — C — OH m
    I II U
    FL O in which: Ri denotes H or CH 3 or C 2 H 5 , that is to say acrylic acid, methacrylic acid or ethacrylic acid units, and of which the hydrophobic unit of alkyl ester type (CrCso) d unsaturated carboxylic acid corresponds to the monomer of formula (II) below:
    H „C = C — C — OR„ g <>
    in which: R 2 denotes H or CH 3 or C 2 H 5 (that is to say acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH 3 (methacrylate units), R 3 denoting an alkyl radical in CrCso, and preferably in
    Among this type of copolymers, use will be made more particularly of those formed from a mixture of monomers comprising:
    (i) essentially acrylic acid, (ii) an ester of formula (II) described above and in which R 2 denotes H or CH 3 , R 3 denotes an alkyl radical having from 1 to 4 carbon atoms, (iii) and a crosslinking agent, which is a well known polyethylene copolymerizable unsaturated monomer, such as diallyl phthalate, trimethylolpropane tri (meth) acrylate, diallyl itaconate, diallyl fumarate, diallyl maleate, zinc (meth) acrylate, (meth ) allyl acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate, methylene-bis-acrylamide, and castor oil.
    According to one embodiment, the crosslinked polymer or the crosslinked copolymer is a polymer or copolymer of acrylic acid and / or methacrylic acid, and / or alkyl acrylate comprising from 1 to 30 carbon atoms, preferably from 1 to 4 carbon atoms, and / or from alkyl methacrylate comprising from 1 to 30 carbon atoms, preferably from 1 to 4 carbon atoms.
    According to one embodiment, the crosslinked copolymer is a crosslinked copolymer of methacrylic acid and of alkyl acrylate comprising from 1 to 4 carbon atoms, preferably 2 carbon atoms.
    In the context of the invention, and unless otherwise stated, the expression “crosslinked copolymer of methacrylic acid and of alkyl acrylate comprising from 1 to 4 carbon atoms” means a crosslinked copolymer resulting from the polymerization of a methacrylic acid monomer and an alkyl acrylate monomer comprising from 1 to 4 carbon atoms.
    Preferably, in this copolymer, the methacrylic acid represents from 20% to 80% by weight, preferably from 35% to 65% by weight of the total weight of the copolymer.
    Preferably, in this copolymer, the alkyl acrylate represents from 15% to 80% by weight, preferably from 35% to 65% by weight of the total weight of the copolymer.
    In particular, the alkyl acrylate is chosen from alkyl methacrylate, ethyl acrylate and butyl acrylate.
    According to one embodiment, the crosslinked polymer or the crosslinked copolymer according to the invention, present in the continuous aqueous phase, is chosen from the group consisting of the following polymers or copolymers: Acrylates Copolymer, Acrylates crosspolymer-4, Acrylates crosspolymer-3, Polyacrylate-2 Crosspolymer and Polyacrylate-14 (INCI names).
    Among said polymers above, very particularly preferred, according to the present invention, the products sold by the company LUBRIZOL under the trade names Fixate Superhold (name INCI = Polyacrylate-2 Crosspolymer), Fixate Freestyle Polymer (name INCI = Acrylates crosspolymer- 3), Carbopol® Aqua SF1 (name INCI = Acrylates copolymer) and Carbopol® Aqua SF2 (name INCI = Acrylates crosspolymer-4).
    Preferably, the crosslinked copolymer is Carbopol® Aqua SF1 (INCI name = Acrylates copolymer).
    According to one embodiment, the crosslinked copolymer is chosen from crosslinked copolymers of acrylic or methacrylic acid and of alkyl acrylates comprising from 1 to 4 carbon atoms.
    According to the invention, the dispersion of the invention can comprise from 0.1% to 10% by weight, preferably from 0.5% to 8% by weight, and preferably from 1% to 3% by weight of polymer ( s) crosslinked or crosslinked copolymer (s) relative to the total weight of said dispersion.
    According to the invention, the dispersions according to the invention can comprise a carbomer and a crosslinked copolymer Carbopol® Aqua SF1 (INCI name = Acrylates copolymer).
    Cationic polymer
    According to one embodiment, the drops, and in particular the shell of said drops, further comprise a cationic type polymer. They can also comprise several polymers of cationic type. This cationic polymer is the one mentioned above which forms the shell by coacervation with the anionic polymer.
    In the context of the present application, and unless otherwise stated, the term “cationic polymer” or “cationic polymer” means a polymer comprising chemical functions of cationic type. We can also speak of a cationic polyelectrolyte.
    Preferably, the cationic polymer is lipophilic or liposoluble.
    In the context of the present application, and unless otherwise stated, by chemical function of cationic type, is meant a chemical function B capable of picking up a proton to give a BIT function. Depending on the conditions of the medium in which it is found, the cationic type polymer therefore has chemical functions in B form, or else in BT form, its conjugated acid.
    As an example of chemical functions of cationic type, mention may be made of the primary, secondary and tertiary amine functions, optionally present in the form of ammonium cations.
    As an example of a polymer of cationic type, mention may be made of any polymer formed by the polymerization of monomers at least part of which carries chemical functions of cationic type, such as primary, secondary or tertiary amine functions.
    Such monomers are, for example, aziridine, or any ethylenically unsaturated monomer comprising at least one primary, secondary or tertiary amine function.
    Among the examples of cationic polymers suitable for implementing the invention, there may be mentioned amodimethicone, derived from a silicone polymer (polydimethylsiloxane, also called dimethicone), modified by primary amine and secondary amine functions.
    Mention may also be made of amodimethicone derivatives, such as for example copolymers of amodimethicone, aminopropyl dimethicone, and more generally linear or branched silicone polymers comprising amine functions.
    Mention may be made of the bis-isobutyl PEG-14 / amodimethicone copolymer, the Bis (C13-15 Alkoxy) PG-Amodimethicone, the Bis-Cetearyl Amodimethicone and the bishydroxy / methoxy amodimethicone.
    Mention may also be made of polymers of polysaccharide type comprising amine functions, such as chitosan or guar gum derivatives (hydroxypropyltrimonium guar chloride).
    Mention may also be made of polymers of the polypeptide type comprising amine functions, such as polylysine.
    Mention may also be made of polymers of polyethyleneimine type comprising amine functions, such as linear or branched polyethyleneimine.
    According to one embodiment, the drops, and in particular the shell of said 30 drops, comprise a cationic polymer which is a silicone polymer modified by a primary, secondary or tertiary amine function, such as amodimethicone.
    According to one embodiment, the drops, and in particular the bark of said drops, include amodimethicone.
    According to a particularly preferred embodiment, the cationic polymer corresponds to the following formula:
    NH 2 in which:
    - R 15 R 2 and R 3 , independently of each other, represent OH or CH 3 ;
    - R 4 represents a group -CH 2 - or a group -X-NH- in which X is a divalent alkylene radical in C3 or C4;
    - x is an integer between 10 and 5000, preferably between 30 and 1000, and better still between 80 and 300;
    - y is an integer between 2 and 1000, preferably between 4 and 100, and better still between 5 and 20; and
    - z is an integer between 0 and 10, preferably between 0 and 1, and better is equal to 1.
    In the above formula, when R 4 represents a group -X-NH-, X is linked to the silicon atom.
    In the above formula, Ri, R 2 and R 3 preferably represent CH 3 .
    In the above formula, R 4 is preferably a group - (CH 2 ) 3 -NH-,
    According to the invention, each drop can comprise from 0.01% to 10%, preferably from 0.05% to 5%, by weight of cationic polymer (s), in particular of amodimethicone (s), by relative to the total weight of the fatty phase.
    According to one embodiment, a decrease in the aggregation of the drops is observed between them at levels of cationic polymer (s) lipophilic (s), in particular amodimethicone, of between 0.15% and 0.8% , preferably between 0.25% and 0.6%, by weight relative to the weight of the fatty phase.
    Fat phase
    According to the invention, the dispersions comprise a dispersed fatty phase, in the form of drops, comprising at least one gelling agent.
    Gelling agent
    As indicated above, the present invention is based on the presence, at the dispersed fatty phase, of at least one gelling agent. Such a gelling agent is different from the anionic and cationic polymers described above.
    In the context of the invention, and unless otherwise stated, the term “gelling agent” means an agent making it possible to increase the viscosity of the fatty phase of the drops of the dispersion devoid of said gelling agent, and to reach a final viscosity of the gelled fatty phase greater than 20,000 mPa.s, preferably greater than 50,000 mPa.s, better still greater than 100,000 mPa.s, and very particularly greater than 200,000 mPa.s.
    Preferably, the viscosity of the fatty phase of the drops of the dispersion in the presence of said gelling agent is between 20,000 and 100,000,000 mPa.s, preferably between 50,000 and 1,000,000 mPa.s, and better still between 100,000 at 500,000 mPa.s, at 25 ° C.
    The choice of gelling agent (s) is made in particular with regard to the nature of the dispersed phase. Thus, for obvious compatibility reasons, the gelling agent is lipophilic.
    According to one embodiment, the gelling agent is chosen from organic or mineral, polymeric or molecular lipophilic gelling agents; solid fatty substances at room temperature and pressure; and their mixtures, in particular chosen from waxes, pasty fatty substances, butters, and their mixtures.
    Lipophilic gelling agent (s)
    The gelling agents which can be used according to the invention can be organic or mineral, polymeric or molecular lipophilic gelling agents.
    As mineral lipophilic gelling agent, mention may be made of clays which may be modified, such as hectorites modified with C 10 -C 22 ammonium chloride, such as hectorite modified with di-stearyl di-methyl ammonium chloride, such as, for example. , that marketed under the name of Bentone 38V® by the company ELEMENTIS. Mention may also be made of hectorite modified with distearyldimethylammonium chloride, also known as quaternium-18 bentonite, such as the products sold or manufactured under the names Bentone 34 by the company Rheox, Claytone XL, Claytone 34 and Claytone 40 sold or manufactured by the company Southern Clay, the modified clays known under the name of benzalkonium and quaternium-18 bentonites and marketed or manufactured under the names Claytone HT, Claytone GR and Claytone PS by the company Southern Clay, clays modified with chloride of stearyldimethylbenzoylammonium, known as steralkonium bentonites, such as the products marketed or manufactured under the names Claytone APA and Claytone AF by the company Southern Clay, and Baragel 24 marketed or manufactured by the company Rheox.
    Mention may also be made of fumed silica optionally hydrophobically treated at the surface, the particle size of which is less than 1 μm. It is indeed possible to chemically modify the surface of the silica, by chemical reaction generating a reduction in the number of silanol groups present on the surface of the silica. Silanol groups can in particular be substituted by hydrophobic groups: a hydrophobic silica is then obtained.
    The hydrophobic groups can be:
    - Trimethylsiloxyl groups, which are obtained in particular by treatment of fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are called "Silica silylate" according to the CTFA (8 th edition, 2000). They are for example marketed under the Aerosil R812® references by the company DEGUSSA, CAB-O-SIL TS-530® by the company CABOT; or
    - Dimethylsilyloxyl or polydimethylsiloxane groups, which are in particular obtained by treatment of fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are called “Silica dimethyl silylate” according to the CTFA (8 th edition, 2000). They are for example marketed under the references Aerosil R972®, and Aerosil R974® by the company DEGUSSA, CAB-O-SIL TS-610® and CAB-O-SIL TS-720® by the company CABOT.
    Hydrophobic fumed silica in particular has a particle size which can be nanometric to micrometric, for example ranging from around 5 to 200 nm.
    The polymeric organic lipophilic gelling agents are, for example partially or totally crosslinked elastomeric organopolysiloxanes, of three-dimensional structure, such as those sold under the names KSG6®, KSG16® and KSG18® by the company SHIN-ETSU, Trefil E-505C® and Trefil E-506C® by the company DOW-CORNING, by Gransil SR-CYC®, SR DMF10®, SR-DC556®, SR 5CYC gel®, SR DMF 10 gel® and SR DC 556 gel® by the company GRANT INDUSTRIES , SF 1204® and JK 113® by GENERAL
    ELECTRIC; ethylcellulose such as that sold under the name Ethocel® by the company DOW CHEMICAL; galactommananes comprising from one to six, and in particular from two to four, hydroxyl groups by dare, substituted by a saturated or unsaturated alkyl chain, such as guar gum alkylated by Ct to C 6 alkyl chains, and in particular by to C 3 and their mixtures. Block copolymers of the “diblock”, “triblock” or “radial” type of the polystyrene / polyisoprene, polystyrene / polybutadiene type such as those marketed under the name Luvitol HSB® by the company BASF, of the polystyrene / copoly type (ethylene- propylene) such as those marketed under the name Kraton® by the company SHELL CHEMICAL CO or else of the polystyrene / copoly (ethylene-butylene) type, mixtures of triblock and radial (star) copolymers in isododecane such as those marketed by the company PENRECO under the name Versagel® such as for example the mixture of triblock butylene / ethylene / styrene copolymer and of ethylene / propylene / styrene star copolymer in isododecane (Versagel M 5960).
    According to one embodiment, the gelling agents which can be used according to the invention can be chosen from the group consisting of polyacrylates; esters of sugar / polysaccharide and fatty acid (s), in particular esters of dextrin and fatty acid (s), esters of glycerol and fatty acid (s) or esters of inulin and d 'Fatty acids ; polyamides, and their mixtures.
    As lipophilic gelling agent, mention may also be made of polymers with an average molecular weight of less than 100,000, comprising a) a polymer backbone having hydrocarbon repeating units provided with at least one heteroatom, and optionally b) at least one fatty chain pendant and / or at least one terminal fatty chain optionally functionalized, having from 6 to 120 carbon atoms and being linked to these hydrocarbon-based units, as described in applications WO 02/056847, WO 02/47619, in particular the resins of polyamides (in particular comprising alkyl groups having from 12 to 22 carbon atoms) such as those described in US 5783657.
    As an example of a polyamide resin which can be used according to the present invention, there may be mentioned UNICLEAR 100 VG® sold by the company ARIZONA CHEMICAL.
    It is also possible to use silicone polyamides of the polyorganosiloxane type such as those described in US 5,874,069, US 5,919,441, US 6,051,216 and US 5,981,680.
    These silicone polymers can belong to the following two families:
    polyorganosiloxanes comprising at least two groups capable of establishing hydrogen interactions, these two groups being located in the polymer chain, and / or
    - polyorganosiloxanes comprising at least two groups capable of establishing hydrogen interactions, these two groups being located on grafts or branches.
    Among the lipophilic gelling agents which can be used in the present invention, mention may also be made of dextrin and fatty acid esters, such as dextrin palmitates.
    According to one embodiment, the ester of dextrin and of fatty acid (s) according to the invention is a mono- or poly-ester of dextrin and of at least one fatty acid corresponding to the following formula (II):
    OR l 4
    O (II) in which:
    ο n is an integer ranging from 2 to 200, preferably ranging from 20 to 150, and in particular ranging from 25 to 50, o the radicals R 4 , R5 and R 6 , identical or different, are chosen from hydrogen or an acyl group -COR a in which the radical R a represents a hydrocarbon radical, linear or branched, saturated or unsaturated, having from 5 to 50, preferably from 5 to 25 carbon atoms, provided that at least one of said radicals R 4 , R 5 or R 6 is different from hydrogen.
    According to one embodiment, R 4j R 5 and R 6 represent, independently of each other, H or an acyl group -COR a in which R a is a hydrocarbon radical as defined above, provided that at least two of said radicals R 4j R 5 or R 6 are identical and different from hydrogen.
    According to one embodiment, when the radicals R 4j R 5 and R 6 , which are identical or different, represent a radical -COR a , these can be chosen from the radicals caprylyl, caproyl, lauroyl, myristyle, palmityl, stearyl, eicosanyl , docosanoyl, isovaleryl, 2-ethyl butyryl, éthylméthylacétyle, isoheptanyle, 2-ethyl hexanyl, isononanyle, isodécanyle, isotridécanyle, isomyristyle, isopalmityle, isostearyl isohexanyle, decenyl, dodecenyl, tetradecenyl, myristyl, hexadécénoyle, palmitoleyl, oleyl, élaidyle, eicosenyl , sorbyle, linoleyle, linolenén, punicyle, arachidonyle, stéarolyle, and their mixtures.
    Among the esters of dextrin and of fatty acid (s), mention may, for example, be made of dextrin palmitates, dextrin myristates, dextrin palmitates / ethylhexanoates and their mixtures.
    Mention may in particular be made of the esters of dextrin and of fatty acid (s) marketed under the names Rheopearl® KL2 (INCI name: dextrin palmitate), Rheopearl® TT2 (INCI name: dextrin palmitate ethylhexanoate), and
    Rheopearl® MKL2 (INCI name: dextrin myristate) by the company Miyoshi Europe.
    Mention may in particular be made of the esters of inulin and of fatty acid (s) sold under the names Rheopearl® ISK2 or Rheopearl® ISL2 (INCI name: Stearoyl Inulin) by the company Miyoshi Europe.
    According to one embodiment, the gelling agent is chosen from the 15 polyacrylates resulting from the polymerization of C 10 -C 30 alkyl acrylate (s), preferably C 14 alkyl acrylate (s) -C 2 4, and even more preferably of C1 8 -C 22 alkyl acrylate (s).
    According to one embodiment, the polyacrylates are polymers of acrylic acid esterified with a fatty alcohol whose saturated carbon chain comprises from 10 to 30 carbon atoms, preferably from 14 to 24 carbon atoms, or a mixture of said fatty alcohols . Preferably, the fatty alcohol comprises 18 carbon atoms or 22 carbon atoms.
    Among the polyacrylates, mention may be made more particularly of stearyl polyacrylate, behenyl polyacrylate. Preferably, the gelling agent is stearyl polyacrylate or behenyl polyacrylate.
    Mention may in particular be made of the polyacrylates sold under the names Interlimer® (INCI name: Poly C 10 -C 30 alkyl acrylate), in particular Interlimer® 13.1 and Interlimer® 13.6, by the company Airproducts.
    According to one embodiment, the gelling agent is an ester of glycerol and fatty acid (s), in particular a mono-, di- or triester of glycerol and fatty acid (s).
    Typically, said glycerol ester and fatty acid (s) can be used alone or as a mixture.
    According to the invention, it may be a glycerol ester and a fatty acid or a glycerol ester and a mixture of fatty acids.
    According to one embodiment, the fatty acid is chosen from the group consisting of behenic acid, isooctadecanoic acid, stearic acid, eicosanoic acid, and their mixtures.
    According to one embodiment, the glycerol ester and fatty acid (s) has the following formula (III):
    (NI) in which: R 1; R 2 and R 3 are, independently of one another, chosen from H and a saturated alkyl chain comprising from 4 to 30 carbon atoms, at least one of FL, R 2 and R 3 being different from H.
    According to one embodiment, R 1; R 2 and R 3 are different.
    According to one embodiment, R 1; R 2 and / or R 3 represents a saturated alkyl chain comprising from 4 to 30, preferably from 12 to 22, and preferably from 18 to 22 carbon atoms.
    According to one embodiment, the glycerol ester and fatty acid (s) corresponds to a compound of formula (III) in which Ri = H, R 2 = C 2 iH 43 and R 3 = Ci 9 H 40 .
    According to one embodiment, the glycerol ester and fatty acid (s) corresponds to a compound of formula (III) in which Ri = R 2 = R 3 = C 2 iH 43 .
    According to one embodiment, the ester of glycerol and of fatty acid (s) corresponds to a compound of formula (III) in which Ri = R 2 = H, and R 3 = Ci 9 H 40 .
    According to one embodiment, the glycerol ester and fatty acid (s) corresponds to a compound of formula (III) in which R 1 = R 2 = H, and R 3 = Ci 7 H 35 .
    Mention may in particular be made of the glycerol and fatty acid esters sold under the names Nomcort HK-G (INCI name: Glyceryl behenate / eicosadioate) and Nomcort SG (INCI name: Glyceryl tribehenate, isostearate, eicosadioate) Nisshin Oillio company.
    Raincoats)
    By “wax” is meant within the meaning of the invention, a lipophilic compound, solid at room temperature (25 ° C), with change of sdide / reversible liquid state, having a melting point greater than or equal to 30 ° It can go up to 120 ° C.
    The protocol for measuring this melting point is described below.
    The waxes capable of being used in a composition according to the invention can be chosen from waxes, solid, deformable or not at room temperature, of animal, vegetable, mineral or synthetic origin and their mixtures.
    It is possible in particular to use hydrocarbon waxes such as beeswax, lanolin wax, and Chinese insect waxes; rice wax, Carnauba wax, Candellila wax, Ouricurry wax, Alfa wax, cork fiber wax, sugar cane wax, Japanese wax and sumac wax ; montan wax, microcrystalline waxes, paraffins and ozokerite; polyethylene waxes, waxes obtained by the Fisher-Tropsch synthesis and waxy copolymers and their esters.
    Mention may in particular be made of the waxes marketed under the names Kahlwax®2039 (INCI name: Candelilla cera) and Kahlwax®6607 (INCI name: Helianthus Annuus Seed Wax) by the company Kahl Wachsraffinerie, Casid HSA (INCI name: Hydroxystearic Acid) SACI CFPA, Performa®260 (INCI name: Synthetic wax) and Performa®103 (INCI name: Synthetic wax) by New Phase, and AJK-CE2046 (INCI name: Cetearyl alcohol, dibutyl lauroyl glutamide, dibutyl ethylhaxanoyl glutamide) by the company Kokyu Alcohol Kogyo.
    Mention may also be made of the waxes obtained by catalytic hydrogenation of animal or vegetable oils having fatty chains, linear or branched, of C 8 -C 32 .
    Among these, mention may in particular be made of hydrogenated jojoba oil, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil and hydrogenated lanolin oil, di- tetrastearate trimethylol-1,1,1 propane) sold under the name "HEST 2T-4S" by the company HETERENE, di- (trimethylol-1,1,1 propane) tetrabehenate sold under the name HEST 2T-4B by the HETERENE company.
    It is also possible to use the waxes obtained by transesterification and hydrogenation of vegetable oils, such as castor oil or olive oil, such as the waxes sold under the names of Phytowax ricin 16L64® and 22L73® and Phytowax Olive 18L57 by the company Sophim. Such waxes are described in application FR2792190.
    It is also possible to use silicone waxes which can advantageously be substituted polysiloxanes, preferably with a low melting point.
    Among the commercial silicone waxes of this type, there may be mentioned in particular those sold under the names Abilwax 9800, 9801 or 9810 (GOLDSCHMIDT), KF910 and KF7002 (SHIN ETSU), or 176-1118-3 and 176-11481 (GENERAL ELECTRIC ).
    The silicone waxes which can be used can also be alkyl or alkoxydimethicones such as the following commercial products: Abilwax 2428, 2434 and 2440 (GOLDSCHMIDT), or VP 1622 and VP 1621 (WACKER), as well as (C 2 oC 6 o) alkyldimethicones , in particular (C 30 -C 4 5) alkyldimethicones such as silicone wax sold under the name SF-1642 by the company GE-Bayer Silicones.
    It is also possible to use hydrocarbon waxes modified with silicone or fluorinated groups such as for example: siliconyl candelilla, siliconyl beeswax and Fluorobeeswax from Koster Keunen.
    The waxes can also be chosen from fluorinated waxes.
    Butter (s) or pasty fatty substances
    By “butter” (also called “pasty fatty substance”) within the meaning of the present invention, is meant a lipophilic fatty compound with reversible solid / liquid state change and comprising at the temperature of 25 ° C. a liquid fraction and a fraction solid, and at atmospheric pressure (760 mm Hg). In other words, the starting melting temperature of the pasty compound can be less than 25 ° C. The liquid fraction of the pasty compound measured at 25 ° C can represent from 9% to 97% by weight of the compound. This liquid fraction at 25 ° C preferably represents between 15% and 85%, more preferably between 40 and 85% by weight. Preferably, the butter or butter has a melting temperature below 60 ° C. Preferably, the butter or butter has a hardness of 6 MPa or less.
    Preferably, the pasty butters or fatty substances have an anisotropic crystalline organization in the solid state, visible by X-ray observations.
    Within the meaning of the invention, the melting point corresponds to the temperature of the most endothermic peak observed in thermal analysis (DSC) as described in standard ISO 11357-3; 1999. The melting point of a pasty or a wax can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name DSC Q2000 by the company TA Instruments.
    Concerning the measurement of the melting temperature and the determination of the end of melting temperature, the protocols for preparing the samples and for measuring are as described in WO2017046305.
    The liquid fraction by weight of the butter (or pasty fatty substance) at 25 ° C is equal to the ratio of the enthalpy of fusion consumed at 25 ° C to the enthalpy of fusion of the butter. The enthalpy of fusion of the butter or pasty compound is the enthalpy consumed by the compound to pass from the solid state to the liquid state.
    Butter is said to be in the solid state when all of its mass is in crystalline solid form. Butter is said to be in a liquid state when all of its mass is in liquid form. The enthalpy of fusion of the butter is equal to the integral of the whole of the melting curve obtained using the above-mentioned calorimeter, with a rise in temperature of 5 ° C. or 10 ° C. per minute, according to the standard. ISO 113573: 1999. The enthalpy of fusion of butter is the amount of energy required to move the compound from the solid state to the liquid state. It is expressed in J / g.
    The enthalpy of fusion consumed at 25 ° C is the amount of energy absorbed by the sample to pass from the solid state to the state it presents at 25 ° C consisting of a liquid fraction and a solid fraction. The liquid fraction of the butter measured at 32 ° C. preferably represents from 30% to 100% in pots of the compound, preferably from 50% to 100%, more preferably from 60% to 100% by weight of the compound. When the liquid fraction of the butter measured at 32 ° C is equal to 100%, the temperature at the end of the melting range of the pasty compound is less than or equal to 32 ° C. The liquid fraction of butter measured at 32 ° C is equal to the ratio of the enthalpy of fusion consumed at 32 ° C on the entha | 3ie of butter melting. The enthalpy of fusion consumed at 32 ° C is calculated in the same way as the enthalpy of fusion consumed at 23 ° C.
    Regarding the hardness measurement, the sample preparation and measurement protocols are as described in WO2017046305.
    The pasty fatty substance or butter can be chosen from synthetic compounds and compounds of plant origin. A pasty fatty substance can be obtained by synthesis from starting materials of plant origin.
    The pasty fatty substance is advantageously chosen from:
    lanolin and its derivatives such as lanolin alcohol, oxyethylenated lanolines, acetylated lanolin, lanolin esters such as isopropyl lanolate, oxypropylenated lanolines,
    - polymeric or non-polymeric silicone compounds such as polydimethysiloxanes of high molecular weights, polydimethysiloxanes with side chains of the alkyl or alkoxy type having from 8 to 24 carbon atoms, in particular stearyl dimethicones,
    - polymeric or non-polymeric fluorinated compounds,
    - vinyl polymers, in particular
    - homopolymers of olefins,
    - olefin copolymers,
    - homopolymers and copolymers of hydrogenated dienes,
    - linear or branched oligomers, homo or copolymers of alkyl (meth) acrylates preferably having a C 8 -C 30 alkyl group,
    - homo oligomers and copolymers of vinyl esters having C 8 -C 30 alkyl groups,
    - homo oligomers and copolymers of vinyl ethers having C 8 -C 30 alkyl groups,
    - the liposoluble polyethers resulting from the polyetherification between one or more C 2 -C 100 , preferably C 2 -C 50 , diols,
    - esters and polyesters, and
    - their mixtures.
    According to a preferred embodiment of the invention, the particular butters are of vegetable origin such as those described in Ullmann's Encyclopedia of Industrial Chemistry ("Fats and Fatty Oils", A. Thomas, published on 06/15/2000, D01 : 10.1002 / 14356007.a10_173, point 13.2.2.2. Shea Butter, Borneo Tallow, and Related Fats (Vegetable Butters)).
    Mention may more particularly be made of C10-C18 triglycerides (INCI name: C10-18 Triglycerides) comprising at the temperature of 25 ° C and at atmospheric pressure (760 mm Hg) a liquid fraction and a solid fraction, shea butter, Nilotica shea butter (Butyrospermum parkii), Galam butter, (Butyrospermum parkii), Borneo or tengkawang tallow butter or fat (Shorea stenoptera), Shorea butter, Illipé butter, Madhuca or Bassia Madhuca butter longifolia, mowrah butter (Madhuca Latifolia), Katiau butter (Madhuca mottleyana), Phulwara butter (M. butyracea), mango butter (Mangifera indica), Murumuru butter (Astrocatyum murumuru), Kokum butter (Garcinia Indica), Ucuuba butter (Virola sebifera), Tucuma butter, Painya butter (Kpangnan) (Pentadesma butyracea), coffee butter (Coffea arabica), apricot butter (Prunus Armeniaca) , Macadamia butter (Macadamia Temifolia), pe butter grape pine (Vitis vinifera), avocado butter (Persea gratissima), olive butter (Olea europaea), sweet almond butter (Prunus amygdalus dulcis), cocoa butter (Theobroma cocoa) and sunflower butter, the butter under the name INCI Astrocaryum Murumuru Seed Butter, the butter under the name INCI Theobroma Grandiflorum Seed Butter, and the butter under the name INCI Irvingia Gabonensis Kernel Butter, the esters of jojoba (mixture of wax and oil hydrogenated jojoba) (INCI name: Jojoba esters) and shea butter ethyl esters (INCI name: Shea butter ethyl esters), and mixtures thereof.
    Among the gelling agents according to the invention, there may also be mentioned THIXCIN® R from Elementis Specialties (INCI: Trihydroxystearin) or Estogel E from PolymerExpert (Proposed INCI name: Castor oil / IPDI Copolymer, Caprylic Capric triglyceride, Castor oil).
    Preferably, the gelling agent is chosen from dextrin palmitates.
    Advantageously, a fatty phase gelling agent according to the invention is a thermosensitive gelling agent, ie one which reacts to heat, and in particular is a gelling agent which is solid at room temperature and liquid at a temperature above 40 ° C., preferably higher. at 50 ° C.
    Advantageously, a fatty phase gelling agent according to the invention is a thixotropic gelling agent or capable of imparting to the solution which comprises it a thixotropic behavior. Such a thixotropic gelling agent is chosen in particular from fumed silicas optionally treated with hydrophobicity, described above.
    According to one embodiment, a dispersion according to the invention can comprise from 0.1% to 75%, preferably from 0.5% to 60%, in particular from 1% to 40%, better still from 1.5% to 20%, and preferably from 1% to 4%, by weight of gelling agent (s) relative to the total weight of the dispersion.
    According to the invention, a dispersion according to the invention can comprise from 0.5% to 99%, preferably from 1% to 70%, in particular from 1.5% to 50%, better still from 2% to 40%, in particular from 2.5% to 30%, and preferably from 10% to 20%, by weight of gelling agent (s) relative to the total weight of the fatty phase.
    As is apparent from the examples below, an increase in the content of gelling agent (s), in particular in RHEOPEARL KL2, contributes to further reducing the phenomenon of aggregation of the drops together.
    Oils
    H1 oil
    A dispersion according to the invention requires the use in the fatty phase of at least one non-volatile hydrocarbon oil H1 containing more than 90%, preferably more than 95%, of fatty acids with chain length greater than or equal to 18 carbon atoms, preferably greater than or equal to 20 carbon atoms.
    Preferably, more than 90%, and preferably more than 95%, of the fatty acids of the non-volatile hydrocarbon oil have a chain length of between C 8 and C 36 , preferably between C 20 and C 28 , and better between C 20 and C 22 .
    “Oil” means a fatty substance which is liquid at room temperature (25 ° C).
    The fatty acid chains of the non-volatile hydrocarbon oil H1 are linear or branched, preferably linear, and saturated or unsaturated, preferably unsaturated, even polyunsaturated.
    The term “unsaturated fatty acid” within the meaning of the present invention means a fatty acid comprising at least one double bond. They are more particularly fatty acids with long chains, that is to say having at least 18, preferably 20, carbon atoms. The unsaturated fatty acids can be in acid form, or in the form of a salt, such as for example their calcium salt, or also in the form of derivatives, in particular of fatty acid ester (s).
    By "non-volatile" is meant an oil whose vapor pressure at room temperature and atmospheric pressure is not zero and less than 0.02 mm Hg (2.66 Pa) and better still less than 10-3 mm from Hg (0.13 Pa).
    Particularly suitable for the invention are unsaturated fatty acids comprising from 18 to 36, preferably from 20 to 28, and better still from 20 to 22, carbon atoms, in particular unsaturated or even polyunsaturated fatty acids, in particular Δ fatty acids -5 and / or Δ-13.
    Among the unsaturated fatty acids of the Δ-5 series, there may be mentioned in particular monounsaturated eicosenoic acid with 20 carbon atoms and an unsaturation (20: 1, Δ-5), monosaturated docosanoic acid with 22 carbon atoms and one unsaturation (22: 1, Δ-5) and docosadienoic acid polyunsaturated with 22 carbon atoms and two unsaturations (22: 2, Δ 5).
    Among the unsaturated fatty acids of the Δ-13 series, there may be mentioned docosanoic acid monounsaturated with 22 carbon atoms and an unsaturation (22: 1, Δ13).
    For the purposes of the invention, the nomenclature "Δχ >> (or" delta-x >>) relates to unsaturated fatty acids, for which each double bond is indicated by the sign Δ and followed by the position of the double bond along of the fatty acid aliphatic chain from the carboxylic end -COOH of the molecule.
    Preferably, a non-volatile hydrocarbon oil according to the invention comprises a mixture of monounsaturated and polyunsaturated fatty acids.
    Preferably, a non-volatile hydrocarbon oil according to the invention comprises more than 90%, and preferably more than 95%, of fatty acids chosen from oleic acid, in particular of the type (C18: 1, Δ-9) , eicosenoic acid, in particular of the type (C20: 1, Δ-5), docosanoic acid, in particular of the type (C22: 1, Δ-5) and / or (C22: 1, Δ-13) , docosadienoic acid, in particular of the (C22: 2, Δ 5) type, and their mixtures, and better still eicosenoic acid, docosanoic acid and / or docosadienoic acid, and their mixtures.
    Preferably, the non-volatile hydrocarbon oil H1 is chosen from vegetable oils. According to one embodiment, the dispersion of the invention comprises several H1 oils, at least one of which is a vegetable oil. According to one embodiment, the dispersion of the invention comprises several H1 oils chosen from vegetable oils.
    Preferably, the non-volatile hydrocarbon oil H1 comprises less than 10%, preferably less than 5%, or even is devoid of fatty acid having a chain length of less than 18 carbon atoms, and better still less than 20 carbon atoms. carbon.
    Preferably, the non-volatile hydrocarbon oil H1 comprises less than 10%, preferably less than 5%, or even is devoid of saturated fatty acid.
    Thus, as non-volatile hydrocarbon oils H1 according to the invention, mention may be made of jojoba oil, linseed oil, Perilla oil, Inca Inchi oil, rosehip oil , rapeseed oil, hemp oil, sweet almond oil, corn oil, apricot oil, castor oil, Meadowfoam oil (INCI: Limnanthes Alba (Meadowfoam) Seed Oil) and their mixtures, preferably jojoba oil and / or Meadowfoam oil, and better still Meadowfoam oil.
    Meadowfoam oil has a particular fatty acid composition, as described in the table below:
    Composition infatty acid Composition(in %) General formula C 20: 1 Δ-5 58-64 H n) C 22: 1 AT 5 3-6 13-20 Q:-U) C 22: 1 Δ-13 10-14 „Υ l · '. . 9 ”) C 2) 2: 2 Δ-SetΔ-13 15-21 oh Total 100
    Meadowfoam oil is for example sold by the company Nikon
    Chemicals under the name NIKKOL Meadowfoam Oil or by the company
    Elementis Specialties under the name FANCOR® MEADOWFOAM SEED
    OIL.
    The use of non-volatile H1 hydrocarbon oils, in particular vegetable oils, and in particular Meadowfoam oil, in compositions, in particular cosmetic compositions, is known. However, it has never been observed that their use in a dispersed fatty phase of macroscopic drops can have advantageous effects in terms of reduction of opacification of the continuous aqueous phase and / or adhesion of the drops to the walls. packaging and / or aggregation of the drops therebetween.
    Advantageously, the fatty phase of a dispersion according to the invention comprises between 1% and 50%, preferably between 5% and 40%, in particular between 10% and 30%, and better still between 15% and 20%, by weight. of oil (s) H1 relative to the total weight of said fatty phase.
    H2 oil
    According to one embodiment, the fatty phase of the dispersion according to the invention also comprises at least one H2 oil, different from the above-mentioned H1 oil.
    The presence of an H2 oil can be advantageous for giving the dispersion according to the invention a different sensorality or ensuring the use of a particular raw material, for example not soluble in an H1 oil. This is particularly the case where the oil H1 is a vegetable oil and the macroscopic drops of the dispersion according to the invention comprise a rind, in particular deriving from the use of amodimethicone. Indeed, as mentioned above, amodimethicone has a lack of compatibility with vegetable oils. H2 oil is therefore preferably an oil in which the cationic polymer is soluble. The H2 oil is therefore advantageously compatible with the cationic polymer and therefore corresponds to a good solvent for the cationic polymer.
    As H2 oils which can be used in the composition of the invention, there may be mentioned for example:
    - hydrocarbon oils of animal origin, such as perhydrosqualene and squalane;
    - synthetic esters and ethers, in particular of fatty acids, such as oils of formulas R1COOR2 and RiOR 2 in which Ri represents the remainder of a fatty acid Cg to C 2 g, and R 2 represents a hydrocarbon chain, branched or not, C 3 to C 30 , such as, for example, Purcellin oil, isononyl isononanoate, isodecyl neopentanoate, isopropyl myristate, ethyl-2-hexyl palmitate, octyl-2-dodecyl stearate, octyl-2-dodecyl erucate, isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octylhydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, heptanoates, octanoates, decanoates of fatty alcohols; polyol esters, such as propylene glycol dioctanoate, neopentylglycol diheptanoate and diethylene glycol diisononanoate; and pentaerythritol esters such as pentaerythrityl tetrabehenate (DUB PTB) or pentaerythrityl tetraisostearate (Prisorin 3631);
    - linear or branched hydrocarbons, of mineral or synthetic origin, such as paraffin oils, volatile or not, and their derivatives, petrolatum, polydecenes, hydrogenated polyisobutene such as Parléam oil;
    - silicone oils, such as, for example, volatile or non-volatile polymethylsiloxanes (PDMS) with a linear or cyclic silicone chain, liquid or pasty at room temperature, in particular cyclopolydimethylsiloxanes (cyclomethicones) such as cyclohexasiloxane and cyclopentasiloxane; polydimethylsiloxanes (or dimethicones) comprising alkyl, alkoxy or phenyl groups, during or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenylated silicones such as phenyltrimethicones, phenyldimethicones, phenyltrimethylsiloxydiphenyl-siloxanes, diphenyldimethicones, diphenylmethyldiphenyl trisiloxanes, 2-phenylethyltrimethylsiloxysilicates, and polymethylphenyls;
    - fatty alcohols having from 8 to 26 carbon atoms, such as cetyl alcohol, stearyl alcohol and their mixture (cetylstearyl alcohol), or octyldodecanol;
    - partially hydrocarbon and / or silicone fluorinated oils such as those described in document JP-A-2-295912;
    - and their mixtures.
    According to a preferred embodiment, the fatty phase of the dispersion according to the invention comprises a mixture between at least one H1 oil and at least one H2 oil, different from the above-mentioned H1 oil.
    According to one embodiment, the mass ratio between the amount of oil (s)
    H1 and the quantity of oil (s) H2 ranges from 0.01 to 1, preferably from 0.05 to 0.66, in particular from 0.1 to 0.43, and better still from 0.17 to 0, 25.
    A dispersion according to the invention can comprise from 0.0001% to 50%, preferably from 0.1% to 40%, and better still from 1% to 25%, by weight of oil (s) H1 and H2 relative to the total weight of said composition.
    According to one embodiment, the fatty phase comprises at least one H1 oil, or even an H2 oil, having a refractive index close to that of the gelling agent (s), in order to improve the transparency of the phase fatty considered, and therefore the transparency of the dispersion according to the invention. In particular, when the fatty phase of a dispersion according to the invention also comprises at least one gelling agent chosen from esters of sugar or polysaccharide and fatty acid (s), in particular dextrin and acid ( s) fatty, and very particularly chosen from the group consisting of dextrin palmitates, dextrin myristates, dextrin palmitates / ethylhexanoates, and their mixtures, the oil H1 and optionally the oil H2 has (s) an index of refraction close to that of the gelling agent (s), namely an oil having a refractive index, at room temperature (25 ° C.) and atmospheric pressure, between 1.2 and 1.8, of preferably between 1.3 and 1.7, in particular between 1.4 and 1.6, and better still between 1.45 and 1.55.
    Advantageously, the H1 oil having a refractive index of between 1.2 and 1.8 is Meadowfoam oil.
    Advantageously, the oil H2 having a refractive index of between 1.2 and 1.8 is a silicone oil, in particular a phenylated silicone oil, for example diphenylsiloxyphenyltrimethicone oil such as KF-56 A from Shin Etsu ( INCI Name: Diphenylsiloxy Phenyl Trimethicone). One such H2 oil can also be LexFeel® Shine oil from INOLEX (INCI Name: Propylene Glycol Dibenzoate).
    Additional compound (s)
    According to the invention, the aqueous continuous phase and / or the dispersed fatty phase may / may also comprise at least one additional compound different from the anionic and cationic polymers, the gelling agent and the abovementioned oils.
    The dispersions according to the invention can thus also comprise powders; Glitter ; coloring agents, in particular chosen from coloring agents which are water-soluble or not, liposoluble or not, organic or inorganic, materials with an optical effect, liquid crystals, and mixtures thereof; particulate agents insoluble in the fatty phase; preservatives; humectants; stabilizers; chelators; emollients; modifiers chosen from texturing agents, viscosity agents (for example gelling agents / texturing agents of aqueous phase different from the above-mentioned base), pH, osmotic force and / or modifiers of refractive index, etc. or any usual cosmetic additive; and their mixtures.
    According to one embodiment, the particulate agents insoluble in the fatty phase of the drops are chosen from the group consisting of pigments, ceramics, polymers, in particular acrylic polymers, and their mixtures.
    The dispersions according to the invention can also further comprise at least one biological / cosmetic active agent chosen from hydrating agents, healing agents, depigmenting agents, UV filters, desquamating agents, antioxidant agents, active agents stimulating the synthesis of dermal and / or epidermal macromoleculars, dermodecontracting agents, antiperspirant agents, soothing agents and / or anti-aging agents, and mixtures thereof.
    According to one embodiment, the dispersion according to the invention comprises from 0.00020% to 10%, preferably from 0.00025% to 5%, and preferably from 0.0026% to 1% by weight of agent (s ) dye (s), and in particular dye (s), relative to the total weight of said dispersion.
    Among the preservatives, mention may in particular be made of phenoxyethanol, pentylene glycol and EDTA.
    According to one embodiment, the dispersions according to the invention comprise at least one preservative, and preferably a mixture of several preservatives.
    Preferably, the content by weight of preservative (s) is between 0.01% to 10%, preferably from 0.5% to 5%, relative to the total weight of said dispersion.
    According to the invention, a dispersion according to the invention, and in particular the core of the drops (i.e. the fatty phase), can also comprise at least one perfuming agent, in particular as defined in WO2016096995.
    The dispersion according to the invention may comprise from 0.01% to 30% by weight of perfuming agent (s), preferably from 0.5% to 20% by weight, relative to the total weight of the dispersion .
    According to one embodiment, the dispersions of the invention can also comprise glycerin. Preferably, a dispersion according to the invention can comprise at least 5% by weight of glycerin relative to the total weight of said dispersion.
    In fact, beyond the texture, the dispersions according to the invention provide another advantage compared to “classic” emulsions because they allow the use of glycerin, which is moreover in high contents.
    They may in particular comprise glycerin in a content greater than or equal to 10%, greater than or equal to 20%, greater than or equal to 30%, greater than or equal to 40%, or even up to 50%, by weight, by relative to the total weight of said dispersion.
    According to one embodiment, the dispersion of the invention also comprises at least one filler.
    A dispersion according to the invention can also comprise at least one filler, of organic or mineral nature, making it possible, in particular, to confer on it additional properties of improved stability with regard to exudation and non-migration properties after application and / or dullness and / or coverage. The term “filler” should be understood to mean colorless or white particles, solid of all shapes, which are in an insoluble form and dispersed in the medium of the composition. Mineral or organic in nature, they make it possible to impart body or rigidity and / or softness, and uniformity to the deposit, in particular in a makeup context. The fillers used in the dispersions according to the invention can be of lamellar, globular, spherical, fiber or any other intermediate form between these defined forms. The fillers according to the invention may or may not be coated superficially, and, in particular, they can be surface-treated with silicones, amino acids, fluorinated derivatives or any other substance promoting the dispersion and compatibility of the charge in the dispersion. Among the fillers which can be used in the compositions according to the invention, mention may be made of talc, mica, kaolin, bentone, precipitated calcium carbonate, magnesium carbonate and hydrogen carbonate, hydroxyapatite, nitride boron, glass or ceramic microcapsules, silica and titanium dioxide composites, such as the TSG series sold by Nippon Sheet Glass, polyamide powders (Nylon Orgasol from Atochem), poly-b-alanine and polyethylene, polytetrafluoroethylene (Teflon) powders, lauroyl lysine, starch, hollow polymer microspheres, such as EXPANCEL (NOBEL INDUSTRIE) or
    Polytrap® (Dow Corning), particles of elastomeric polyorganosiloxanes, metal soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example, zinc stearate, magnesium or lithium, zinc laurate, magnesium myristate, Polypore L 200 (Chemdal Corporation), microbeads of silicone resin (Tospearl from Toshiba, for example), polyurethane powders, in particular, powders of crosslinked polyurethane comprising a copolymer, said copolymer comprising trimethylol hexyllactone. In particular, it may be a polymer of hexamethylene diisocyanate / trimethylol hexyllactone. Such particles are in particular commercially available, for example, under the name of PLASTIC POWDER D-400 or PLASTIC POWDER D-800 from the company TOSHIKI, and their mixtures.
    The choice of fillers, for obvious reasons, must take into account the process used (in particular of the "non-microfluidic" or "microfluidic" type) for the manufacture of the dispersion according to the invention. This choice falls within the general knowledge of a person skilled in the art.
    Texture agent (s)
    Depending on the fluidity of the dispersion that it is desired to obtain, one or more texture agent (s) different from the cationic and anionic polymers, the gelling agent, oils and charges described above.
    Of course, a person skilled in the art will take care to choose any texturing agent (s) and / or their amount in such a way that the advantageous properties of the dispersion according to the invention are not or not substantially altered by the addition envisaged. . Also, a person skilled in the art will take care to choose the nature and / or the amount of texture agent (s) according to the aqueous or fatty nature of the phase considered of the dispersion according to the invention.
    Thus, in a dispersion according to the invention, the aqueous phase can comprise at least one texture agent different from the anionic polymer and the cationic polymer.
    As hydrophilic texturing agents, that is to say soluble or dispersible in water, and therefore possibly being present in the aqueous phase of a composition according to the invention, there may be mentioned:
    - natural texture agents, in particular chosen from algae extracts, plant exudates, seed extracts, exudates from microorganisms, such as alkasealan (INCI: Alcaligenes Polysaccharides), and other natural agents, in particular hyaluronic acid,
    - semi-synthetic texture agents, in particular chosen from cellulose derivatives and modified starches,
    - synthetic texturing agents, in particular chosen from homopolymers of (meth) acrylic acid or one of their esters, copolymers of (meth) acrylic acid or one of their esters, copolymers of AMPS (2acrylamido-2- methylpropane sulfonic acid), associative polymers,
    the other texturing agents, in particular chosen from polyethylene glycols (marketed under the name Carbowax), clays, silicas such as those marketed under the names Aérosil® 90/130/150/200/300/380), glycerin, and
    - their mixtures.
    By “associative polymer” within the meaning of the present invention, is meant any amphiphilic polymer comprising in its structure at least one fatty chain and at least one hydrophilic portion; the associative polymers in accordance with the present invention can be anionic, cationic, nonionic or amphoteric; these are in particular those described in FR 2 999 921. Preferably, these are amphiphilic and anionic associative polymers and amphiphilic and nonionic associative polymers as described below.
    These hydrophilic texturing agents are described in more detail in FR3041251.
    Of course, the person skilled in the art will take care to choose any additional compound (s) and / or their amount in such a way that the advantageous properties of the dispersion according to the invention are not or not substantially altered by the planned addition. In particular, the nature and / or the amount of the additional compound (s) depends on the aqueous or fatty nature of the phase considered of the dispersion according to the invention. These adjustments fall within the competence of a person skilled in the art.
    Preparation process
    The dispersions according to the invention can be prepared by various methods.
    Thus, the dispersions according to the invention have the advantage of being able to be prepared according to a simple “non-microfluidic” process, namely by simple emulsification.
    As in a conventional emulsion, an aqueous solution and a fatty solution are prepared separately. It is the addition, with stirring, of the fatty phase in the aqueous phase which creates the direct emulsion.
    The viscosity of the aqueous phase can be controlled, in particular, by varying the quantity of anionic polymer (in particular carbomer) and the pH of the solution. In general, the pH of the aqueous phase is less than 4.5, which may involve the addition of a third sodium hydroxide solution (BF) as a last step to reach a pH between 5.5 and 6, 5.
    The viscosity of the aqueous phase and the shear force applied to the mixture are the two main parameters which influence the size and the monodispersity of the emulsion.
    Those skilled in the art will know how to adjust the non-microfluidic process to meet the criterion of average diameter of the drops of the dispersion according to the invention.
    The emulsions according to the invention can also be prepared according to a microfluidic process, in particular as described in international applications WO2012 / 120043 or WO2015 / 055748.
    According to this embodiment, the drops obtained by this microfluidic process have a uniform size distribution.
    Preferably, the dispersions of the invention consist of a population of monodispersed drops, in particular such that they have an average diameter D of from 500 μm to 3,000 μm and a coefficient of variation Cv of less than 10%, or even less at 3%.
    In the context of the present description, the term “monodispersed drops” means the fact that the population of drops of the dispersion according to the invention has a uniform size distribution. Monodispersed drops have good monodispersity. Conversely, drops with poor monodispersity are said to be polydispersed.
    According to one mode, the average diameter D of the drops is for example measured by analysis of a photograph of a batch consisting of N drops, by image processing software (Image J). Typically, according to this method, the diameter is measured in pixels, then reported in pm, depending on the size of the container containing the drops of the dispersion.
    Preferably, the value of N is chosen to be greater than or equal to 30, so that this analysis statistically significantly reflects the distribution of diameters of the drops of said emulsion.
    The diameter Di of each drop is measured, then the average diameter D is obtained by calculating the arithmetic mean of these values:
    From these values D ,, it is also possible to obtain the standard deviation σ of the diameters of the drops of the dispersion:
    The standard deviation σ of a dispersion reflects the distribution of diameters D, drops of the dispersion around the mean diameter D.
    By knowing the mean diameter D e t the standard deviation σ of a dispersion, we can determine that 95.4% of the droplet population is found in the diameter range | p _ 2cr, £> + 2σ] and q ue μ οη finds 58.2% of the population in the interval ~ σ '· ^ + σ 1.
    To characterize the monodispersity of the dispersion according to this mode of the invention, the coefficient of variation can be calculated:
    This parameter reflects the distribution of droplet diameters as a function of their average diameter.
    The coefficient of variation Cv of the drop diameters according to this mode of the invention is less than 10%, preferably less than 5%, or even less than 3%.
    Alternatively, the monodispersity can be demonstrated by placing a dispersion sample in a bottle with a constant circular section. A gentle agitation by rotation of a quarter of a turn for half a second around the axis of symmetry crossing the flask, followed by a rest of half a second is carried out, before repeating the operation in reverse, and this four times in a row.
    The drops of the dispersed phase are organized in a crystalline form when they are monodispersed. Thus, they have a stack in a repeating pattern following in three dimensions. It is then possible to observe, a regular stacking which indicates a good monodispersity, an irregular stacking translating the polydispersity of the dispersion.
    To obtain monodisperse drops, one can also use the microfluidic technique (Utada et al. MRS Bulletin 32, 702-708 (2007); Cramer et al. Chem. Eng. Sci. 59, 15, 3045-3058 (2004)), and more particularly microfluidic devices of the co-flow type (the fluids go in the same direction) or flow-focusing (the fluids go in different directions, and typically in opposite directions).
    The presence, in the fatty phase, of gelling agent (s) may require adjustments in terms of the process for preparing a dispersion according to the invention. In particular, the process for preparing such an emulsion according to the invention may comprise a heating step (between 40 ° C and 15 ° C, in particular between 50 ° C and 90 ° C) at least of the fatty phase before mixing / contact in contact with said fatty phase with the aqueous phase and, if necessary and in the case of a "non-microfluidic" process as mentioned above, maintaining this heating during stirring until obtaining the desired dispersion.
    According to one embodiment, the process for preparing the dispersions of the invention comprises a step of forming the drops comprising:
    - bringing into contact an aqueous fluid FE and an oily fluid Fl as defined below; and
    - The formation of drops of fatty phase, consisting of oily fluid F1, dispersed in a continuous aqueous phase, consisting of fluid FE, said drops optionally comprising a bark isolating the heart from the drops of the fatty phase of the dispersion.
    According to one embodiment, the fluid F1 is initially prepared by mixing an oily phase intended to form the heart of the drops, at least one gelling agent and at least one oil H1 and in addition, optionally, at least one first precursor polymer coacervation such as a cationic polymer as defined above, at least one H 2 oil and / or at least one additional compound as mentioned above.
    According to one embodiment, the FE fluid is initially prepared by mixing an aqueous phase intended to form the continuous phase of the dispersion with, optionally, at least one base, at least one second precursor polymer of coacervation, such as an anionic polymer as defined above, at least one additional compound, preservatives and / or other water-soluble products such as glycerin.
    According to one embodiment, the cationic polymer optionally present in said oily fluid F1 is used in particular for the formation of the bark of the drops.
    According to one embodiment, the continuous aqueous phase of the dispersion formed comprises, or even is represented by, the aqueous phase of the fluid FE. The anionic polymer optionally present in said fluid FE is used in particular for the formation of the bark of the drops. Said anionic polymer also contributes to increasing the viscosity of the FE fluid, and therefore of the continuous aqueous phase.
    According to one embodiment, the step of forming the drops may also comprise a step of injecting a solution for increasing the viscosity of the continuous aqueous phase of the FE fluid. Preferably, the viscosity increasing solution is aqueous. This viscosity increasing solution is typically injected into the aqueous external fluid FE after formation of the dispersion according to the invention, and therefore after formation of the drops.
    According to one embodiment, the viscosity increasing solution comprises a base, in particular an alkali hydroxide, such as sodium hydroxide.
    According to one embodiment, the method for preparing a dispersion according to the invention comprises a step of heating the oily fluid F1, comprising the fatty phase of the dispersion, at a temperature between 40 ° C and 150 ° C, preferably from 50 ° C to 90 ° C, prior to the above-mentioned step of formation of the drops, and therefore before mixing / bringing said fatty phase into contact with the aqueous phase. In the case of a "non-microfluidic" process as mentioned above, this heating step can be maintained during stirring allowing the desired dispersion to be obtained.
    According to one embodiment, the temperature of the heating step is between 50 ° C to 80 ° C, preferably from 50 ° C to 70C, and more preferably from 55 to 65 ° C.
    According to one embodiment, when the oily fluid F1 comprises from 5% to 15% by weight of gelling agent (s) relative to the total weight of said oily fluid F1, said oily fluid F1 is advantageously heated to a temperature from 65 to 70 ° C.
    According to one embodiment, when the oily fluid F1 comprises from 15% to
    99%, preferably from 15% to 40%, by weight of gelling agent (s) relative to the total weight of said oily fluid F1, said oily fluid F1 is heated to a temperature of 80 to 90 ° C.
    According to this embodiment, the process for preparing the dispersions of the invention comprises the following steps:
    - Optionally, the heating of the oily fluid F1 as described above, or even of the aqueous fluid FE, to a temperature between 40 ° C and 150 ° C, preferably from 50 ° C to 90 ° C;
    - bringing the aqueous fluid FE as described above into contact with the oily fluid F1; and
    the formation of the fatty phase drops, consisting of the oily fluid F1, dispersed in a continuous aqueous phase consisting of the FE fluid, said drops optionally comprising a shell isolating the heart from the drops of the fatty phase of the dispersion, in which:
    the oily fluid F1 comprises at least one gelling agent and at least one oil H1 and, optionally, at least one cationic polymer as defined above, in particular amodimethicone, at least one oil H2 and / or at least one additional compound as mentioned above; and
    - The aqueous fluid FE comprises at least water and, optionally, at least one anionic polymer as defined above, in particular a carbomer, at least one additional compound as mentioned above.
    uses
    Preferably, the dispersion according to the invention can be used directly, at the end of the aforementioned preparation processes, as a composition, in particular a cosmetic. The dispersion according to the invention, when prepared by means of a microfluidic process as described above, can also be used as a composition, in particular cosmetic, after separation of the drops and redispersion of these in a second phase appropriate.
    The invention also relates to the use of a dispersion according to the invention for the preparation of a composition, in particular cosmetic.
    The present invention thus also relates to a composition, in particular a cosmetic composition, comprising at least one dispersion according to the invention, in association with a physiologically acceptable medium.
    The dispersions or compositions according to the invention can in particular be used in the cosmetic field.
    They can comprise, in addition to the abovementioned ingredients, at least one physiologically acceptable medium.
    In the context of the invention, and unless otherwise stated, the term “physiologically acceptable medium” means a medium suitable for cosmetic applications, and in particular suitable for applying a composition of the invention to a keratin material, in particular the skin and / or the hair, and more particularly 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 physiologically acceptable medium is represented directly by the aqueous continuous phase as described above.
    The cosmetic compositions of the invention can be for example a cream, an emulsion, a lotion, a serum, a gel and an oil for the skin (hands, face, feet, etc.), a foundation (liquid, paste ) a preparation for baths and showers (salts, foams, oils, gels, etc.), a hair care product (hair dyes and bleaches), a cleaning product (lotions, powders, shampoos), a maintenance product for hair (lotions, creams, oils), a styling product (lotions, hairsprays, brilliants), a shaving product (soaps, mousses, lotions, etc.), a product intended to be applied to the lips, a product sunscreen, a sunless tanning product, a product for whitening the skin, an anti-wrinkle product. In particular, the cosmetic compositions of the invention can be an anti-aging serum, a youth serum, a hydrating serum or a scented water.
    The present invention also relates to a non-therapeutic method of cosmetic treatment of a keratinous material, in particular the skin and / or the hair, and more particularly the skin, comprising a step of applying to said keratinous material at least one dispersion or at least one layer of a cosmetic composition mentioned above.
    The present invention also relates to the use of at least one non-volatile hydrocarbon H1 oil containing more than 90%, preferably more than 95%, of fatty acids having at least 18 carbon atoms, preferably at least 20 carbon atoms. carbon, as defined above, to improve the transparency of a dispersion according to the invention, and in particular to reduce, or even prevent:
    - the phenomenon of opacification of the continuous aqueous phase,
    - leakage of materials, in particular oil (s) and / or gelling agent (s), from the dispersed phase to the continuous aqueous phase,
    - the adhesion of the drops to the walls of the packaging, and / or
    - The aggregation of the drops together, and therefore preserving, or even improving, the stability over time and the visual of said dispersion according to the invention.
    Throughout the description, the expression “comprising a” should be understood as being synonymous with “comprising at least one”, unless otherwise specified.
    The expressions "between ... and ... >>," ranging from ... to ... >> and "ranging from ... to ... >> must be understood bounds included, unless the contrary is specified.
    The amounts of the ingredients appearing in the examples are expressed as a percentage by weight relative to the total weight of the composition, unless otherwise indicated.
    The examples which follow illustrate the present invention without limiting its scope.
    EXAMPLES
    Unless otherwise indicated, the dispersions described below result from a microfluidic process, in particular as described above or in WO2017046305. The microfluidic device used is broken down into two parts, a first part where hot (between 75 and 90 ° C.) is brought into contact between the IF (or Fl) and the OF (or FE) so to form the dispersion, and a second part ensuring rapid cooling of the dispersion thus formed to accelerate the kinetics of gelation of the drops and thus prevent the risks of coalescence of the drops after formation (cooling temperature: between 5 and 28 ° C.) .
    Example 1 Preparation of Dispersions of Macroscopic Drops with or Without Non-Volatile Hydrocarbon Oil According to the Invention
    This example consisted in preparing dispersions of macroscopic drops of a gelled fatty phase dispersed in a continuous aqueous phase.
    The compositions of the phases (fluids) allowing the preparation of the dispersions are as follows:
    1A(Comp.) 1B(Comp.) 1 C(Inv.) 2A(Comp.) 2B(Comp.) 2C(Inv.) Fluid Last name INCI % W / w % W / w % W / w % W / w % W / w % W / w IF(phaseoilygelled) DUB IN IN Grade A 'isononylisononanoate QSP * Argan Oil Argania spinosa kernel oil 0 18,00 0 0 18,00 0 Meadowfoam Oil Limnanthes alba seed oil 0 0 18,00 0 0 18,00 Rheopearl KL2 Dextrin palmitate, Palmitic Acid, Aqua 20.00 PH AT BLUE DC6204 Cl 61565 (and) Cl 60725 0.00092 CAS-3131PILOT amodimethicone 0 0.15 Total 100 OF(phaseaqueouskeep on going) Osmotic water Aqua qs Microcare PE phenoxyethanol,aqua 0.89 Microcare emollient PTG Pentylene glycol, aqua 2.22 Glycerin codex Glycerin, aqua 11.11 Edeta BD Disodium EDTA 0.044 Carbopol ETD 2050 polymer carbomer 0.33 Sodium hydroxide pellets PRSpharmacopoeia Sodiumhydroxide 0,013 Total 100 BF(based) Osmotic water Aqua qs Sodium hydroxide pellets PRSpharmacopoeia Sodiumhydroxide 0.35 Total 100
    * QSP: sufficient quantity for
    The 2A-2C tests differ from the 1A-1C tests by the presence of amodimethicone in the gelled fatty phase. This leads to the formation of a membrane at the water-oil interface deriving from a complex interfacial coacervation reaction between the amodimethicone and the carbomer.
    Preparation protocol:
    For the OF:
    Phenoxyethanol, Pentylene glycol and EDTA are incorporated into water. The mixture is stirred for 5 min.
    The carbomer is then dispersed in the preceding mixture with stirring for 30 minutes using a pale deflocculator.
    The glycerin is then added and the mixture is stirred for 10 min.
    The sodium hydroxide is then added and the solution is mixed for 10 minutes.
    Pourl'IF:
    The amodimethicone, when present (i.e. tests 2A to 2C), is added to the isononyl isononanoate and then mixed using a magnetic bar for 5 min. The PHAT BLUE DC6204 dye is then added with stirring.
    With stirring, add argan oil or Meadowfoam oil.
    The mixture is heated to 80 ° C. and then the Rheqoearl KL2 is added with magnetic stirring until a homogeneous solution is obtained.
    The heated IF solution is introduced into a syringe connected to a heater allowing the IF to be kept hot (80 ° C.). To reduce heat loss, the microfluidic device was installed directly at the syringe outlet.
    For BF: soda and water are mixed using a magnetic bar for 5 min.
    In these tests, the following rates were used:
    OF 150 mL / hr IF 20.35 mL / hr BF 16.667 mL / hr
    Parameters observed:
    At the end of production, each test of Example 1 is packaged in three half-filled polypropylene (PP) receptacles of 30 ml. After 1 day at room temperature, each test undergoes one of the following three transport tests (one receptacle per test), namely:
    - roller test (i.e. horizontal circular movement): Wheaton reference, for 1 hour;
    - vibrating table (i.e. vertical circular movement): Heidolph reference
    Unimax 1010, for 1 hour; and
    - 3D mixer (i.e. random movements): for 6 minutes.
    At the end of these 3 tests, the adhesion, aggregation and turbidity (or opacification) parameters of the continuous aqueous phase are analyzed (visual observation).
    MEMBERSHIP AGGREGATION TURBIDITY Attaching the drops to the packaging wall Agglomeration of the drops between them (the aggregation is likely to promote coalescence) Transfer of fatty phase into the continuous aqueous phase
    Rating criteria :
    RATING CRITERIA 0 1 2 3 MEMBERSHIP Absencemembership Slight adhesion membershipaverage Strong adhesion AGGREGATION Absenceaggregation Slight aggregation Aggregationaverage Strong aggregation GEL TURBIDITY Transparent gel Slightly cloudy gel Gelmoderatelytrouble Cloudy gel
    Results:
    1A(Comp.) 1B(Comp.) 1 C(invention) 2A(Comp.) 2B(Comp.) 2C(invention) MEMBERSHIP 3 3 2 2 2 1 AGGREGATION 2 2 1 2 2 0 TURBIDITYGEL 2 2 0 1 1 0
    The above tests have been reproduced, replacing, for tests 1C and 2C, the meadowfoam oil by jojoba oil (at% identical). Slightly less good results than with meadowfoam oil are obtained but nevertheless clearly more satisfactory than with argan oil.
    In a context of dispersion formed by macroscopic drops of a fatty phase gelled in a continuous aqueous phase, the use of at least one non-volatile hydrocarbon oil according to the invention therefore effectively reduces the phenomenon of clouding of the aqueous phase continuous but also of aggregation of the drops between them (and therefore the risks of coalescence) and the adhesion of the drops to the walls of the packaging.
    We also observe that the presence of a membrane (ie 2A-2C) reinforces these advantages in terms of reduction of the phenomenon of opacification of the continuous aqueous phase and adhesion of the drops to the walls of the packaging, or even of aggregation. drops between them.
    This helps to maintain the original and differentiating visual of such dispersions.
    Example 2 Influence of the Content of Non-Volatile Hydrocarbon Oil According to the Invention
    This example consisted in preparing dispersions of macroscopic drops of a gelled fatty phase dispersed in a continuous aqueous phase.
    The compositions of the phases (fluids) allowing the preparation of the dispersions are as follows:
    3A(Comp.) 3C(Inv.) 3D(Inv.) Fluid Last name INCI % W / w % W / w % W / w IF(phaseoilygelled) DUB ININ Grade A 'isononylisononanoate qs Meadowfoam Oil Limnanthes alba seed oïl 0 18,00 30,00 Rheopearl KL2 Dextrin palmitate, Palmitic Acid, Aqua 15,00 PHAT BLUE DC6204 Cl 61565 (and)Cl 60725 0.00092 CAS-3131PILOT amodimethicone 0.15 Total 100 OF(phaseaqueouskeep on going) Osmotic water Aqua qs Microcare PE phenoxyethanol,aqua 0.89 Microcare emollient PTG Pentylene glycol, aqua 2.22 Glycerin codex Glycerin, aqua 15,00 Zemeapropanediol Propanediol, aqua 4.80 Butylene glycol 1.3 Butylene glycol, aqua 5.30 Edeta BD Disodium EDTA 0.044 Carbopol ETD 2050 polymer carbomer 0.33 Sodiumhydroxide pellets PRS codex Sodium hydroxide 0,013 Total 100 BF(based) Osmotic water Aqua qs Sodiumhydroxide pellets PRS codex Sodium hydroxide 0.35 Total 100
    The preparation protocol, the parameters observed and the scoring criteria are identical to those described in example 1.
    Results:
    3A(comparative) 3C(invention) 3D(invention) MEMBERSHIP 2 1 1 AGGREGATION 2 1 1 GEL TURBIDITY 1 0 0
    An increase in the oil content of meadowfoam (ie 3C vs 3D) has no impact on the phenomenon of clouding of the continuous aqueous phase, the aggregation of the drops between them (and therefore the risks of coalescence) and the adhesion of the drops on the packaging walls.
    Also, an increase in the content of gelling agent in the dispersed fatty phase (i.e.
    2C vs 3C) further reduces the aggregation of the drops between them, and therefore the risk of coalescence.
    权利要求:
    Claims (14)
    [1" id="c-fr-0001]
    1. Dispersion containing a dispersed phase comprising drops and a continuous aqueous phase, preferably in the form of a gel, in which the drops comprise a fatty phase containing at least one gelling agent, and in which the fatty phase comprises at least one oil H1 non-volatile hydrocarbon containing more than 90%, preferably more than 95%, of fatty acids having at least 18 carbon atoms, preferably at least 20 carbon atoms.
    [2" id="c-fr-0002]
    2. Dispersion according to claim 1, in which at least 60%, or even at least 70%, preferably at least 80%, and better still at least 90%, of the drops have an average diameter greater than or equal to 500 μm, or even greater. or equal to 1000 pm, and better still between 500 pm and 3000 pm, preferably between 1000 pm and 2000 pm, in particular between 800 pm and 1500 pm.
    [3" id="c-fr-0003]
    3. Dispersion according to claim 1 or 2, in which the drops comprise a shell, said shell preferably comprising at least one anionic polymer and at least one cationic polymer.
    [4" id="c-fr-0004]
    4. Dispersion according to any one of claims 1 to 3, in which the fatty phase comprises between 1% and 50%, preferably between 5% and 40%, in particular between 10% and 30%, and in particular between 15% and 20%, by weight of oil (s) H1 relative to the total weight of said fatty phase.
    [5" id="c-fr-0005]
    5. Dispersion according to any one of claims 1 to 4, in which the H1 oil is chosen from vegetable oils.
    [6" id="c-fr-0006]
    6. Dispersion according to any one of claims 1 to 5, in which the oil H1 comprises more than 90%, and preferably more than 95%, of fatty acids chosen from oleic acid, in particular of type ( C18: 1, Δ-9), eicosenoic acid, in particular of the type (C20: 1, Δ-5), docosanoic acid, in particular of the type (C22: 1, Δ-5) and / or ( C22: 1, Δ-13), docosadienoic acid, in particular of the (C22: 2, Δ 5) type, and their mixtures, and better still eicosenoic acid, docosanoic acid and / or docosadienoic acid, and their mixtures.
    [7" id="c-fr-0007]
    7. Dispersion according to any one of claims 1 to 6, in which the gelling agent is chosen from organic or mineral, polymeric or molecular lipophilic gelling agents; solid fatty substances at room temperature and pressure; and their mixtures, and is especially chosen from the group consisting of polyacrylates, dextrin esters and fatty acid (s), glycerol esters and fatty acid (s), polyamides, and their mixtures.
    [8" id="c-fr-0008]
    8. Dispersion according to any one of claims 1 to 7, comprising from 0.5% to 99%, preferably from 1% to 70%, in particular from 1.5% to 50%, better still from 2% to 40 %, in particular from 2.5% to 30%, and preferably from 10% to 20%, by weight of gelling agent (s) relative to the total weight of the fatty phase.
    [9" id="c-fr-0009]
    9. Dispersion according to any one of claims 3 to 8, in which the cationic polymer is a silicone polymer modified by a primary, secondary or tertiary amine function, such as amodimethicone, and in particular corresponds to the following formula:
    NH 2 in which:
    - Ri, R 2 and R 3 , independently of each other, represent OH or CH 3 ;
    - R 4 represents a group -CH 2 - or a group -X-NH- in which X is a divalent alkylene radical in C3 or C4;
    - x is an integer between 10 and 5000;
    - y is an integer between 2 and 1000; and
    - z is an integer between 0 and 10.
    [10" id="c-fr-0010]
    10. Dispersion according to any one of claims 3 to 9, in which the anionic polymer is a polymer comprising monomer units comprising at least one chemical carboxylic acid function, preferably chosen from carbomers and crosslinked acrylate / Ci 0 - copolymers 30 alkyl acrylate.
    [11" id="c-fr-0011]
    11. Method for preparing a dispersion as defined according to any one of claims 1 to 10, comprising the following steps:
    - optionally, the heating of an oily fluid F1, at a temperature between 40 ° C and 150 ° C;
    - bringing an aqueous fluid FE into contact with the oily fluid Fl; and
    the formation of the fatty phase drops, consisting of the oily fluid F1, dispersed in a continuous aqueous phase, consisting of the FE fluid, said drops optionally comprising a bark isolating the heart from the drops of the fatty phase of the dispersion, in which:
    - the oily fluid F1 comprises at least one gelling agent and at least one non-volatile hydrocarbon H1 oil containing more than 90%, preferably more than 95%, of fatty acids having at least 18 carbon atoms, preferably at least 20 carbon atoms and, optionally, at least one cationic polymer, in particular amodimethicone and / or at least one H 2 oil, and
    - The aqueous fluid FE comprises at least water and, optionally, at least one anionic polymer, in particular a carbomer.
    [12" id="c-fr-0012]
    12. Composition, in particular cosmetic, comprising a dispersion according to any one of claims 1 to 10, in association with a physiologically acceptable medium.
    [13" id="c-fr-0013]
    13. Non-therapeutic method of cosmetic treatment of a keratinous material, in particular the skin and / or the hair, and more particularly the skin, comprising a step of applying to said keratinous material a dispersion according to any one of claims 1 to 10 or at least one layer of a cosmetic composition according to claim 12.
    [14" id="c-fr-0014]
    14. Use of at least one non-volatile hydrocarbon H1 oil containing more than 90%, preferably more than 95%, of fatty acids having at least 18 carbon atoms, preferably at least 20 carbon atoms, to improve the transparency of a dispersion as defined according to any one of claims 1 to 10, and in particular for (i) reducing, or even preventing:
    - the phenomenon of opacification of the continuous aqueous phase,
    - leakage of materials, in particular oil (s) and / or gelling agent (s), from the dispersed phase to the continuous aqueous phase,
    - the adhesion of the drops to the walls of the packaging, and / or
    - the aggregation of the drops together,
    5 and (ii) preserve, or even improve, the stability over time and the visual of said dispersion.
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    同族专利:
    公开号 | 公开日
    WO2019002308A1|2019-01-03|
    FR3067930B1|2020-01-10|
    US20200129413A1|2020-04-30|
    CN110972462A|2020-04-07|
    EP3644957A1|2020-05-06|
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    FR3041251B1|2015-09-18|2019-01-25|Capsum|COMPOSITIONS IN THE FORM OF OIL-IN-WATER EMULSIONS WHOSE FATTY PHASE IS IN THE FORM OF DROPS|FR3098113A1|2019-07-04|2021-01-08|Capsum|Composition in the form of an oil-in-water emulsion with a fatty phase in the form of drops and aggregates|
    FR3110405A1|2020-05-21|2021-11-26|Capsum|Double stable emulsion without bark|
    FR3110406A1|2020-05-21|2021-11-26|Capsum|Stable dispersion without bark|
    法律状态:
    2018-12-28| PLSC| Search report ready|Effective date: 20181228 |
    2019-05-23| PLFP| Fee payment|Year of fee payment: 3 |
    2020-05-14| PLFP| Fee payment|Year of fee payment: 4 |
    2021-05-14| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1755907A|FR3067930B1|2017-06-27|2017-06-27|DISPERSIONS COMPRISING AT LEAST ONE HYDROCARBON VOLATILE OIL|
    FR1755907|2017-06-27|FR1755907A| FR3067930B1|2017-06-27|2017-06-27|DISPERSIONS COMPRISING AT LEAST ONE HYDROCARBON VOLATILE OIL|
    PCT/EP2018/067140| WO2019002308A1|2017-06-27|2018-06-26|Dispersions comprising at least one non-volatile hydrocarbon oil|
    CN201880043179.5A| CN110972462A|2017-06-27|2018-06-26|Dispersion comprising at least one non-volatile hydrocarbon oil|
    EP18734218.3A| EP3644957A1|2017-06-27|2018-06-26|Dispersions comprising at least one non-volatile hydrocarbon oil|
    US16/626,820| US20200129413A1|2017-06-27|2018-06-26|Dispersions comprising at least one non-volatile hydrocarbon oil|
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