Dispersion comprising an oil phase in the form of droplets dispersed in a fluid, carbomer-free, gelled aqueous phase and associated manufacturing process

Abstract

Dispersion comprising an oil phase in the form of droplets dispersed in a fluid, carbomer-free, gelled aqueous phase and associated manufacturing process. The invention relates to a dispersion comprising an oil phase (14) in the form of droplets (12) dispersed in a continuous aqueous phase (22), the oil phase (14) and the aqueous phase (22) being immiscible, wherein the aqueous phase (22) comprises water, at least one base, and at least one first hydrophilic gelling agent selected from at least one starch derivative comprising at least one carboxylic acid group, the dispersion being carbomer-free. Figure for abstract: None

Description

Title of the invention: Dispersion comprising an oil phase in the form of droplets dispersed in a fluid, carbomer-free, gelled aqueous phase and associated manufacturing process

[0001] The present invention relates to a dispersion comprising a fatty phase in the form of drops dispersed in a continuous fluid gelled aqueous phase comprising at least one base and at least one first hydrophilic gelling agent selected from at least one starch derivative comprising at least one carboxylic function, said aqueous phase being free of carbomer, as well as its manufacturing process.

[0002] The manufacturing industry, like the cosmetics industry, is seeking natural or at least more eco-friendly alternatives for its formulations. Indeed, many raw materials used in compositions, particularly cosmetic ones, are of petrochemical origin and / or do not have satisfactory biodegradability properties. This is notably the case for hydrophilic gelling polymers such as homopolymers of acrylic acid crosslinked with pentaerythritol allylic ethers or sucrose allylic ethers, known as carbomers (INCI name: CARBOMER), for example those marketed by Lubrizol under the name Carbopol, such as Ultrez 10 or ETD 2050.

[0003] These raw materials possess numerous qualities, such as transparency, a non-sticky texture, suspending power, shear-thinning behavior, and good temperature stability. Furthermore, these raw materials have the ability to modulate the viscosity of the aqueous phase containing them according to the pH. This property is very useful for the production of emulsions, since it allows the formation of droplets of an oily phase dispersed in a continuous fluid aqueous phase, before increasing the viscosity of the latter by raising the pH, particularly by adding sodium hydroxide, and thus achieving the desired texture and, in the case of oil-in-water emulsions, a viscosity sufficient to suspend the dispersed oily phase droplets while remaining fluid.

[0004] We can thus speak of an aqueous phase with a tunable, evolving, or activatable viscosity. This activatable characteristic is particularly useful in the case of a microfluidic manufacturing process, as described in WO2015055748, which requires, before dispersion formation, a continuous aqueous phase with a fluid viscosity to be compatible with microfluidic constraints, said viscosity then being increased after dispersion formation in order to ensure a satisfactory suspension of the oil phase droplets dispersed in the continuous aqueous phase.

[0005] Numerous attempts to substitute carbomers with natural hydrophilic gelling agents have been considered.

[0006] While many natural hydrophilic gelling agents are sensitive to temperature, few of them have the property of modulating their viscosity upwards as a function of a physicochemical parameter at room temperature, like carbomers.

[0007] In addition, this substitution is difficult because of the generally lower performance of these natural hydrophilic gelling agents in terms, in particular, of transparency, non-stickiness and / or kinetic stability.

[0008] Moreover, when seeking a fluid, gelled aqueous phase with a certain viscosity, gels based on natural hydrophilic gelling agent(s) are often firm and brittle, whereas gels based on carbomer(s) are flexible, fluid, and slightly cohesive. By "slightly cohesive," we mean a gel exhibiting a balanced compromise between the ability to stick to itself, unlike a brittle gel, without this property being too pronounced, lest the gel have an "egg white" texture / behavior, which is undesirable.

[0009] There is therefore a need for new dispersions whose gelled aqueous phase, although devoid of carbomer, remains endowed with a modulating viscosity and which, after activation, has satisfactory performance in terms of flexibility, fluidity, cohesiveness and kinetic stability.

[0010] The invention therefore aims to provide a dispersion in which the gelled aqueous phase, although devoid of carbomer, remains endowed with a modulating viscosity and which, after activation, has satisfactory performance in terms of flexibility, fluidity, and cohesiveness.

[0011] The invention further aims to provide such a dispersion whose continuous aqueous phase is capable of stably suspending the oil phase drops at 50°C, and which is compatible with a microfluidic manufacturing process at room temperature.

[0012] Contrary to expectations, the inventors observed that the invention makes it possible to obtain a dispersion comprising a continuous aqueous phase in the form of a fluid gel with properties similar to those observed with carbomer gels, in particular in terms of transparency, non-stickiness, suspensivity and kinetic stability, particularly over time and during transport.

[0013] Thus, the present invention relates to a dispersion comprising an oily phase (14) in the form of droplets (12) dispersed in a continuous aqueous phase (22), the oily phase (14) and the aqueous phase (22) being immiscible, in which the phase aqueous (22) comprises water, at least one base and at least one first hydrophilic gelling agent selected from at least one starch derivative comprising at least one carboxylic function, the dispersion being devoid of carbomer.

[0014] By "stable" or "kinetic stability", we mean, at the level of a dispersion according to the invention, the absence of creaming or sedimentation of the dispersed phase drops in the continuous phase, the absence of opacification of the continuous phase, the absence of aggregation of the drops among themselves, and in particular the absence of coalescence or Oswald ripening of the drops among themselves, and the absence of leakage of materials, from the dispersed phase to the continuous phase, or vice versa, and in particular the absence of leakage of oil(s) from the dispersed phase to the continuous phase.

[0015] Unexpectedly, a gelled aqueous phase (22) according to the invention remains compatible with a microfluidic manufacturing process, moreover at room temperature, without prejudice to the aforementioned advantages.

[0016] Furthermore, a dispersion according to the invention, when applied to a keratinous material, particularly to the skin, exhibits satisfactory sensory performance, and in particular retains the "water-breaking" sensory experience specific to carbomer gels, that is, the sensation felt when an aqueous gel breaks under applied pressure and releases the water it contains, giving a feeling of freshness and hydration. This sensory experience is all the more remarkable as it is accompanied by satisfactory properties in terms of play-time and non-stickiness. Thus, upon application, particularly to a keratinous material, a dispersion according to the invention advantageously has an average play-time of less than 3 minutes, preferably less than 2 minutes, and more preferably less than 1 minute.

[0017] Preferably, the aqueous phase (22) is a "fluid gelled aqueous phase" or "liquid gelled aqueous phase".

[0018] For the purposes of this invention, "fluid" means an aqueous phase which, at room temperature and atmospheric pressure, although gelled, retains the ability to flow under its own weight. In particular, a fluid gelled aqueous phase according to the invention retains the ability to conform to the shape of its container. In other words, a fluid gelled aqueous phase according to the invention is not in the form of a solid block, and in particular is not in the form of a firm and brittle solid gel. Thus, for the purposes of this invention, the term "fluid" may be referred to interchangeably as "liquid." Also, for the purposes of this invention, the characteristic "fluid gel" may be referred to interchangeably as "liquid gel," "gelled liquid," "fluid gel," or "liquid gel."

[0019] Preferably, the aqueous phase (22) of a dispersion according to the invention, or even said dispersion, is natural, and preferably biodegradable.

[0020] For the purposes of this invention, "natural" means a composition comprising a percentage of ingredients of natural origin greater than or equal to 85%, preferably greater than or equal to 90%, and in particular greater than or equal to 95%, according to ISO 16128. The percentage of ingredients of natural origin can be calculated using the method described in FR3119317.

[0021] Preferably, a dispersion according to the invention has a pH between 6.0 and 8.0, preferably between 6.5 and 7.5.

[0022] Unless otherwise indicated, in all that follows, it is assumed that we are at ambient temperature (for example T=25°C ± 2°C) and atmospheric pressure (760 mm of Hg, i.e. 1.013.105 Pa or 1013 mbar).

[0023] According to a preferred embodiment, a dispersion according to the invention does not comprise a surfactant.

[0024] In the context of the present invention, the aforementioned dispersion may be referred to interchangeably as "emulsion". Aqueous phase

[0025] Unless otherwise specified, "aqueous phase" in the present invention means either the aqueous phase (16) or the aqueous phase (22).

[0026] An aqueous phase according to the invention necessarily comprises at least water. In addition to distilled or deionized water, water suitable for the invention may also be natural spring water or floral water.

[0027] According to one embodiment, the mass percentage of water in an aqueous phase according to the invention is at least 30%, preferably at least 40%, in particular at least 50%, and better at least 60%, in particular between 70% and 98%, and preferably between 75% and 95%, relative to the total mass of said aqueous phase.

[0028] For the purposes of the present invention, the "aqueous phase (16)" therefore comprises at least water, at least the first hydrophilic gelling agent, and optionally at least a portion of the base. Preferably, the aqueous phase (16) does not comprise a base. Preferably, the aqueous phase (16) comprises at least a first portion of the base.

[0029] For the purposes of the present invention, the "aqueous phase (22)" therefore comprises at least water, at least the first hydrophilic gelling agent, and furthermore at least one base. In other words, the "aqueous phase (22)" corresponds to the aqueous phase (16) comprising all the required base.

[0030] When the aqueous phase (16) comprises the entire base, as explained in more detail below, said aqueous phase (16) is identical to the aqueous phase (22).

[0031] For the purposes of the present invention, the "aqueous phase (22)" may be referred to interchangeably as "fluid gelled aqueous phase" or "liquid gelled aqueous phase".

[0032] The aqueous phase (22) preferably has a viscosity, as measured at 25°C and under a shear stress of 2 s1, of 500 mPa.s to 50,000 mPa.s, preferably from 1,000 mPa.s to 25,000 mPa.s, in particular from 500 mPa.s to 15,000 mPa.s, in particular from 1,000 mPa.s to 10,000 mPa.s, and most particularly from 1,000 mPa.s to 5,000 mPa.s.

[0033] The viscosity is determined according to the protocol described in the example below.

[0034] The aqueous phase (22) is a non-Newtonian fluid. It is a fluid shear-thinning agent.

[0035] Preferably, the aqueous phase (22), or even a dispersion according to the invention, is transparent or at least translucent. The property of transparency or translucency is determined according to the protocol described in the example below.

[0036] Advantageously, the gelled aqueous phase (22) of the dispersion has a suitable flow threshold value to ensure the suspension (or suspensivity) of the oil phase droplets (14) dispersed over a period of time greater than or equal to 1 month, preferably greater than or equal to 3 months, or even greater than or equal to 6 months at a temperature of 50°C. In addition to the associated visual effect, this stable suspensive property at 50°C ensures even improved kinetic stability of the dispersion, in particular preventing / limiting the phenomena of droplet coalescence and / or creaming and / or sedimentation of the droplets in the continuous phase, and thus effectively preventing any alterations to the visual appearance of a dispersion according to the invention.

[0037] Thus, the aqueous phase (22) preferably has a yield stress greater than or equal to 0.1 Pa, in particular greater than or equal to 1 Pa, and preferably between 0.25 Pa and 100 Pa, in particular between 0.5 Pa and 75 Pa, especially between 1 Pa and 50 Pa, or even between 2 Pa and 25 Pa, and better between 3 Pa and 20 Pa.

[0038] The yield stress can be evaluated using a shear rate sweep protocol with a rheometer (reference TA Instruments), according to the method described in HA Bames, A Handbook of Elementary Rheology; Institute of Non-Newtonian Fluid Mechanics. University of Wales, 2000 or in http: / / www.tainstruments.com / pdf / literature / RH025.pdf.

[0039] The aqueous phase (22) according to the invention is not in the form of a dispersion of gel microfragments. "Microfragment" is understood to mean gel fragments with a size less than 1 mm, preferably less than 0.5 mm, or even less than 0.1 mm, in particular between 10 and 100 microns, preferably between 25 and 50 microns. Preferably, a microfragment is a microscopic fragment.

[0040] An aqueous phase (22) according to the invention is advantageously slightly cohesive, namely that it exhibits a balanced compromise between the ability to stick to itself, unlike a brittle gel, without this property being excessively exacerbated, under penalty to be faced with a gel having an "egg white" type texture / behavior, which would not be desirable. First hydrophilic gelling agent

[0041] The first hydrophilic gelling agent is selected from a starch derivative comprising at least one carboxylic acid group. For the purposes of the present invention, the first hydrophilic gelling agent is capable of gelling in the presence of at least one base.

[0042] A first hydrophilic gelling agent according to the invention is therefore not a thermosensitive or ionosensitive gelling agent.

[0043] For the purposes of this invention, "hydrophilic" means a gelling agent that is soluble or dispersible in water.

[0044] A first hydrophilic gelling agent thus makes it possible to modulate the viscosity and fluidity of the aqueous phase (16) comprising it in the presence of at least one base, and therefore its texture and / or its sensoriality, and also makes it possible to suspend the drops of phase dispersed in the aqueous phase.

[0045] Advantageously, a first hydrophilic gelling agent according to the invention can be processed at room temperature, that is to say, the viscosity and fluidity of the aqueous phase comprising it, in the presence of at least one base, are obtained at room temperature. This makes it possible to manufacture a dispersion according to the invention without heating the aqueous phase (16), which is particularly advantageous, especially from an economic, environmental, and safety standpoint for operators, and even more so on an industrial scale.

[0046] Preferably, the first hydrophilic gelling agent is of natural origin.

[0047] Advantageously, a first hydrophilic gelling agent according to the invention is biodegradable (OECD 301B) and preferably has a raw material content of natural origin greater than or equal to 70%, preferably greater than or equal to 80%, and even greater than or equal to 85% (ISO 16128).

[0048] Advantageously, a first hydrophilic gelling agent according to the invention is free from genetically modified organisms (GMOs), ethoxylated ingredients (EOs) and / or polyethylene glycol (PEG).

[0049] A first hydrophilic gelling agent according to the invention can be chosen from a carboxymethylated starch (CMC), a carboxyethyl starch (ECS), an oxidized starch, a grafted starch, one of their derivatives and mixtures, and preferably chosen from a grafted starch or one of its derivatives.

[0050] A first hydrophilic gelling agent according to the invention is in particular as described in patent application WO2023059784

[0051] Preferably, the first hydrophilic gelling agent has the INCI name: “Starch Acetate / Adipate (and) Citric Acid”.

[0052] As a first hydrophilic gelling agent according to the invention, we can cite the reference Carbopol Fusion S-20 polymer marketed by the company Lubrizol.

[0053] As previously stated, the dispersion is carbomer-free. In other words, a first hydrophilic gelling agent according to the invention is different from a carbomer.

[0054] For the purposes of this invention, "carbomer" means a hydrophilic gelling polymer of the type of acrylic acid homopolymers crosslinked with pentaerythritol allylic ethers or sucrose allylic ethers (having the INCI name CARBOMER), for example those marketed by Lubrizol under the name Carbopol Ultrez 10.

[0055] Naturally, a person skilled in the art will take care to choose the first hydrophilic gelling agent and / or its quantity in such a way that the advantageous properties of a dispersion according to the invention are not, or are not substantially, altered by the envisaged addition. These adjustments fall within the general knowledge of a person skilled in the art.

[0056] An aqueous phase (22) according to the invention advantageously comprises between 0.1% and 10%, preferably between 0.5% and 7.5%, more preferably between 1% and 5%, and particularly between 2% and 4%, by weight of the first hydrophilic gelling agent(s) relative to the total weight of said aqueous phase (22). To avoid any ambiguity, this refers to the active ingredient included in the reference of the first hydrophilic gelling agent used. Indeed, by way of illustration, the aforementioned Carbopol Fusion S-20 polymer is a composition (or premix) comprising 21% of the active ingredient providing the desired gelling / suspension properties.

[0057] When the first hydrophilic gelling agent is in the form of a composition or premix, such as Carbopol Fusion S-20 polymer, an aqueous phase (22) according to the invention advantageously comprises between 1% and 50%, preferably between 5% and 40%, better between 10% and 30%, and particularly between 10% and 20%, by weight of first hydrophilic gelling agent(s) relative to the total weight of said aqueous phase (22). Base

[0058] The base acts as a gelling activator of the first hydrophilic gelling agent.

[0059] The base can be added to the aqueous phase (16) as such, i.e. in the form of crystals, or as a pre-dispersion in an aqueous solution.

[0060] Such a pre-dispersion can be referred to interchangeably as "viscosity increase solution (62)", "additional solution (62)", "additional solution", "solution (62)" or "BF".

[0061] For obvious reasons, the additional solution (62) is miscible with the aqueous phase (16). By "miscible" in the context of the present invention, we mean that the solubility of a first phase in a second phase is advantageously greater than 5% by mass.

[0062] In other words, the base is capable of reacting with the first hydrophilic gelling agent, that is to say, of modulating, and in particular increasing, the viscosity of the aqueous phase (16). In other words, the base or the additional solution (62), added to the aqueous phase (16), has the effect of interacting with the first hydrophilic gelling agent, and thus inducing the gelation of the aqueous phase (16) and therefore an increase in its viscosity, thereby obtaining an aqueous phase (22).

[0063] The additional base or solution (62) further has the effect of inducing the suspension of the aqueous phase (22) with respect to the drops (12) of dispersed oily phase, preferably over a period of time of at least 1 month, preferably at least 3 months, better at least 6 months, and particularly at least 12 months.

[0064] A base according to the invention can be a strong base or a weak base, and a mixture thereof, and preferably a strong base.

[0065] As a strong base, we can mention sodium hydroxide (or NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH)2), and mixtures thereof, and preferably sodium hydroxide (or NaOH).

[0066] Examples of weak bases include sodium bicarbonate (NaHCO3), Trôna (sodium sesquicarbonate), and mixtures thereof.

[0067] Advantageously, a base is chosen from an alkali hydroxide, and the reference base is sodium hydroxide (or NaOH).

[0068] A base according to the invention is not a salt.

[0069] The aqueous phase (22) advantageously comprises between 0.1% and 20%, preferably between 0.25% and 15%, better between 0.5% and 10%, and particularly between 0.25% and 5%, in weight of base(s) relative to the total weight of the aqueous phase (22).

[0070] The additional solution (62) may advantageously comprise between 1% and 40%, preferably between 4% and 30%, and better between 8% and 10%, in weight of base(s) relative to the total weight of the additional solution (62).

[0071] The weight ratio of "first hydrophilic gelling agent(s) / base(s)" is advantageously between 0.1 and 50, better between 0.5 and 40, in particular between 1 and 30, preferably between 2 and 15, and better between 5 and 10, when reasoning in terms of the active matter of the first hydrophilic gelling agent(s).

[0072] When the first hydrophilic gelling agent is in the form of a composition or premix, such as Carbopol Fusion S-20 polymer, the weight ratio of "first hydrophilic gelling agent(s) / base(s)" is advantageously understood to be between 2.5 and 300, better between 5 and 250, especially between 10 and 200, preferably between 15 and 100, and better between 20 and 50.

[0073] According to a first embodiment, the aqueous phase (22) does not include any hydrophilic gelling agent other than the first hydrophilic gelling agent.

[0074] According to another particular embodiment, the aqueous phase (22) may further comprise at least one second hydrophilic gelling agent different from the first hydrophilic gelling agent, preferably chosen from at least one non-ionosensitive and non-thermosensitive hydrophilic gelling agent, in particular chosen from a vegetable gum, and preferably chosen from xanthan gum, sclerotium gum, cellulose or one of its derivatives, starch or one of its derivatives, locust bean gum, acacia gum, Alcasealane, lambda carrageenan, glucomannan, tamarind gum, konjac gum, and mixtures thereof.

[0075] Here again, the second hydrophilic gelling agent is necessarily different from an acrylic polymer, and in particular from a carbomer.

[0076] Naturally, a person skilled in the art will take care to choose the second hydrophilic gelling agent and / or its quantity in such a way that the advantageous properties of a dispersion according to the invention are not, or are not substantially, altered by the envisaged addition. These adjustments fall within the general knowledge of a person skilled in the art.

[0077] Preferably, the aqueous phase (22) may further comprise at least one second hydrophilic gelling agent that is non-ionosensitive and non-thermosensitive.

[0078] Preferably, the aqueous phase (22) does not comprise an ionosensitive hydrophilic gelling agent, preferably selected from carrageenan, in particular kappa and iota-carrageenan; gellan gum, in particular Low Acyl gellan; alginate; pectin, in particular Low Methoxyl pectin; diutan gum; furcellarane; or one of their derivatives; and mixtures thereof, and preferably from alginate, gellan gum and / or carrageenan, and particularly from gellan gum and iota-carrageenan.

[0079] Advantageously, the gelled aqueous phase (22), or even a dispersion according to the invention, does not comprise cellulose or any of its derivatives, and in particular does not comprise:

[0080] - preBIULIN C90 (INCI: Cellulose Gum (and) Xanthan Gum (and) Inulin (and) Cellulose (and) Glucose (and) Fructose);

[0081] - Sucraclear HC-31 (INCI: Chondrus Crispus Powder (and) Cellulose Gum (and) Ceratonia Siliqua (Carob) Gum (and) Glucose);

[0082] - Sucraclear V2 (INCI: Cellulose Gum, Chondrus Cripsus Powder (Carageenan), Ceratonia Siliqua Gum, Glucose); And

[0083] - their mixtures. Fatty phase

[0084] The oily phase (14) and the aqueous phase (22) of a dispersion according to the invention are immiscible.

[0085] For the purposes of this invention, "immiscible" means that the solubility of a first phase in a second phase is advantageously less than 5% by mass.

[0086] The oily phase (14) comprises at least one oil and optionally at least one lipophilic gelling agent, preferably thermosensitive, and in particular chosen from among lipophilic gelling agents, organic or mineral, polymeric or molecular; solid fats at ambient temperature and pressure; and mixtures thereof. Oils

[0087] The term "oil" means a liquid fat at room temperature.

[0088] Examples of oils that can be used in a dispersion of the invention include:

[0089] - vegetable-derived hydrocarbon oils, such as jojoba oil hydrogenated, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil, Meadowfoam oil, Caprylic / Capric Triglyceride (e.g., the Labrafac CC MB reference marketed by Gattefossé);

[0090] - hydrocarbon oils of animal origin, such as perhydrosqualene and squalane;

[0091] - synthetic esters and ethers, particularly of fatty acids, such as oils of formulas R1COOR2 and R1OR2 in which RI represents the remainder of a fatty acid in C8 to C29, and R2 represents a hydrocarbon chain, branched or unbranched, in C3 to C30, such as 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, neopentyl glycol diheptanoate and diethylene glycol diisononanoate; and pentaerythritol esters such as pentaerythrityl tetrabehenate (DUB PTB) or pentaerythrityl tetraisostearate (Prisorine 3631);

[0092] - linear or branched hydrocarbons, of mineral or synthetic origin, such as paraffin oils, volatile or not, and their derivatives, petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam oil;

[0093] - silicone oils, such as polymethylsiloxanes (PDMS) volatile or non-volatile linear or cyclic silicone chain, liquid or pasty at room temperature, including cyclopolydimethylsiloxanes (cyclomethicones) such as cyclohexasiloxane and cyclopentasiloxane; polydimethylsiloxanes (or dimethicones) containing alkyl, alkoxy or phenyl groups, pendant or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenyl silicones such as phenyltrimethicones, phenyldimethicones, phenyltrimethylsiloxydiphenyl-siloxanes, diphenyl-dimethicones, diphenylmethyldiphenyl trisiloxanes, 2-phenylethyltrimethyl-siloxysilicates, and polymethylphenylsiloxanes;

[0094] - liquid fatty alcohols having from 8 to 26 carbon atoms, such as octyldodecanol, oleic alcohol, isostearic alcohol or mixtures thereof;

[0095] - partially hydrocarbon and / or silicone-containing fluorinated oils such as those described in document JP-A-2-295912;

[0096] - and their mixtures.

[0097] According to a preferred embodiment, the oil is chosen from the group consisting of vegetable hydrocarbon oils, synthetic esters and ethers, fatty alcohols having 8 to 26 carbon atoms, and mixtures thereof.

[0098] Advantageously, the oily phase does not include animal-derived hydrocarbon oil, linear or branched hydrocarbon oil, silicone oil, fluorinated oil, and mixtures thereof.

[0099] According to a preferred embodiment, the oily phase does not include silicone oil, and preferably does not include polydimethylsiloxane (PDMS).

[0100] A person skilled in the art will know how to adjust the nature and / or content of oil(s), in particular to ensure satisfactory kinetic stability of the dispersion according to the invention and to preserve the aforementioned advantageous technical effects.

[0101] According to one embodiment, a dispersion according to the invention comprises between 30% and 100%, in particular between 40% and 90%, preferably between 50% and 80%, and in particular between 60% and 70%, by weight of oil(s) relative to the total weight of the oil phase (14). Lipophilic gelling agents

[0102] A lipophilic gelling agent, i.e. soluble or dispersible in the fat phase, may be chosen from organic or mineral, polymeric or molecular gelling agents; solid fats at ambient temperature and pressure, in particular chosen from waxes, pasty fats, butters; and mixtures thereof, and preferably from polymeric gelling agents.

[0103] Such lipophilic gelling agents are described in particular in WO2019002308.

[0104] Among lipophilic gelling agents, we can also mention:

[0105] - dextrin and fatty acid esters, such as dextrin palmitates, dextrin myristates and / or dextrin palmitates / ethylhexanoates, such as those 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 Miyoshi Europe

[0106] - the glycerin and hydroxystearic acid triester, such as that marketed under the name THIXCIN® R from Elementis Specialties (INCI: Trihydroxystearin),

[0107] - polyurethane-79, such as that marketed under the name OILKEMIA™ 5S polymer by Lubrizol (INCI: Caprylic / Capric Triglyceride (and) Polyurethane-79), or its palm oil-free alternative marketed under the name OILKEMIA™ Alpha POF polymer by Lubrizol (INCI: Hydrogenated Poly(C6-20 Olefin) (and) HDI / Trimethylol Hexyllactone Crosspolymer),

[0108] - the crosslinked polymer hexamethylene diisocyanate (HDI) / trimethylol hexyllactone, such as that marketed under the name Oilkemia™ 5S CC polymer (INCI: Caprylic / Capric Triglyceride (and) Hydrogenated Poly(C6-20 Olefin) (and) HDI / Trimethylol Hexyllactone Crosspolymer),

[0109] - castor oil / isophorone diisocyanate (IPDI) copolymer, such as those marketed under the name Estogel M by the company PolymerExpert (INCI: CASTOR OIL / IPDI COPOLYMER & CAPRYLIC / CAPRIC TRIGLYCERIDE), or under the name EMC30 (INCI: Caprylic / Capric Triglyceride (and) Castor Oil / IPDI Copolymer), or even under the name EMI30 (INCI: Isononyl Isononanoate (and) Castor Oil / IPDI Copolymer (and) Caprylic / Capric Triglyceride),

[0110] - hydrogenated castor oil / sebacylic acid copolymer (name INCI: Hydrogenated Castor Oil / Sebacic Acid Copolymer), as well as its derivatives, notably marketed respectively under the names Estogel Green (or Estogel G) and Estogel Green 40 by PolymerExpert, and [YES] - their mixture.

[0112] Advantageously, a lipophilic gelling agent is a thermosensitive gelling agent.

[0113] The term "temperature-sensitive gelling agent" refers to a gelling agent that allows the phase comprising it to change from a liquid to a solid form in the form of a gel block, this gelling being reversible under the effect of temperature. In particular, the temperature-sensitive gelling agent, and mechanically the phase comprising it, is solid at room temperature and liquid at a temperature above 40°C, preferably above 50°C.

[0114] Advantageously, a lipophilic gelling agent is a thixotropic gelling agent or one capable of imparting thixotropic behavior to the oil phase. Such a thixotropic gelling agent is notably chosen from among pyrogenated silicas, possibly treated hydrophobically.

[0115] According to the invention, a dispersion according to the invention can comprise from 0.5% to 30%, preferably from 1% to 25%, in particular from 1.5% to 20%, better from 2% to 15%, and most particularly from 5% to 12%, by weight of lipophilic gelling agent(s) relative to the total weight of the fat phase (14).

[0116] According to a first embodiment, a dispersion according to the invention can be a simple emulsion, and in particular a direct oil-in-water type emulsion.

[0117] According to a second embodiment, a dispersion according to the invention can be a multiple emulsion and therefore comprise at least one third phase (19) (or internal dispersed phase), in which case the oily phase (14) is located between the third phase (19) and the continuous aqueous phase (22), and can therefore be described as an "intermediate dispersed phase." According to a first embodiment, the oily phase (14) and the third phase (19) are substantially immiscible, and the oily phase (14) and the aqueous phase (22) are substantially immiscible. In particular, a multiple dispersion according to the invention is of the type:

[0118] - water-in-oil-in-water, or

[0119] - oil-in-oil-in-water, in which case the third phase (19) and the oil phase (14) include oils that are substantially immiscible.

[0120] For the purposes of this invention, "substantially immiscible oils" or "immiscible oils" means that the mixture of these two oils does not result in a homogeneous, one-phase solution. Those skilled in the art will be able to adjust the choice of oils to satisfy the aforementioned "immiscible" criterion. Oils that are immiscible with each other are described in particular in FR1752204.

[0121] According to a second embodiment, the oily phase (14) and the third phase (19) are miscible, in which case the multiple emulsion is a transient stage that will evolve towards a final stage of a simple emulsion. Thus, in a transient multiple emulsion, the third phase (19) is oily and is miscible with the oily phase (14).

[0122] A dispersion according to the invention may comprise from 1% to 60%, in particular from 5% to 50%, preferably from 10% to 40%, and better from 15% to 30%, by weight of fat phase (14) relative to the total weight of the dispersion.

[0123] Preferably, the dispersion according to the invention, and in particular the oily phase, does not comprise a lipophilic cationic polymer, and in particular does not comprise amodimethicone (or amino-silicone). Drops

[0124] The dispersed oily phase (14) of a dispersion according to the invention is in the form of drops, preferably macroscopic, i.e. visible to the naked eye.

[0125] The drops (12) are advantageously substantially spherical.

[0126] In the remainder of this description, the drops (12) of oily phase (14) may be referred to interchangeably as "drops" or "drop (Gl)".

[0127] Preferably, the drops (12) having a diameter greater than or equal to 100 pm, better greater than or equal to 250 pm, preferably greater than or equal to 500 pm, in particular greater than or equal to 750 pm, and better greater than or equal to 1000 pm, represent a volume greater than or equal to 60%, or even greater than or equal to 70%, preferably greater than or equal to 80%, and better greater than or equal to 90% of the total volume of the dispersed oily phase and / or at least 60%, or even at least 70%, preferably at least 80%, and better at least 90%, of the drops having an average diameter greater than or equal to 100 pm, better greater than or equal to 250 pm, preferably greater than or equal to 500 pm, in particular greater than or equal to 750 pm, and better greater than or equal to 1000 pm.

[0128] Preferably, the diameter of the drops (Gl) is between 250 microns and 3,000 microns, preferably between 500 microns and 2,000 microns, or even between 750 microns and 1,500 microns.

[0129] Thus, in a dispersion according to the invention, the phases constituting it form a macroscopically inhomogeneous mixture. In other words, a dispersion according to the invention is in the form of a macroscopically inhomogeneous mixture.

[0130] Advantageously, the drops advantageously exhibit apparent monodispersity (i.e., they are perceived by the eye as spheres identical in diameter).

[0131] Preferably, the dispersions of the invention consist of a population of monodisperse droplets, in particular such that they have an average diameter of 100 pm to 3,000 pm, in particular 500 pm to 3,000 pm and a coefficient of variation Cv of less than 10%, or even less than 3%.

[0132] For the purposes of this description, "monodispersed droplets" means that the droplet population of the dispersion according to the invention has a uniform size distribution. Monodispersed droplets exhibit good monodispersity. Conversely, droplets exhibiting poor monodispersity are said to be "polydispersed".

[0133] According to one method, the average diameter of the drops is, for example, measured by Analysis of a photograph of a batch consisting of N drops, using 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 holding the drops of the dispersion.

[0134] 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 drops of said emulsion. N is advantageously greater than or equal to 100, particularly in the case where the dispersion is polydisperse.

[0135] The diameter Di of each drop is measured, then the average diameter is obtained by calculating the arithmetic mean of these values:

[0136] [Math.l] — 15 n = — yd,

[0137] From these values ​​D h, we can also obtain the standard deviation θ of the diameters of the dispersion drops:

[0138] [Math.2]

[0139] The standard deviation o of a dispersion reflects the distribution of the diameters D t of the drops of the dispersion around the mean diameter.

[0140] By knowing the mean diameter and the standard deviation θ of a dispersion, one can determine that 95.4% of the droplet population is found within the diameter range

[0141] [Math.3] [d-2ct:D + 2ct]

[0142] and that 68.2% of the population is found in the interval

[0143] [Math.4] [D cD + <t]

[0144] To characterize the monodispersity of the dispersion according to this method of the invention, the coefficient of variation can be calculated:

[0145] [Math.5]

[0146] This parameter reflects the distribution of droplet diameters as a function of their average diameter.

[0147] 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%.

[0148] Alternatively, monodispersity can be demonstrated by placing a dispersion sample in a flask with a constant circular cross-section. Gentle agitation by rotating the flask a quarter turn for half a second around the axis of symmetry passing through the flask, followed by a half-second rest, is carried out before repeating the operation in the opposite direction, and this four times in succession.

[0149] The droplets of the dispersed phase organize themselves in a crystalline form when they are monodisperse. Thus, they exhibit a stacking pattern that repeats in three dimensions. It is then possible to observe a regular stacking, indicating good monodispersity, or an irregular stacking, reflecting the polydispersity of the dispersion.

[0150] Such a monodisperse character results directly from the microfluidic manufacturing process according to the invention.

[0151] As previously stated, the drops may be monophasic or multiphasic. For example, they comprise a core (which includes at least the oily phase), and optionally a shell (or envelope or membrane) totally encapsulating the core, the core itself possibly comprising one or more phases.

[0152] According to a first embodiment, a drop according to the invention is a solid (or monophasic) particle, which can be referred to interchangeably as "pearl" or "ball".

[0153] According to a second embodiment, a drop according to the invention is a core / shell type particle. Thus, a core / shell type drop is a capsule which comprises a core, preferably liquid or at least partly gelled or at least partly thixotropic, and a shell, totally encapsulating said core, said core being monophasic, and therefore based on the oil phase.

[0154] In the case where the drops are multiphasic, a drop can then be a solid particle or of core / bark type comprising an intermediate drop (Gl) of an intermediate oily phase (14), this intermediate phase being placed in contact with the aqueous phase or the bark (when present), and at least one, preferably a single, internal drop (G2) of an internal phase (or third phase 19) disposed in the intermediate drop (Gl).

[0155] According to this variant, the intermediate fatty phase (14) advantageously comprises at least one lipophilic gelling agent, in particular as defined above, in particular to improve the suspension of the drop(s) (G2) disposed in the drop (Gl) and thus prevent / avoid the phenomena of creaming or sedimentation of the drop(s) (G2).

[0156] Preferably, the dispersed oily phase is transparent or at least translucent.

[0157] According to a particular embodiment:

[0158] - the aqueous phase (22) can itself be in the form of an emulsion direct comprising an oily phase dispersed in the form of droplets (G3) whose size is preferably smaller than the size of the droplets (G1), or even the droplets (G2); and / or

[0159] - the dispersed fat phase, or even the intermediate fat phase and / or the internal phase in the case of a multiple dispersion (or complex droplet) as defined above, may be presented in the form of a direct or inverse emulsion comprising (G4) and / or (G5) droplets, the size of the (G4) and / or (G5) droplets being necessarily smaller than the size of the (G1) droplets, or even the (G2) droplets.

[0160] The drops (G3) and / or (G4) and / or (G5) are preferably microscopic, i.e. not visible to the naked eye and in particular of a size less than 100 pm, preferably less than 20 pm, and better less than 10 pm.

[0161] In other words, the drops (G3) and / or (G4) and / or (G5) are different and independent of the drops (G1), or even of the drops (G2).

[0162] According to a first embodiment, the droplets (Gl) of a dispersion according to the invention are advantageously devoid of a shell, in particular a polymeric membrane or one formed by interfacial polymerization. In particular, the droplets (Gl) 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 continuous aqueous phase and the dispersed oily phase is preferably direct.

[0163] According to another embodiment, the drops (Gl) comprise a bark. According to this embodiment, the drops (12) of a dispersion according to the invention comprise a core (17) formed of the oily phase (14) and a bark (18), preferably formed of a coacervate layer interposed between the oily phase (14) and the aqueous phase (22).

[0164] Preferably, the bark (18) is derived from a complex interfacial coacervation reaction between the first hydrophilic gelling agent and at least one lipophilic cationic polymer capable of reacting with said first hydrophilic gelling agent, preferably selected from amodimethicone.

[0165] The presence of a bark advantageously enhances the kinetic stability of the drops (Gl), and therefore of the dispersion. Additional component(s)

[0166] A dispersion according to the invention, and in particular the aqueous phase, the oily phase, the additional solution (62) and / or the third phase (19), may further comprise at least one additional compound different from the aforementioned first hydrophilic gelling agents, oils and lipophilic gelling agents.

[0167] A dispersion according to the invention, and in particular the aqueous phase, the oily phase, the additional solution (62) and / or the third phase (19), may further comprise powders; salts; coloring agents, in particular selected from water-soluble or insoluble, fat-soluble or insoluble, organic or inorganic coloring agents, optical effect materials, liquid crystals, and mixtures thereof; fillers, in particular pigments and / or pearlescent pigments, in particular as described in FR3067930; emulsifying and / or non-emulsifying silicone elastomers, in particular as described in EP2353577; texturizing agents; hydrophilic ion-sensitive, thermosensitive, non-ion-sensitive and non-thermosensitive second gelling agents as described above; glycerin; preservatives; humectants; stabilizers; pH stabilizing agents, in particular a pH buffer (e.g. HEPES, PBS); chelating agents;emollients; retardants; etc... or any common cosmetic additive; alcohols, anti-foaming agents; silicones; and mixtures thereof.

[0168] Preferably, a dispersion according to the invention does not comprise a thermosensitive hydrophilic gelling agent, and in particular does not comprise agar, gelatin, and mixtures thereof.

[0169] Also, a dispersion according to the invention, and in particular the aqueous phase, the oily phase, the additional solution (62) and / or the third phase (19), may further comprise at least one biological and / or cosmetic active ingredient selected from among moisturizing agents, healing agents, depigmenting agents, UV filters, desquamating agents, antioxidant agents, active ingredients stimulating the synthesis of dermal and / or epidermal macromolecules, dermo-contracting agents, antiperspirant agents, soothing agents, anti-aging agents, perfumer agents, anticoagulants, antithrombogenics, antimitotic agents, antiproliferative agents, antiadhesion, antimigration agents, cell adhesion promoters, growth factors, antiparasitic molecules, anti-inflammatories, angiogenics, angiogenesis inhibitors, vitamins, hormones, the proteins, antifungals,Antimicrobial molecules, antiseptics or antibiotics, and mixtures thereof. Such active ingredients are described in particular in FR 1 558 849.

[0170] Naturally, a person skilled in the art will take care to choose any additional compound(s) and / or their quantity in such a way that the advantageous properties of a dispersion according to the invention are not, or are not substantially, altered by the envisaged addition. Likewise, a person skilled in the art will take care to choose the nature and / or quantity of the additional compound(s) according to whether the phase in question is aqueous or oily and / or with regard to the manufacturing process of the dispersion.

[0171] These adjustments fall within the general knowledge of a person skilled in the art Process

[0172] The dispersions according to the invention can be obtained by different manufacturing processes.

[0173] Thus, the dispersions according to the invention have the advantage of being able to be prepared according to a simple "non-microfluidic" manufacturing process, namely by simple emulsification.

[0174] As in a conventional emulsion, an aqueous solution and an oily solution are prepared separately. It is the addition, under agitation, of the oily phase to the aqueous phase that creates the direct emulsion, and thus the dispersion according to the invention.

[0175] The viscosity of the aqueous phase and the shear force applied to the mixture are the two main parameters that influence the size (and therefore the macroscopic character) and the monodispersity of the droplets of the dispersion according to the invention.

[0176] A person skilled in the art will be able to adjust the non-microfluidic process to satisfy the mean diameter criterion of the dispersion droplets according to the invention.

[0177] The dispersions according to the invention can also be prepared using a microfluidic manufacturing process. A microfluidic process suitable for manufacturing dispersions according to the invention is described in particular in WO2015 / 055748 or WO2019145424.

[0178] According to a first embodiment, the manufacturing process for a dispersion according to the invention is a microfluidic process, and comprises at least the steps of:

[0179] (a) have an aqueous phase (16) in a liquid form comprising water, at least one first hydrophilic gelling agent selected from a starch derivative comprising at least one carboxylic function, and optionally at least part of at least one base;

[0180] (b) have a fatty phase (14) in a substantially immiscible liquid form with the aqueous phase (16), and comprising at least one oil and optionally at least one lipophilic gelling agent;

[0181] (c) flow, in a circulation conduit (38), of drops (12) of oily phase (14) in the aqueous phase (16); and

[0182] (d) recovery of the dispersion as defined above in a container (33),

[0183] optionally the process further comprising at least one step (e) of injecting, upstream of the container (33), all or part of at least one solution (62) for increasing the viscosity of the aqueous phase (16), into the circulation conduit (38) and / or at the outlet of the circulation conduit (38), and preferably at the outlet of the circulation conduit (38), said solution (62) comprising at least the other part of the base.

[0184] Preferably, in such a microfluidic process, the drops (12) and the phase (16) flow along a local axis in the circulation conduit (38), the injection of the viscosity-increasing solution (62) being carried out substantially coaxially with the local axis.

[0185] Preferably, in such a microfluidic process, the injection of the viscosity-increasing solution (62) in step (e) involves bringing at least a portion of the viscosity-increasing solution (62) (i) to the center of the flow of the drops (12) and the aqueous phase (16) and / or (ii) to the periphery of the flow of the drops (12) and the aqueous phase (16).

[0186] Preferably, such a microfluidic process is characterized in that it includes, upstream of the flow step (c), a drop formation step (12) in the circulation conduit (38).

[0187] According to a first embodiment, a manufacturing process according to the invention without additional solution (62), in which case the base is entirely contained in the aqueous phase (16).

[0188] According to a second embodiment, the manufacturing process according to the invention uses the additional solution (62), said additional solution (62) comprising all the base. Mechanically, the aqueous phase (16) is then devoid of base.

[0189] According to a third embodiment, a manufacturing process according to the invention uses an aqueous phase (16) comprising a portion of the base and an additional solution (62) comprising the other portion of the base. In other words, the gelation of the aqueous phase continues according to this third embodiment at two different stages of the process. According to this third embodiment, the bases present in the aqueous phase (16) and in the additional solution (62) may be identical or different. Such an embodiment is particularly advantageous in that it can improve the stability and robustness of the manufacturing process, and in particular improve the proper formation of the droplets.

[0190] Contrary to expectations, the properties of the aqueous phase in step (a) allow the aqueous phase (16) in step (c) to be used at room temperature, which, for obvious reasons, is advantageous from an economic and environmental standpoint, and even more so when considering an industrial scale. Indeed, such a process according to the invention does not require heating the aqueous phase (16) for step (c). This also has the advantage of eliminating the need for cooling in step (d). In fact, it is now the aqueous phase (16) that will cool the oily phase (14) when the latter is preheated for step (c).

[0191] Contrary to expectations, the inventors observed that, even when endowed with high contents of first hydrophilic gelling agent, the aqueous phase (16) remains in a fluid form at room temperature and therefore remains compatible with a microfluidic process according to the invention.

[0192] The liquid character of the fat phase (14) required in step (c) can be obtained by means of sufficient shear and / or an increase in temperature, in particular when the fat phase (14) includes at least one lipophilic gelling agent.

[0193] In particular, this step (c) can be carried out at a temperature greater than or equal to the highest melting point of the lipophilic gelling agent(s), and preferably at a temperature between 70°C and 120°C, and in particular between 80°C and 100°C.

[0194] The microfluidic steps of the manufacturing process according to the invention may be as described in WO2012 / 120043, WO2015 / 055748 or WO2019145424.

[0195] A method for manufacturing a dispersion according to the invention is advantageously implemented using the apparatus (30) illustrated by [Fig.1], which includes a nozzle (32) for forming the drops (12), a receptacle (33) for receiving the drops (12) formed, and optionally a stage (31) for injecting the additional solution (62).

[0196] In the case of a simple dispersion, the forming nozzle (32) includes at least one internal conduit (34) for supplying an internal fluid (36) comprising a first phase (14), and an external circulation conduit (38), arranged around the internal conduit (34) to supply and circulate an external fluid (40) comprising the phase (16).

[0197] The apparatus (30) further includes means (46) for supplying internal fluid (36) into the internal conduit (34), and means (48) for supplying external fluid (40) into the annular space delimited between the internal conduit (34) and the external conduit (38).

[0198] In the example shown in [Fig.1], the maximum diameter of the conduits (34) and (38) is less than 3 mm to preserve the microfluidic character of the process.

[0199] The internal conduit (34) is advantageously arranged coaxially in the external conduit (38). It is connected upstream to the supply means (46). It opens downstream through a downstream opening (54) arranged in the external conduit (38).

[0200] The external conduit (38) delimits with the internal conduit (34) an annular space connected upstream to the supply means (48).

[0201] The external conduit (38) has a downstream opening (55) which is located above and away from the container (33). The embodiment described in [Fig. 1] includes the use of an additional solution (62). In fact, the downstream opening (55) leads into the injection stage of the solution (62).

[0202] The supply means (46) and (48) each include, for example, a syringe pump, a peristaltic pump or another pressure-generating system controlling the flow, such as, for example, a pressure pot coupled with a flow meter and a flow regulation system.

[0203] Each of the supply means (46) and (48) is suitable for conveying a respective fluid (36) and (40) at a controlled and adjustable flow rate.

[0204] The container (33) is arranged below a distribution opening (66) for the dispersion (72) according to the invention.

[0205] In the case of multiple dispersion, the forming nozzle (32) (not shown) comprises at least one internal conduit (34) for supplying a third fluid (36) intended to form a third phase (19), and an intermediate conduit (37) for supplying the internal fluid (39) comprising the first phase (14), arranged around the internal conduit (34). Such a forming nozzle (32) is described in particular in Figure 5 of patent application filed under No. FR3129605.

[0206] The forming nozzle (32) further includes an external circulation conduit (38), arranged around the internal conduit (34) and / or the intermediate conduit (37) to bring in and circulate an external fluid (40).

[0207] The apparatus (30) further comprises means (46) for supplying the third fluid (36) into the internal conduit (34), means (47) for supplying internal fluid (39) into the intermediate conduit (37), and means (48) for supplying external fluid (40) into the annular space delimited between the internal conduit (34) and the external conduit (38).

[0208] The internal conduit (34) is advantageously arranged coaxially in the external conduit (38). It is connected upstream to the supply means (46). It opens downstream through a downstream opening (52) arranged in the external conduit (38), set back from the downstream opening (54) defined by the intermediate conduit (37), above this opening (54).

[0209] The intermediate conduit (37) extends around the internal conduit (34). It delimits, together with the internal conduit (34), an annular space connected upstream to the supply means (47). The intermediate conduit (37) opens through the downstream opening (54).

[0210] The external conduit (38) delimits with the intermediate conduit (37) and / or the internal conduit (34) an annular space connected upstream to the supply means (48).

[0211] The external conduit (38) has a downstream opening (55) which is located above and away from the container (33). According to the embodiment of the manufacturing process considered, the downstream opening (55) may lead into the injection stage of the phase (16b) which may represent an additional solution (62).

[0212] The supply means (46), (47) and (48) each include, for example, a syringe pump, a peristaltic pump or another pressure-generating system controlling the flow, such as, for example, a pressure pot coupled with a flow meter and a flow regulation system.

[0213] Each of the supply means (46), (47) and (48) is suitable for conveying a respective fluid (36), (39), (40) at a controlled and adjustable flow rate.

[0214] According to the invention, the stage (31) includes at least one conduit (60) for injecting a solution (62), and means for bringing (64) the solution (62) into the conduit (60).

[0215] The supply means (64) comprise a reservoir (68) containing the solution (62), and a conveying unit (not shown).

[0216] The conveying unit includes, for example, a syringe pump, a peristaltic pump or another pressure generating system controlling the flow, such as, for example, a pressure pot coupled with a flow meter and a flow regulation system.

[0217] For the manufacturing process according to the first embodiment described above, the container (33) is arranged below the dispensing opening (55) (not shown).

[0218] For the manufacturing process according to the second embodiment described above, the container (33) is arranged below the dispensing opening (66).

[0219] Alternatively, the container (33) contains a volume (70) of liquid intended to form part of the continuous aqueous phase.

[0220] In the example shown in [Fig. 1], the device (30) has been illustrated with a single nozzle (32) associated with a single stage (31). In an advantageous embodiment, illustrated in Figure 8 of patent application filed under No. FR3129605, the system (30) comprises a plurality of nozzles (32), all connected downstream to a common stage (31), the nozzles (32) being arranged in parallel above a container (33). The nozzles (32) are offset laterally with respect to the stage (31). A collection circuit gathers the droplets (12) in the liquid (40) exiting each nozzle (32) to collect them and introduce them into the stage (31). Uses

[0221] Preferably, a dispersion according to the invention is directly usable, at the end of the aforementioned preparation process, as a composition, in particular cosmetic, pharmaceutical, nutritional or agri-food, and preferably cosmetic.

[0222] The invention also relates to the use of a dispersion according to the invention for the preparation of a composition, in particular cosmetic, pharmaceutical, nutritional or food composition, preferably cosmetic and in particular a skincare and / or makeup composition of a keratinous material, in particular from human beings, in particular from the skin.

[0223] Thus, the present invention also relates to a composition, in particular cosmetic, in particular for skincare and / or makeup, of a keratinous material, in particular of the skin and / or hair, and more particularly of the skin, comprising at least one dispersion according to the invention, optionally in association with at least one physiologically acceptable medium.

[0224] Preferably, a dispersion according to the invention is not a cleaning product, and in particular is not a personal cleansing product, and especially is not a shampoo, shower gel or other cleaning product.

[0225] Preferably, a dispersion according to the invention is not a rinse-off product. In other words, a dispersion according to the invention, particularly when intended for cosmetic use, is preferably a leave-on product.

[0226] In the context of the invention, and unless otherwise stated, "physiologically acceptable medium" means a medium suitable for cosmetic applications, and suitable in particular for the application of a composition of the invention on a keratinous material, in particular the skin and / or hair, and more particularly the skin.

[0227] A dispersion or composition, according to the invention, is intended for oral or topical application, preferably topical.

[0228] A cosmetic dispersion or composition of the invention may be, for example, a cream, lotion, serum, or gel for the skin (hands, face, feet, etc.), a foundation (liquid, paste), a hair care product (hair dyes and bleaches), a hair conditioning product (lotions, creams, oils), a styling product (lotions, hairsprays, glosses), a product for application to the lips, a sunscreen, a sunless tanning product, a skin-whitening product, or an anti-wrinkle product. In particular, a cosmetic composition of the invention may be an anti-aging serum, a youth serum, a moisturizing serum, or a perfumed water.

[0229] According to one embodiment, a dispersion or composition according to the invention may be in the form of a foundation, a makeup remover, a face and / or body and / or hair care product, an anti-aging treatment, a sunscreen, an oily skin care product, a whitening treatment, a moisturizing treatment, a BB cream, tinted cream or foundation.

[0230] Preferably, a dispersion or composition according to the invention is not a face and / or body cleanser, a shower gel or a shampoo.

[0231] The present invention also relates to a non-therapeutic cosmetic treatment method for keratinous material, in particular skin and / or hair, comprising at least one step of applying to the keratinous material at least one of the aforementioned cosmetic dispersions or compositions.

[0232] The present invention also relates to the use of a dispersion or composition according to the invention, to improve the surface appearance of the skin, in particular for to hydrate, protect, treat the skin and / or reduce the signs of skin aging, in particular and / or reduce wrinkles and fine lines.

[0233] Throughout the description, the expression "including one" shall be understood as synonymous with "including at least one", unless otherwise specified. The expressions "between ... and ...", "from ... to ..." and "ranging from ... to ..." shall be understood inclusive, unless otherwise specified.

[0234] Specific examples of implementing the process according to the invention for obtaining compositions in the form of dispersions will now be described. EXAMPLES

[0235] Unless otherwise indicated, in the following examples:

[0236] - the production of the dispersions is carried out using a microfluidic device as described in WO2012120043. If necessary, the device is adapted to allow the injection of an additional solution (BF) after drop formation, as described in WO2015055748, and / or to heat the oil phase to 80°C. - Viscosity is measured at ambient temperature and pressure using the following method: - A Brookfield-type viscometer is used, typically a Brookfield RVDV-E digital viscometer (spring torque of 7187.0 dyne-cm), which is a rotational viscometer with imposed speed equipped with a spindle. A speed is imposed on the rotating spindle, and the measurement of the torque exerted on the spindle allows the viscosity to be determined by knowing the geometry / shape parameters of the spindle used. - For example, a No. 04 size rotary vane (Brookfield reference: RV4) is used. The shear rate corresponding to the viscosity measurement is defined by the rotary vane used and its rotation speed. The viscosity measurement is performed over 1 minute at room temperature (T=25°C ± 2°C). Approximately 150 g of solution is placed in a 250 ml beaker with a diameter of approximately 7 cm, ensuring that the volume occupied by the 150 g of solution is sufficient to reach the mark on the measuring device. The viscometer is then started at a speed of 10 rpm and the reading on the screen is allowed to stabilize. This measurement provides the viscosity of the fluid tested, as described in the present invention. - Suspensivity is evaluated after placing half-filled 30 ml polypropylene (PP) receptacles of the different tests to be tested for 1 month at 50°C. - The transparency of the continuous aqueous phase is determined as follows: the composition to be tested is poured into a 30 mL Volga flask, left for 24 hours at room temperature, and a white sheet of paper is placed underneath, on which a cross approximately 2 mm thick is drawn with a black marker. If the cross is visible to the naked eye in daylight at an observation distance of 40 cm, the composition is transparent. - Scoring criteria: the tests in the examples below are evaluated in terms of compatibility with the microfluidic manufacturing process, viscosity, suspensivity and transparency, as described in Tables 1 and 2 below.

[0237] [Tables 1] Table 1 Compatibility of OF* with the microfluidic manufacturing process Aqueous phase viscosity (22) Aqueous phase suspensivity (22) Aqueous phase transparency (22) Aqueous phase stickiness (22) Occurrence of any phenomena impacting the manufacturing process, for example: - ejection of drops from a dripping mode to a dejetting mode; - nozzle clogging; and / or - formation of non-spherical bubbles More or less liquid / viscous / solid character Creaming of oil phase droplets More or less opaque character More or less sticky character

[0238] * OF: Aqueous phase injected into the microfluidic device

[0239] [Tables2] Table 2 RATING CRITERIA 0 1 2 3 OF* compatibility with the microfluidic manufacturing process Robust process (no clogging or spherical bubbles) Slight instability (slight clogging or not-too-spherical bubbles) Medium instability (clogging and not-totally-spherical bubbles) High instabilities (clogging and non-spherical bubbles or no (spherical) bubbles produced) Viscosity Aqueous phase (22) in the form of a liquid gel Aqueous phase (22) slightly viscous liquid Aqueous phase (22) viscous liquid Aqueous phase (22) very viscous, even solid Suspensivity Suspension stable for at least 1 month at 50°C Suspension stable between 2 weeks and 1 month at 50°C Suspension stable between 1 and 2 weeks at 50°C Suspension stable for less than 1 week at 50°C Transparency Aqueous phase (22) transparent Aqueous phase (22) slightly opaque Aqueous phase (22) moderately opaque Aqueous phase (22) very opaque Stickiness Aqueous phase (22) non-sticky Aqueous phase (22) slightly sticky Aqueous phase (22) sticky Aqueous phase (22) very sticky

[0240] * OF: Aqueous phase injected into the microfluidic device

[0241] For each trial, a score of 3 on at least one of the parameters evaluated above is considered disqualifying.

[0242] Six dispersions are prepared using the microfluidic device described above, tests 1 to 5 being outside the scope of the invention and test 6 being according to the invention. The composition of the starting phases is described in Tables 3 and 4 below.

[0243] [Tables3] Phase Raw materials iNCÏ %w / w phase Fatty phase (PG) Labrafac CC [MB] Ca p ry bind / G a prie triglyceride Qsp* Nikkol Meadowfoam oil Lirnnanthes Allas (Meadowfoam) Seed Oil 20 EMC30 Castor Oü / IPDI Copoiymer (and) Capryltc / Capric Triglyceride 33 Total 190 Aqueous phase (PA) Water bone m osée Agita Qsp* NaMquesi E30 Aqua, tnsodiumelytenediamlne disuccinate 0.17 Microcaré Emollient PTG Pentyfené Glycoi 2.22 Glycerin 4811 Glycerin 77 Zemeà Select Propanediol Propanediol 1.9 Nipaguard CP Chlorphenesin 0.3 Makilene GC Butylene giycoi. Aqua 2.56 Hydrophilic gelling agent(s) See Table 4 Total 100 Additional solution (BF)** Gelling activator See Table 4 Water Qsp* Total 106 * Sufficient Quantity For. BP not present for tests 2 and 8 to 10.

[0244] * Sufficient Quantity For.

[0245] ** BF not present for test 2.

[0246] [Tables4] Table 4 Gelling Agents (Hydrophilic) (% by weight relative to the weight of the aqueous phase (22)) Gelling Activator (% by weight relative to the weight of the aqueous phase (22)) Test Carbopol Uitrez 10 JNA KANTEN CS-200 STR Satiagef VPC 508 P Sclerothix Keîcogel CG LA Carbopol Fusion S-20 NaOH Salt Carbomer Agar loia-Carrageenan (and) Chondrus Crispus Extract Xanthan Gum (and) Sclerotium Gum (and) Asqin Geftan gum Starch Acetate / Adipate, Citric Acid Sodium Hydroxide SODIUM CHLORIDE CALCIUM CHLORIDE 1 0.28 - 0.7 2 0.3 - - MA* 3 0.4 - 1 4 - 0.4 - - 1 - 5 - 0.1 - 0.2 6 - - 15'* 0.6 - -

[0247] * NA: Not Applicable; agar being a thermosensitive hydrophilic gelling agent, its presence in OF does not require a gelling activator.

[0248] ** 15% of Carbopol Fusion S-20 corresponds to 3.15% of active material. Preparation protocol:

[0249] The preparation of the aqueous and oily phases falls within the general knowledge of a person skilled in the art. The aqueous phase is prepared at room temperature. The oily phase is prepared at 80°C to allow the solubilization of all the materials. For tests 1 and 3 to 6, the BF is injected into the aqueous phase (PA) after droplet formation. Test 2 does not include BF.

[0250] The flow rates (in mL / hr per nozzle) used are described in Table 5.

[0251] [Tableaux5] Table 5 OF IF BF 1 and 3 to 6 Trial 150 20.35 16.67 2 166.67 20.35 -

[0252] In relation to the different embodiments of the manufacturing process described above, the aqueous phase injected into the microfluidic device:

[0253] - for tests 1 and 3 to 6, corresponds to an aqueous phase (16); and

[0254] - for test 2, corresponds to the aqueous phase (22). Results#:

[0255] [Tableauxô] Table 6 Test Compatibility with Microfluidic Manufacturing Process Viscosity Suspensivity Transparency Stickiness Rating Value (in cP) 1 0 1 8000 0 0 0 2 0 3 NA* NA* NA* NA* 3 0 1 4000 3 0 1 4 0 1 1500 3 0 1 5 0 1 300 3 1 0 6 0 1 2000 0 0 0

[0256] * NA = Not Applicable

[0257] The dispersions obtained include drops having an average diameter of 800 pm.

[0258] Test 1, which comprises an aqueous phase (22) comprising Carbomer, is the Control.

[0259] Test 2 is in the form of a firm and brittle gel.

[0260] Tests 3 to 5, in terms of suspensivity, although satisfactory at room temperature, have insufficient performance at 50°C.

[0261] Test 6 according to the invention is the one that exhibits the characteristics closest to the Control. This observation is all the more unexpected given that such an aqueous phase is:

[0262] - compatible with the constraints inherent in a microfluidic process, in particular in terms of viscosity limit,

[0263] - compatible with injection into the microfluidic device at temperature ambient, which is particularly advantageous from a safety, simplicity and energy-saving point of view,

[0264] - satisfactory in terms of fluidity and transparency, and

[0265] - suspensive with respect to oil phase drops, which is unexpected given of a viscosity much lower than the viscosity of test 1.

[0266] Test 6 is stable and has satisfactory performance at least similar to that of test 1 in terms of non-stickiness and play-time, which again is unexpected.

[0267] This example shows that it is therefore possible to manufacture a macroscopic dispersion comprising a fluid gelled aqueous phase devoid of carbomer but still having a tunable viscosity and which after activation remains flexible, fluid and slightly cohesive.

Claims

Demands

1. Dispersion comprising a fat phase (14) in the form of drops (12) dispersed in a continuous aqueous phase (22), the fat phase (14) and the aqueous phase (22) being immiscible, in which the aqueous phase (22) comprises water, at least one base and at least one first hydrophilic gelling agent selected from at least one starch derivative comprising at least one carboxylic function, the dispersion being devoid of carbomer.

2. Dispersion according to the preceding claim, wherein the aqueous phase (22) is a fluid gelled aqueous phase.

3. Dispersion according to claim 1 or 2, wherein the aqueous phase (22) has a viscosity, as measured at 25°C and under a shear stress of 2 s'1, of 500 mPa.s to 50,000 mPa.s, preferably from 1,000 mPa.s to 25,000 mPa.s, in particular from 500 mPa.s to 15,000 mPa.s, in particular from 1,000 mPa.s to 10,000 mPa.s, and most particularly from 1,000 mPa.s to 5,000 mPa.s.

4. Dispersion according to any one of the preceding claims, wherein the aqueous phase (22) has a yield stress greater than or equal to 0.1 Pa, in particular greater than or equal to 1 Pa, and preferably between 0.25 Pa and 100 Pa, in particular between 0.5 Pa and 75 Pa, especially between 1 Pa and 50 Pa, or even between 2 Pa and 25 Pa, and better between 3 Pa and 20 Pa.

5. Dispersion according to any one of the preceding claims, wherein the first hydrophilic gelling agent is selected from a carboxymethylated starch, a carboxyethyl starch, an oxidized starch, a grafted starch, one of their derivatives, and mixtures thereof, and preferably selected from a grafted starch or one of its derivatives.

6. Dispersion according to any one of the preceding claims, wherein the first hydrophilic gelling agent has the INCI name: “Starch Acetate / Adipate (and) Citric Acid”.

7. Dispersion according to any one of the preceding claims, wherein the aqueous phase (22) comprises between 0.1% and 10%, preferably between 0.5% and 7.5%, better between 1% and 5%, and particularly between 2% and 4%, by weight of first hydrophilic gelling agent(s) relative to the total weight of the aqueous phase (22).

8. Dispersion according to any one of the preceding claims, wherein the base is selected from an alkali hydroxide, and preferably sodium hydroxide.

9. Dispersion according to any one of the preceding claims, wherein the aqueous phase (22) comprises between 0.1% and 20%, preferably between 0.25% and 15%, better between 0.5% and 10%, and most particularly between 0.25% and 5%, by weight of base(s) relative to the total weight of the aqueous phase (22).

10. Dispersion according to any one of the preceding claims, wherein the drops (12) having a diameter greater than or equal to 100 pm represent a volume greater than or equal to 60%, or even greater than or equal to 70%, preferably greater than or equal to 80%, and better than or equal to 90% of the total volume of the dispersed oil phase and / or at least 60%, or even at least 70%, preferably at least 80%, and better than at least 90%, of the drops have an average diameter greater than or equal to 100 pm.

11. Dispersion according to any one of the preceding claims, wherein the dispersion comprises from 1% to 60%, in particular from 5% to 50%, preferably from 10% to 40%, and better from 15% to 30%, by weight of fat phase (14) relative to the total weight of the dispersion.

12. Dispersion according to any one of the preceding claims, wherein the oil phase (14) comprises at least one oil and optionally at least one lipophilic gelling agent, preferably heat-sensitive, and in particular selected from lipophilic gelling agents, organic or mineral, polymeric or molecular; solid fats at ambient temperature and pressure; and mixtures thereof.

13. Dispersion according to any one of the preceding claims, wherein the drops (12) comprise a core (17) formed from the oily phase (14) and a bark (18), preferably formed from a layer of coacervate interposed between the oily phase (14) and the aqueous phase (22).

14. Dispersion according to the preceding claim, wherein the bark (18) is derived from a complex interfacial coacervation reaction between the first hydrophilic gelling agent and at least one lipophilic cationic polymer capable of reacting with said first hydrophilic gelling agent, preferably selected from amodimethicone.

15. Dispersion according to any one of the preceding claims, said dispersion not being a cleaning product, and in particular not being a personal cleaning product, and especially not being a shampoo, shower gel or other cleaning product.

16. A method for manufacturing a dispersion according to any one of the preceding claims, the method comprising at least the steps of: (a) having an aqueous phase (16) in liquid form comprising water, at least one first hydrophilic gelling agent selected from a starch derivative comprising at least one carboxylic function, and optionally at least a portion of at least one base; (b) having an oily phase (14) in liquid form, substantially immiscible with the aqueous phase (16), and comprising at least one oil and optionally at least one lipophilic gelling agent; (c) flowing, through a circulation conduit (38), droplets (12) of oily phase (14) into the aqueous phase (16);and (d) recovery of the dispersion according to any one of the preceding claims in a container (33), optionally the process further comprising at least one step (e) of injecting, upstream of the container (33), all or part of at least one solution (62) for increasing the viscosity of the aqueous phase (16), into the circulation conduit (38) and / or at the outlet of the circulation conduit (38), and preferably at the outlet of the circulation conduit (38), said solution (62) comprising at least the other part of the base.

17. A method according to the preceding claim, characterized in that it comprises, upstream of the flow step (c), a drop formation step (12) in the circulation conduit (38).

18. A composition, in particular a cosmetic, in particular a skincare and / or makeup composition of a keratinous material, in particular of the skin and / or hair, and more particularly of the skin, comprising at least one dispersion according to any one of claims 1 to 15, optionally in association with at least one physiologically acceptable medium 34

19. A non-therapeutic cosmetic treatment process for keratinous material, in particular skin and / or hair, comprising a step of applying to the keratinous material at least one dispersion according to any one of claims 1 to 15 or a composition according to claim 18.

Images