EP1667636A2

EP1667636A2 - Emulsions comprising a dendritic polymer and use of a dendritic polymer as an emulsification agent

Info

Publication number: EP1667636A2
Application number: EP04787480A
Authority: EP
Inventors: Mikel Morvan; Alain Senechal; Olivier Anthony; Franck Hameau de Normandie TOURAUD; Jean-François SASSI; Katerina Karagianni; René Les Hauts du Golf ROSSIN
Original assignee: Rhodia Chimie SAS
Current assignee: Rhodia Chimie SAS
Priority date: 2003-09-29
Filing date: 2004-09-29
Publication date: 2006-06-14
Also published as: WO2005032497A2; WO2005032497A3; US20070202071A1

Abstract

The invention relates to novel emulsions comprising a dendritic polymer. The invention also relates to the use of a dendritic polymer as an emulsification agent. The inventive emulsions are suitable for use in the cosmetics, detergents, paint and coatings industries.

Description

Emulsions comprising a dendritic polymer and use of a dendritic polymer as an emulsifying agent

The present invention relates to new emulsions, comprising a dendritic polymer. It also relates to the use of a dendritic polymer as an emulsifying agent. Emulsions are physico-chemical structures, or systems, which find applications in many fields. We also speak of formulations in the form of emulsions. Areas of application include cosmetic formulations, detergency formulations, coating formulations

(paint, etc.), certain polymerization processes (preparation of latex, preparation of polymers or copolymers based on polyacrylamide), phytosanitary formulations. Emulsions are also a means of vectorization or protection of a compound (internal phase or compound included in the internal phase). An emulsion comprises at least two immiscible liquid phases, an external phase and an internal phase dispersed in the form of droplets in the external phase. Often one of the two phases is an aqueous phase. If the external phase is aqueous, we often speak of a direct emulsion, or an "oil in water" emulsion. If the internal phase is aqueous, we often speak of an inverse emulsion, or a "water in oil" emulsion. An emulsion also generally comprises an emulsifying agent, playing a role at the interfaces of the droplets. An emulsion is generally prepared by more or less vigorous mixing of the two phases and, where appropriate, of the emulsifying agent. If the mixture obtained is at thermodynamic equilibrium, we generally speak of a microemulsion. If the mixture obtained is out of thermodynamic equilibrium, energy having been conferred on the system by the mixture, one generally speaks simply of emulsion. In the present application, the term “emulsion” naturally covers emulsions, and also microemulsions. The size of the droplets, and their stability over time, depend in particular on the nature and the quantity of the different phases and of the emulsifying agent. They also generally depend on the strength of the mixture used to obtain them (amount of energy imparted to the system). Thus, an emulsifying agent, and its quantity, can be chosen according to the phases to be emulsified. Many emulsifying agents are known. Among the most used, there may be mentioned surfactants. They are often molecules of relatively low molecular weight comprising a hydrophilic part and a hydrophobic part. These agents can have drawbacks in certain applications. They are often irritating, which has a major drawback, for example in the areas of cosmetics and pharmacy. They can also have a negative impact on the environment. Their presence in certain formulations, in particular in coating formulations such as paints, can induce migration phenomena at the interfaces, and thus induce problems of appearance or cohesion with the coated object. Finally, they are often strongly foaming, which is not always desired for the formulation and can induce difficulties during the preparation of a formulation. Polymeric emulsifiers are also known. Mention may be made, for example, of poly (ethylene oxide) -poly (propylene oxide) - poly (ethylene oxide) block copolymers used for producing direct emulsions. Mention may also be made of the polyhydroxystearate-PEG-polyhydroxystearate type copolymers, for example sold under the name Arlacel or Superonic, by Uniquema, used for the production of reverse emulsions. The use of polysaccharides and polysaccharide derivatives is also known. These polymeric agents provide solutions for the emulsification of particular systems for which a sufficiently effective surfactant is not known (quantity introduced, stability over time, etc.), or for which a surfactant would have drawbacks, such as those which were mentioned above. However, the possibilities of using these polymeric compounds are limited. For example, they may exhibit low resistance at high temperature, or significant degradability in formulations comprising enzymes. The present invention relates to new emulsions, new in particular by the emulsifying agent, constituting an alternative to known emulsions. It therefore relates to the new use of a polymeric compound as an emulsifying agent. The emulsions according to the invention, and the use according to the invention, have in particular the advantage of low foaming, and / or resistance at high temperature, and / or low degradability in formulations comprising enzymes and / or a great versatility of use. The emulsions according to the invention, and the use according to the invention, have the advantage, for reverse emulsions, of making it possible to obtain small, stable dispersions. In addition, the emulsions according to the invention have the advantage of being stable in a wide variety of media. They are also stable when the external phase is an aqueous phase, which can contain a wide variety of products. They can be used in the presence of a significant amount of a detergent such as a surfactant, for example an anionic surfactant. Under certain conditions and formulations, the emulsifying agent can be adsorbed on surfaces, and thus serve as a vector for deposition of the internal phase on a surface. In particular, such vectorization by the emulsifying agent is not screened by the presence of anionic surfactants. This is particularly useful for detergents or shampoos.

Thus, the invention provides an emulsion comprising an internal phase, an external phase, and an emulsifying polymer, one of the phases being an aqueous phase, characterized in that the emulsifying polymer is a dendritic polymer. Likewise, the invention proposes the use of a dendritic polymer as an emulsifying agent. It is specified that the emulsions according to the invention comprise the dendritic polymer as an emulsifying agent, but that it is not excluded that they additionally comprise one or more other emulsifying agents. We sometimes speak of co-emulsifiers or emulsifier toner, for example surfactant toner ("surfactant booster"). In the context of reverse emulsions, the dendritic polymer is advantageously used as the sole emulsifying agent.

Emulsion phases The emulsion comprises at least two immiscible liquid phases, an internal phase and an external phase, one of which is aqueous. It is not excluded that the emulsion comprises three immiscible phases, the emulsion then having an aqueous phase, a first group of droplets (first internal phase) dispersed in the external phase, and a second group of droplets (second phase internal) dispersed in the external phase. It is also not excluded that a phase (aqueous phase or not) immiscible with the internal phase are dispersed in the form of droplets inside the droplets of the internal phase. In this case we often speak of multiple emulsions, including an internal emulsion and an external emulsion. For example, they can be water in oil in water emulsions, comprising an internal phase (water), an intermediate phase (oil) and an external phase. The dispersion of the internal phase in the intermediate phase constitutes an internal inverse emulsion, the dispersion of the intermediate phase in the external phase constitutes a direct external emulsion. Similarly, in the present application, we can speak of an internal or external emulsifying agent. In the present application, the notion of reverse emulsion covers both a simple reverse emulsion and an internal reverse emulsion of a multiple emulsion. The notion of direct emulsion covers both a simple direct emulsion and an external direct emulsion of a multiple emulsion. Aqueous phase The aqueous phase can be an external phase, if necessary an external phase of a multiple emulsion. We are talking about direct emulsions. The aqueous phase is an internal phase, if necessary the external phase of a multiple emulsion. We are talking about reverse emulsions. The aqueous phase naturally includes water, and if necessary other compounds. The other compounds can be solvents or co-solvents, dissolved or solid compounds dispersed in water, for example active materials. By "other compounds" of the aqueous phase, we do not mean the internal liquid phase or the intermediate phase of a multiple emulsion. The dendritic polymer is preferably dispersible or soluble in water. The aqueous phase may also contain compounds intended to give the solution a certain pH, and / or salts having no appreciable influence on the pH. It is specified that the pH can have an influence on the water solubility of the dendritic polymer and on the hydrophilicity of groups included in the dendritic polymer. This is particularly the case for carboxylic acid groups, and for amino groups. It is preferable to be placed under pH and concentration conditions such that the dendritic polymer is dispersible or soluble in water, and / or such that groups sensitive to pH are in ionic form. If there is a pH limit above or below which the dendritic polymer is dispersible or soluble, the pH is preferably within a range from the limit to 2 units above or below the limit, in the area of dispersibility or solubility. Such conditions and groups are detailed below, in connection with the description of dendritic polymers. The aqueous phase can also comprise compounds usually used in the fields of formulations in the form of emulsions or comprising emulsions, for example in the fields of household care (detergency, detergents, cleaning of hard surfaces, dishes), in the fields of cosmetics (hair care, shampoo, shower gels, creams, milks, lotions, gels, deodorants), in the industrial fields (emulsion polymerization, surface treatments in industrial processes, lubrication, etc.), in the fields of coatings , for example in paintings. It may for example be surfactants, anionic, cationic, amphoteric, onical zwitte, or nonionic, detergency builders (hydrosolics), hydrophilic active agents, salts, viscosifiers. Non-aqueous phase The emulsion comprises a phase which is immiscible with the aqueous phase. To put it simply, this phase will be designated by "non-aqueous phase" or by "oil phase", or by "hydrophobic phase". By immiscible phases is meant that one phase is not more than 10% soluble in the other phase, at a temperature of 20 ° C. The non-aqueous phase can be the internal phase (direct emulsions), or the external phase (reverse emulsions). It may especially be an intermediate phase of a multiple emulsion. Examples of compounds constituting the non-aqueous phase, or included in the non-aqueous phase include: - organic oils / fats / waxes of animal or vegetable origin;

- mineral oils / waxes, for example hydrocarbon paraffins;

- products derived from the alcoholysis of the abovementioned oils and possibly from a subsequent esterification;

- the products resulting from the trans-esterification of the abovementioned oils; - essential oils;

- mono-, di- and tri-glycerides;

- fatty acids, saturated or not, comprising 10 to 40 carbon atoms; esters of such acids and of alcohol comprising 1 to 6 carbon atoms;

- monoalcohols, saturated or not, comprising 2 to 40 carbon atoms; - polyols comprising 2 to 10 carbon atoms;

- silicones, in particular amino silicones;

- hydrocarbons or cuts of hydrocarbons;

- water-insoluble monomers, in particular used for isocyanate polymerizations with polyols or for latex polymerizations, - water insoluble resins or macromonomers precursors, such as alkyd or isocyanate compounds. As organic oils / fats / waxes of animal origin, there may be mentioned, among others, sperm whale oil, whale oil, seal oil, shark oil, cod liver oil, pork and mutton fats (tallow), perhydrosqualene, beeswax, alone or in a mixture. As examples of organic oils / fats / waxes of vegetable origin, there may be mentioned, inter alia, rapeseed oil, sunflower oil, peanut oil, olive oil , walnut oil, corn oil, soybean oil, avocado oil, linseed oil, hemp oil, grape seed oil, copra, palm oil, cotton seed oil, babassu oil, jojoba oil, sesame oil, castor oil, macadamia oil, d oil sweet almond, camauba wax, shea butter, cocoa butter, peanut butter, alone or in a mixture. As regards mineral oils / waxes, there may be mentioned, inter alia, naphthenic, paraffinic (petrolatum), isoparaffinic oils, paraffinic waxes, alone or as a mixture. The products derived from the alcoholysis of the abovementioned oils can also be used. Among the essential oils that may be mentioned without intending to be limited thereto, oils and / or essences of mint, spearmint, peppermint, menthol, vanilla, cinnamon, bay leaf, anise, d 'eucalyptus, thyme, sage, cedar leaf, nutmeg, citrus (lemon, lime, grapefruit, orange), fruit (apple, pear, peach, cherry, plum, strawberry, raspberry, apricot , pineapple, grapes, etc.), alone or in mixtures. As regards fatty acids, the latter, saturated or unsaturated, contain 10 to 40 carbon atoms, more particularly 18 to 40 carbon atoms, and can comprise one or more ethylenic unsaturations, conjugated or not. It should be noted that said acids may comprise one or more hydroxyl groups. As examples of saturated fatty acids, mention may be made of palmitic, stearic and behenic acids. As examples of unsaturated fatty acids, there may be mentioned myristoleic, palmitoleic, oleic, erucic, linoleic, linolenic, arachidonic, ricinoleic acids, as well as their mixtures. As regards fatty acid esters, mention may be made of the esters of the acids listed above, for which the part deriving from the alcohol comprises 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, etc. As an example of alcohols of these esters, mention may be made of ethanol and those corresponding to the abovementioned acids. Among the suitable polyols of these esters, mention may preferably be made of glycerol. The nonaqueous phase can comprise a silicone or a mixture of several of them. We often speak of silicone oils. Amino silicones are particularly useful in the areas of detergency. More details are given below as regards the silicones. It may in particular be an oil, a wax or a resin in a linear, cyclic, branched or crosslinked polyorganosiloxane. Said polyorganosiloxane preferably has a dynamic viscosity measured at 25 ° C. and at a shear rate of 0.01 Hz for a stress of 1500 Pa (carried out on a Carrimed® of the CSL2-500 type) of between 10 ⁴ and 10 ⁹ cP. It can notably be:

• a non-ionic polyorganosiloxane • a polyorganosiloxane having at least one cationic or potentially cationic function

• a polyorganosiloxane having at least one anionic or potentially anionic function • an amphoteric polyorganosiloxane having at least one cationic or potentially cationic function and at least one anionic or potentially anionic function Preferably, it is a nonorganic polyorganosiloxane -ionic or amino. As examples of polyorganosiloxanes, there may be mentioned: linear, cyclic or crosslinked polyorganosiloxanes formed from nonionic organosiloxane units of general formula (R) a (X) bS O) [4- (a + b)] / 2 0) formula in which

• the symbols R are identical or different and represent an alkyl hydrocarbon radical, linear or branched, having from 1 to 4 carbon atoms, aryl, phenyl in particular;

The symbols X are identical or different and represent a hydroxyl group, an alkoxy radical, linear or branched, having from 1 to 12 carbon atoms, an OCOR 'function, where R' represents an alkyl group containing from 1 to 12 atoms carbon, preferably 1 carbon atom;

• a is 0, 1, 2 or 3

• b is 0, 1, 2 or 3

• a + b is 0, 1, 2 or 3

Preferably, said polyorganosiloxane is at least substantially linear, and most preferably linear. By way of example, mention may in particular be made of α-ω bis (hydroxy) polydimethylsiloxane oils, α-ω bis (trimethyl) polydimethylsiloxane oils, cyclic polydimethylsiloxanes, polymethylphenylsiloxanes. linear, cyclic or crosslinked polyorganosiloxanes comprising, per mole, at least one ionic or nonionic organosiloxane unit of general formula (R) a (X) b (B) cSi (O) _[4 - (a + b + c) ] / 2 00 formula in which

• the symbols R are identical or different and represent a monovalent alkyl linear or branched hydrocarbon radical having from 1 to 4 carbon atoms, aryl, phenyl in particular; The symbols X are identical or different and represent a hydroxyl group, an alkoxy radical, linear or branched, having from 1 to 12 carbon atoms, an OCOR 'function, where R' represents an alkyl group containing from 1 to 12 carbon atoms, preferably 1 carbon atom;

The symbols B are identical or different and represent an aliphatic and / or aromatic and / or cyclic hydrocarbon radical containing up to 30 carbon atoms, optionally interrupted by one or more heteroatoms of oxygen and / or nitrogen and / or sulfur, optionally carrying one or more ether, ester, thiol, hydroxyl, optionally quaternized amine, carboxylate functions, the symbol B being bonded to silicon preferably via an Si-C- bond;

• a is equal to 0, 1 or 2 • b is equal to 0, 1 or 2

• c is equal to 1 or 2

• a + b + c is 1, 2 or 3

As examples of substituents corresponding to the symbol (B) in the formula (II) above, there may be mentioned - the polyether groups of formula - (CH ₂ ) _n - (OC ₂ H ₄ ) _m - (OC ₃ H ₆ ) _p -OR ', where n is equal to 2 or 3, m and p each go from 0 to 30 and R' represents an alkyl residue containing from 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms , primary, secondary, tertiary or quaternized amino groups, such as those of formula - R ¹ -N (R ² ) (R ³ ) where

^• the symbol R ¹ represents an alkylene group containing 2 to 6 carbon atoms, optionally substituted or interrupted by one or more nitrogen atoms or oxygen atoms,

^• the symbols R ² and R ³ , identical or different, represent H,. an alkyl or hydroxyalkyl group containing from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms,. an amino alkyl group, preferably primary, the alkyl group of which contains from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms, optionally substituted and / or interrupted by at least one nitrogen atom and / or d oxygen, said amino group being optionally quaternized, for example by a hydrohalic acid or an alkyl or aryl halide. We can notably mention those of formulas - (CH ₂ ) ₃ NH ₂ - (CH ₂ ) ₃ NH ₃ ⁺ X '

- (CH ₂ ) ₃ N (CH ₃ ) _2. (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₂ (C ₁₈ H ₃₇ ) X '

- (CH ₂ ) ₃ NHCH ₂ CH ₂ NH ₂ - (CH ₂ ) ₃ N (CH ₂ CH ₂ OH) ₂

- (CH ₂ ) ₃ N (CH ₂ CH ₂ NH ₂ ) ₂

Preferably, the polyorganosiloxanes carrying amino functions, present in their chain, for 100 total silicon atoms, from 0.1 to 50, preferably from 0.3 to 10, very particularly from 0.5 to 5 atoms of aminofunctionalized silicon. sterically hindered piperidinyl groups of formula III

where ^* R ⁴ is a divalent hydrocarbon radical chosen from: * linear or branched alkylene radicals, having 2 to 18 carbon atoms; * alkylene-carbonyl radicals, the linear or branched alkylene part of which contains 2 to 20 carbon atoms; * alkylene-cyclohexylene radicals, the linear or branched alkylene part of which comprises 2 to 12 carbon atoms and the cyclohexylene part comprises an OH group and optionally 1 or 2 alkyl radicals having 1 to 4 carbon atoms; * the radicals of formula -R ⁷ - O - R ⁷ in which the identical or different radicals R ⁷ represent alkylene radicals having 1 to 12 carbon atoms; * the radicals of formula -R ⁷ - O - R ⁷ in which the radicals R ⁷ have the meanings indicated above and one of them or both are substituted by one or two group (s) -OH; * the radicals of formula -R ⁷ - COO - R ⁷ in which the radicals R ⁷ have the meanings indicated above; the radicals of formula -R ⁸ -O -R ⁹ - O-CO-R ⁸ in which the radicals R ⁸ and R ⁹ identical or different, represent alkylene radicals having 2 to 12 carbon atoms and the radical R ⁹ is optionally substituted with a hydroxyl radical; U represents -O- or -NR ¹⁰ -, R ¹⁰ being a radical chosen from a hydrogen atom, a linear or branched alkyl radical containing 1 to 6 carbon atoms and a divalent radical of formula:

in which R ⁴ has the meaning indicated above, R ⁵ and R ⁶ have the meanings indicated below and R ¹¹ represents a divalent alkylene radical, linear or branched, having from 1 to 12 carbon atoms, one of the valential bonds (that of R ¹¹ ) being connected to the atom of -NR ¹⁰ -, the other (that of R ⁴ ) being connected to a atom of silicon; the radicals R ⁵ are identical or different, chosen from linear or branched alkyl radicals having 1 to 3 carbon atoms and the phenyl radical; the radical R ⁶ represents a hydrogen radical or the radical R ⁵ or O ^' .

or the sterically hindered piperidinyl groups of formula IV

* R ' ⁴ is chosen from a trivalent radical of formula: - (CH,) CH m \ ^co where m represents a number from 2 to 20, and a trivalent radical of formula:

where p represents a number from 2 to 20; * U 'represents -O- or NR ^{12 "} , R ¹² being a radical chosen from a hydrogen atom, a linear or branched alkyl radical containing 1 to 6 carbon atoms; * R ⁵ and R ⁶ have the same meanings as those given above with regard to formula III. Preferably, said sterically hindered amino-functional polyorganosiloxane is a linear, cyclic or three-dimensional polyorganosiloxane of formula (V):

in which: (1) the symbols Z, identical or different, represent R ¹ below and / or the symbol B below; (2) the symbols R ¹ , R ² and R ³ , which are identical and / or different, represent a monovalent hydrocarbon radical chosen from linear or branched alkyl radicals having from 1 to 4 carbon atoms, linear or branched alkoxy radicals having from 1 to 4 carbon atoms, a phenyl radical and preferably a hydroxy radical, an ethoxy radical, a methoxy radical or a methyl radical; (3) the symbols B, identical and / or different functional groups, represent a group with sterically hindered piperidinyl function (s) chosen from those mentioned above; and (4) - the number of organosiloxy units without group B ranges from 10 to 450, preferably from 50 to 250; - The number of organosiloxy units with a group B ranges from 1 to 5, preferably from 1 to 3; - 0 <w <10 and 8 <x <448. Most preferably, said polyorganosiloxane is linear. By way of example of commercial polyorganosiloxane products which can be used as hydrophobic phase (A), there may be mentioned in particular the oils RHODORSIL® 21645, RHODORSIL® Extrasoft marketed by Rhodia.

The non-aqueous phase may comprise monomers which are insoluble in water, in particular usable for emulsion polymerization processes, for example for the manufacture of latex. Finally, it is specified that it is not excluded that the nonaqueous phase comprises an amount of water, or of monomers soluble in water, which does not exceed the limit of solubility of water or in monomers in said phase. Examples of monomers which can constitute or be included in the non-aqueous phase include, alone or in mixtures:

- esters of mono- or polycarboxylic acids, linear, branched, cyclic or aromatic, comprising at least one ethylenic unsaturation;

- esters of saturated carboxylic acids comprising 8 to 30 carbon atoms, optionally carrying a hydroxyl group;

- β-ethylenically unsaturated nitriles, vinyl ethers, vinyl esters, vinyl aromatic monomers, vinyl or vinylidene halides; - hydrocarbon monomers, linear or branched, aromatic or not, comprising at least one ethylenic unsaturation;

- macromonomers derived from such monomers. We can cite more particularly:

- (meth) acrylic acid esters with an alcohol comprising 1 to 12 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate,

propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl acrylate, isodecyl acrylate ;

- vinyl acetate, vinyl Versatate®, vinyl propionate, vinyl chloride, vinylidene chloride, methyl vinyl ether, ethyl vinyl ether; the vinyl nitriles more particularly include those having 3 to 12 carbon atoms, such as in particular acrylonitrile and methacrylonitrile;

- styrene, α-methylstyrene, vinyltoluene, butadiene, chloroprene. It is noted that the non-aqueous internal phase can comprise a phase, aqueous or not, dispersed in the form of an emulsion within it. The emulsion is then a multiple emulsion.

Dendritic polymer The emulsion according to the invention comprises, as emulsifying agent, a dendritic polymer. The term "dendritic polymer" refers to macromolecular compounds comprising several branches. They can be regular dendrimers, or hyperbranched polymers. The dendritic polymer includes hydrophobic groups and hydrophilic groups. The hydrophobic groups can be included in repeating units within the polymer. They may, for example, be at least divalent alkylene groups with at least 3 consecutive carbon atoms, or at least divalent groups comprising a phenyl unit, for example the phenylene group. It is advantageously a group of formula - (CH ₂ ) _n - where n is greater than or equal to 3, for example 4, 5, 6, or 11, and / or a group of formula -C ₆ H -. The hydrophilic groups can be included in repeating units within the polymer and / or can be included at the end of the polymer chains. When the emulsion is a direct emulsion, the aqueous phase being the external phase, at least part of the hydrophilic or potentially hydrophilic groups are advantageously groups present at the ends of polymer chains. The hydrophilic groups included in repeating units are often considered as polymerization functions. These are for example groups, or functions, of formulas -COO- (polyesters), -O- (polyethers), -CONH- (polyamide), -OCOO- (polycarbonate), -NH-COO- (polyurethane) , -N <(polyamine), -NH-CO-NH- (urea), -CO- NH-CO- (imide). It should be noted that it is not excluded that the ends of polymer chains include hydrophobic groups, such as alkyl groups. The presence of such groups can help modulate the emulsifying properties of the dendritic polymer. The hydrophobic groups can be included in repeating units within the polymer and / or can be included at the end of the polymer chains. When the emulsion is a reverse emulsion, the aqueous phase being the internal phase, at least part of the hydrophobic groups are advantageously groups present at the ends of polymer chains. It should be noted that it is not excluded that the ends of polymer chains include hydrophilic or potentially hydrophilic groups. The presence of such groups can help modulate the emulsifying properties of the dendritic polymer. When the emulsion is a multiple emulsion comprising an internal aqueous phase, an intermediate phase, and an external aqueous phase, the internal phase and the intermediate phase constituting an internal reverse emulsion, the intermediate phase and the external phase constituting an external direct emulsion, and when the external direct emulsion and the internal reverse emulsion comprise the dendritic polymer, the latter preferably comprises hydrophobic groups and hydrophilic (or potentially hydrophilic) groups at the end of the polymer chains.

The dendritic polymer may preferably comprise hydrophilic or potentially hydrophilic groups (depending for example on the pH) at the ends of the polymer chains. In addition, the nature and properties of these groups can be more easily controlled, modified or varied, either during the polymerization or after, by post-functionalization. The dendritic polymer may preferably comprise hydrophobic groups at the ends of the polymer chains. In addition, the nature and properties of these groups can be more easily controlled, modified or varied, either during the polymerization or after, by post-functionalization.

Examples of hydrophilic groups include: - acid groups such as sulfonic, phosphonic, carboxylic acids, and their basic forms sulfonates, phosphate, phosphonate, carboxylate, - amino, primary, secondary, tertiary groups, their ammonium acid forms, and quaternary ammonium groups. It is mentioned that the hydrophilicity of a group may depend on the pH. In the present application, the term “hydrophilic group” designates groups which are hydrophilic at any pH, as well as groups whose hydrophilicity depends on the pH (potentially hydrophilic groups). Examples of hydrophobic groups include: - alkyl groups, saturated or unsaturated, aryl, aralkyl or alkylaryl groups, for example phenyl or naphthyl, silicone or silane groups, - fluorinated groups.

Examples of dendritic polymers include: - the polypropylene imine skeleton dendrimers, such as the Straburst® range marketed by the company DS, - the polyamidoester (or polyesteramide) skeleton dendrimers, such as the Hybrane® range sold on the marketed by DSM, - polyamidoamine skeleton dendrimers (PAMAM) - polyether dendrimers - diaminobutane-aminopropyl polymers DAB (PA) _n - hyperbranched polyesters, such as the BOLTORN® range marketed by Perstorp . The hyperbranched polyesters and the hyperbranched polyamides are in particular dendritic polymers which are particularly suitable for implementing the invention.

According to an advantageous embodiment, the dendritic polymer is a polymer capable of being obtained by a process comprising the following steps:

Step a) polycondensation of at least one multifunctional monomer of formula (I), comprising at least three reactive polycondensation functions, AR- (B) _f (I) formula in which - f is an integer greater than or equal to 2, preferably goes from 2 to 10, very particularly is equal to 2 - the symbol A represents a reactive function or a group carrying a reactive function chosen from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato, or their precursors - the symbol B represents a reactive function or a group carrying a reactive function chosen from the amino, carboxy, hydroxy, oxiranyl, halogen, isocyanato or their precursor functions, antagonist of A - the symbol R represents a linear aliphatic polyvalent hydrocarbon residue or branched, cycloaliphatic or aromatic containing from 1 to 50, preferably from 3 to 20 carbon atoms, optionally interrupted by one or more heteroatoms of oxygen , nitrogen, sulfur or phosphorus, said residue bearing optionally functions or functional groups which are not capable of reacting with functions A and B, Step b) optionally, at least partial hydrophilic functionalization of the polymer obtained in the polycondensation step. The symbol B represents a reactive function antagonistic to the reactive function A; this means that function B is likely to react with function A by condensation. So the antagonistic functions

- of an amino function, are in particular the carboxy (formation of an amide), isocyanato (formation of a urea), oxiranyl (formation of a secondary or tertiary β-hydroxylated amine) functions

- of a carboxy function, are in particular the amino (formation of an amide), hydroxy (formation of an ester), isocyanato (formation of an amide) functions.

- of a hydroxy function, are in particular the carboxy (formation of an ester), oxiranyl (formation of an ether), isocyanato (formation of an amide) functions

- of an oxiranyl function, are in particular the hydroxy functions (formation of an ether), carboxy (formation of an ester), amino (formation of a secondary or tertiary amine β-hydroxylated)

- of an isocyanato function, are in particular the amino, hydroxy, carboxy functions - of a halogeno function, are in particular the hydroxy functions. Among the amino function precursors, mention may in particular be made of amine salts, such as hydrochlorides.

Among the precursors of carboxy function, there may be mentioned in particular esters, preferably of C1-C4, very particularly of C1-C2, acid halides, anhydrides, amides.

Among the hydroxy function precursors, mention may in particular be made of epoxies. According to an alternative embodiment, said polycondensation operation is also carried out in the presence of:

• at least one bifunctional monomer in linear form of formula (II) or in the corresponding cyclic form, comprising two reactive polycondensation / polymerization functions A'-R'-B '(II) formula in which: - the symbol A ', identical to or different from A, represents a reactive function chosen from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato, or their precursors, antagonist of B and B' - the symbol B ', identical to or different from B, represents a reactive function chosen from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato, or their precursors, antagonist of A and A' - the symbol R ', identical with or different from R, represents a polyvalent hydrocarbon residue linear or branched aliphatic, cycloaliphatic or aromatic containing from 1 to 50, preferably from 3 to 20 carbon atoms, optionally interrupted by one or more heteroatoms of oxygen, nitrogen, of sulfur or phosphorus, said residue optionally carrying functions or functional groups which are not capable of reacting with functions A, A ', B and B' * the reactive function A ', being capable of reacting with function B and / or function B 'by condensation; ^* the reactive function B ', being capable of reacting with function A and / or function A' by condensation;

• and / or at least one “core” monomer of formula (III), comprising at least one function capable of reacting by condensation with the monomer of formula (I) and / or the monomer of formula (II) R ¹ - (B ") _n (III) formula in which - n is an integer greater than or equal to 1, preferably goes from 1 to 100, very particularly from 1 to 20 - the symbol B" represents a reactive function, identical or different of B or B ', chosen from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato, or their precursors, antagonist of A and A' - the symbol R ¹ represents a polyvalent linear or branched aliphatic hydrocarbon residue, cycloaliphatic or aromatic containing from 1 to 50, preferably from 3 to 20 carbon atoms, optionally interrupted by one or more heteroatoms of oxygen, nitrogen, sulfur or phosphorus, or an organosiloxane or polyorganosiloxane residue, said residue R ¹ optionally carrying functions or d es functional groups not capable of reacting with functions A, A ', B, B' and B "* reactive function B", being capable of reacting with function A and / or function A 'by condensation;

• and / or at least monofunctional “chain limiter” monomer of formula (IV) A "-R ² (IV) formula in which - the symbol A "represents a reactive function, identical to or different from A or A ', chosen from amino, carboxy, hydroxy, oxiranyl, halogen, isocyanato, or their precursors, antagonist of B, B' and B" - the symbol R ² represents a polyvalent linear or branched aliphatic, cycloaliphatic or aromatic hydrocarbon residue containing from 1 to 50, preferably from 3 to 20 carbon atoms, optionally interrupted by one or more heteroatoms of oxygen, nitrogen, sulfur or of phosphorus, or an organosiloxane or polyorganosiloxane residue, said residue R ² optionally carrying functions or functional groups which are not capable of reacting with the functions A, A ', A ", B, B' and B" * the reactive function A ", being capable of reacting with function B and / or function B 'and / or function B" by condensation; • at least one of the reactive functions of at least one of the monomers of formula (II), (III) or (IV) being capable of reacting with an antagonistic function of the multifunctional monomer of formula (I). Preferably, the functions A, A ', A "and B, B', B" are chosen from reactive functions or a group carrying reactive functions chosen from amino, carboxy, hydroxy, oxiranyl functions or their precursors . Even more preferably, said functions are chosen from reactive functions or a group carrying amino and carboxy reactive functions, or their precursors. For a good realization of the invention:

- The molar ratio of the monomer of formula (I) to the monomer of formula (II) is advantageously greater than 0.05, preferably ranges from 0.125 to 2;

- The molar ratio of the monomer of formula (III) to the monomer of formula (I) is advantageously less than or equal to 1, preferably less than or equal to 1/2, and even more preferably ranges from 0 to 1/3; said ratio is very particularly from 0 to 1/5;

- The molar ratio of the monomer of formula (IV) to the monomer of formula (I) is advantageously less than or equal to 10, preferably less than or equal to 5; said ratio goes very particularly from 0 to 2, when f is equal to 2. The elementary entity considered to define the different molar ratios is the molecule. It goes without saying that the expression “condensation reaction” also includes the notion of addition reaction when one or more antagonistic functions of at least one of the monomers used is included in a cycle (lactams, lactones, epoxides for example). By way of example of monomer (I), there may be mentioned: - 5-amino-isophthalic acid,

- 6-amino-undecanedioic acid,

- the 3-aminopimelic acid,

- aspartic acid, - glutamic acid,

- 3,5-diaminobenzoic acid,

- 3,4-diaminobenzoic acid,

- lysine,

- α, α-bis (hydroxymethyl) -propionic acid - α, α-bis (hydroxymethyl) -butyric acid

- α,, α-tris (hydroxymethyl) -acetic acid

- α, α-bis (hydroxymethyl) -valeric acid

- α, α-bis (hydroxy) -propionic acid

- 3,5-dihydroxybenzoic acid - or mixtures thereof As an example of a bifunctional monomer of formula (II), there may be mentioned:

- ε-caprolactam

- aminocaproic acid,

- para or metaaminobenzoic acid, - amino-11-undecanoic acid,

- the lauryllactame

- amino-12-dodecanoic acid

- hydroxyacetic acid (glycolic acid)

- hydroxyvaleric acid - hydroxypropionic acid

- hydroxypivalic acid

- glycolide

- δ-valerolactone

- β-propiolactone - ε-caprolactone

- lactide

- lactic acid

- or their mixtures More preferably, the bifunctional monomers of formula (II) are the monomers used for the manufacture of linear thermoplastic polyamides.

Thus, mention may be made of ω-aminoalkanoic compounds comprising a chain hydrocarbon having 4 to 12 carbon atoms, or lactams derived from these amino acids such as ε-caprolactam. The preferred bifunctional monomer for implementing the invention is ε-caprolactam. According to an advantageous embodiment of the invention, at least part of the bifunctional monomers (II) are in the form of a prepolymer. As examples of monomer (III), there may be mentioned:

- aromatic or aliphatic monoamines, such as dodecylamine, octadecylamine, benzylamine ...

- aromatic or aliphatic monoacids containing from 1 to 32 carbon atoms, such as benzoic acid, acetic acid, propionic acid, saturated or unsaturated fatty acids (dodecanoic, oleic, palmitic, stearic acid, etc.)

- monofunctional alcohols or epoxides, such as ethylene oxide, epichlorohydrin ...

- isocyanates such as phenylisocyanate ... - biprimary diamines, preferably linear or branched saturated aliphatic having from 6 to 36 carbon atoms such as, for example, hexamethylenediamine, trimethylhexamethylene diamine, tetramethylenediamine, n- xylene diamine

- saturated aliphatic dicarboxylic acids having from 6 to 36 carbon atoms such as, for example, adipic acid, azelaic acid, sebacic acid, maleic acid or anhydride

- difunctional alcohols or epoxides, such as ethylene glycol, diethylene glycol, pentanediol, glycidyl ethers of monofunctional alcohols containing from 1 to 24 carbon atoms

- diisocyanates, such as toluene diisocyanates, hexamethylene diisocyante, phenyl diisocyanate, isophorone diisocyanate

- triamines, triacids or aromatic or aliphatic polyacids, triols or polyols like N, N, N-tris (2-aminoethyl) amino, melamine ..., citric acid, acid 1, 3,5- tricarboxylic benzene ..., 2,2,6,6-tetra- (β-carboxyethyl) cyclohexanone, trimethylolpropane, glycerol, pentaerythritol, glycidyl ethers of di-, tri- or polyfunctional alcohols

- polymeric compounds such as poly amino mono- or polyoxyalkylene marketed under the trademark JEFFAMINE ^®,

- amino polyorganosiloxanes, such as amino polydimethylsiloxane.

The monomers (III), preferred "core" are: hexamethylene diamine, adipic acid, JEFFAMINE ^® T403 sold by the company Huntsman acid, 1, 3,5-benzenetricarboxylic acid, 2,2, 6,6-tetra- (β-carboxyethyl) cyclohexanone. By way of examples, the monomers (IV), there may be mentioned:

- aromatic or aliphatic monoamines, such as dodecylamine, octadecylamine, benzylamine. Most of these compounds are generally considered to be hydrophobic. - aromatic or aliphatic monoacids containing from 1 to 32 carbon atoms, such as benzoic acid, acetic acid, propionic acid, saturated or unsaturated fatty acids (dodecanoic, oleic, palmitic, stearic acid, etc.) . Most of these compounds are generally considered to be hydrophobic.

- monofunctional alcohols or epoxides, such as ethylene oxide, epichlorohydrin. Most of these compounds are generally considered to be hydrophobic.

- isocyanates such as phenylisocyanate. Most of these compounds are generally considered to be hydrophobic.

- polymeric compounds such as monoamine polyoxyalkylenes, for example sold under the brand JEFFAMINE M ^® , such as JEFFAMINE M 1000 ^® and

JEFFAMINE M 2070 ^® . Most of these compounds are generally considered to be hydrophilic.

- monoamine silicone chains, such as monoamine polydimethylsiloxane. Most of these compounds are generally considered to be hydrophobic. - N, N-DiMethyl Amino Propyl A iné (hydrophilic or potentially hydrophilic, because basic or quaternizable for example with dimethylsufate).

- N, N-DiEthyl Amino Propyl Amine (hydrophilic or potentially hydrophilic, because basic or quaternizable for example with dimethylsufate).

- N, N-DiButhyl Amino Propyl Amine (hydrophilic or potentially hydrophilic, because basic or quaternizable for example with dimethylsufate).

- N- (3-amino propyl) morpholine (hydrophilic or potentially hydrophilic, because basic or quaternizable for example with dimethylsufate).

- N-Methyl N '- 3-Amino-Propyl) Piperazine (hydrophilic or potentially hydrophilic, because basic or quaternizable for example with dimethylsufate). - N- (Amino-3 Propyl) Piperidine (hydrophilic or potentially hydrophilic, because basic or quaternizable for example with dimethylsufate).

- mixtures of these compounds. Among the functional groups which may be present in the monomers (I) to

(IV), and not capable of reacting with the functions A, A ', A ", B, B' and B", mention may in particular be made of functions capable of providing or improving the hydrophilicity of the dendritic polymers used work according to the invention. As for example, the quaternary ammonium, nitrile, sulfonate, phosphonate, phosphate, hydroxyl, polyethylene oxide, ether, ternary amine (basic or quaternizable) functions may be mentioned. Mention may in particular be made of: - 4-amino-benzene sulfonic acid and its ammonium or alkali metal, sodium salts in particular [monomer of formula (II)]

- 5-sulfo salicylic acid [monomer of formula (II)]

- D or L 2-amino 5-phosphoro valeric acid [monomer of formula (II)]

- sulfobenzoic acid and its ammonium or alkali metal salts (monomer of formula (III) or (IV))

- epoxypropyltrimethylarnmonium chloride (monomer of formula (III) or (IV))

- polytioxyle polyethylene glycol,

- amino methyl phosphonic acid [monomer of formula (IV)]. The hydrophilic functions can in particular be carried by the monomer (IV), for example by one of the following monomers:

- polymeric compounds such as monoamine polyoxyalkylenes, for example sold under the brand JEFFAMINE M ^® , such as JEFFAMINE M 1000 ^® and JEFFAMINE M 2070 ^® . Most of these compounds are generally considered to be hydrophilic. - N, N-DiMethyl Amino Propyl Amine (hydrophilic or potentially hydrophilic, because basic or quaternizable for example with dimethylsufate).

- N-Methyl N '- (Amino-3) Propyl Piperazine (hydrophilic or potentially hydrophilic, because basic or quaternizable for example with dimethylsufate). - N- (Amino-3 Propyl) Piperidine (hydrophilic or potentially hydrophilic, because basic or quaternizable for example with dimethylsufate).

Finally, the dendritic polymer can carry at the ends of the polymer chains a mixture of hydrophilic groups and hydrophobic groups, for example provided by monomers (IV) and / or acid-base control. We can thus modulate the emulsifying properties, and if necessary make the action of dendritic polymer sensitive to external conditions which can trigger stabilization or destabilization of the emulsion. This mode is preferable in the context of the production of multiple emulsions. An association of -COOH or COO ^' groups and alkyl groups is cited, for example.

The dendritic polymers described above can be assimilated to tree structures provided with a focal point formed by the function A and with a periphery furnished with B terminations. It is specified that the fact that the periphery is furnished with B terminations 'does not exclude that B terminations are present at chain ends located more at the heart of the dendritic polymer. Furthermore, when they are present, the bifunctional monomers (II) are spacers in the three-dimensional structure. They allow control of the connection density. When they are present, the monomers (III) form nuclei. The monofunctional monomers (IV) "chain limiter", are located at the periphery of the dendrimers. It is specified that the fact that the periphery is packed with monofunctional monomers (IV) does not exclude that monofunctional monomers (IV) are present at the ends of chains located more at the heart of the dendritic polymer. The presence of monomers (III) and (IV) makes it possible in particular to control the molecular weight. Preferably, the dendritic polymers used according to the invention are hyperbranched polyamides; they are obtained from at least one monomer of formula (I) having, as reactive polycondensation functions, amino functions, and carboxy antogonist functions, or from a monomer composition further containing at least one monomer of formula (II ) and / or (III) and / or (IV) having the same type (s) of reactive polycondensation function (s), all or part of the monomer (s) of formula (II) which can be replaced by a lactam. The polycondensation / polymerization operation can be carried out in a known manner in the molten or solvent phase, the monomer of formula (II), when it is present, can favorably play the role of solvent. The operation can be carried out favorably in the presence of at least one polycondensation catalyst and optionally of at least one antioxidant compound. Such catalysts and antioxidant compounds are known to those skilled in the art. Examples of catalysts that may be mentioned include phosphorus compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid, phenylphosphonic acids, such as 2- (2'-pyridyl) ethylphosphonic acid, the phosphites such as ts (2,4-di-tert-butylphenyl) phosphite. As an example of an antioxidant, mention may be made of biobuttered phenolic-based antioxidants, such as N, N'-hexamethylene bis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 5- tert-butyl-4-hydroxy-2-methylphenyl sulfide. Hyperbranched polyamides having nonreactive hydrophilic functionalities with the functions A, A ', A ", B, B' and B", can be obtained by using a monomer of formula (III) and / or (IV) having one or more polyoxyethylene groups (for example monomer from the family of amino polyoxyalkylenes JEFFAMINES) and / or a monomer of formula (IV) having quaternary ammonium, nitrile, sulfonate, phosphonate, phosphate functions. Another embodiment consists, after preparation of a hyperbranched polymer by polycondensation of nonfunctionalized monomers, in modifying the terminal functions of said hyperbranched polyamide by reaction with a compound having hydrophilic functions. It may for example be a compound having a tertiary amino group, quaternary ammonium, nitrile, sulfonate, phosphonate, phosphate or polyoxyethylene groups. The terminal functions can also be modified by a simple acid-base reaction, by totally or partially ionizing the groups included at the chain ends. For example end groups of carboxylic acid type (for example groups B, B ′, and / or B ″) can be made anionic by adding a base. End groups of amino type (for example groups B, B ', and / or B ") can be made cationic by adding an acid. Note that the functionalization can be total or partial. It is preferably greater than 25% in number, relative to all of the free functional groups carried (B, B ′, B ″). It should be noted that it is not excluded to carry out a partial hydrophobic functionalization after the preparation of the dendritic polymer, which can modulate the emulsifying properties, and if necessary make the action of the dendritic polymer sensitive to external conditions which can trigger stabilization or destabilization of the emulsion.

The molar mass by weight of said dendritic polymers, hyperbranched polyamides in particular, can range from 500 to 1,000,000 g / mol, preferably from 1,000 to 500,000 g / mol, even more preferably from 3,000 to 20,000 g / mol. The molar mass by weight can be measured by size exclusion chromatography. The measurement is carried out in an eluting phase composed of 70% in volume of Millipore water 18 megaohms and 30% by volume of methanol, containing 0.1 M NaNO ₃ ; it is adjusted to pH 10 (1/1000 NH ₄ OH 25%). The molar mass by weight is established in a known manner by means of light scattering values.

Quantities - Formulation The weight ratio between the quantities of internal phase and external phase is preferably between 0.1 / 99.9 and 95/5, more preferably between 1/99 and 10/90. The weight ratio between the amounts of dendritic polymer and of internal phase is preferably between 0.05 / 100 and 20/100, more preferably between 0.5 and 20/100, or even between 5/100 and 20/100 . Furthermore, the proportion by weight of dendritic polymer in the whole of the emulsion is preferably between 0.05% and 10%, even more preferably between 0.1% and 5%, for example of the order of 1 %. The size of the droplets of the emulsion may depend on the amount of emulsifying agent (dendritic polymer with possibly other agents, such as surfactants) used and / or the amount of energy used to prepare the emulsion. 'emulsion. At a small proportion of emulsifying agent, the size of the droplets can be for the most part limited (lower limit, large droplets) by the quantity of emulsifying agent. The greater the proportion of emulsifying agent, the smaller the droplets. We often speak of a poor diet. With a higher proportion of emulsifying agent, the size can be largely limited (lower limit) by the amount of energy. The greater the amount of energy, the smaller the droplets. We often talk about a rich diet. In the case where the emulsion does not comprise any other emulsifying agent than the dendritic polymer, the limit between the lean diet and the rich diet can be of the order of a few%, for example 1/100 to 2 / 100 (weight ratio between the quantities of dendritic polymer and of internal phase), for a direct emulsion. It is mentioned, without this constituting a limitation to the invention, that it has been noticed, that the critical concentration (by weight of dendritic polymer) between the poor diet and the rich diet seems not to depend on the molecular weight of the polymer dendritic. Without wishing to be bound by any theory, it is believed that the dendritic polymer is present at the interface between the aqueous phase and the hydrophobic phase, in the form of objects aggregated around the droplets. Thus, for example, the size of the droplets can be adjusted by varying the nature of the internal phase, the proportions of the various constituents, in particular of the emulsifying agent, and on process parameters (speed and duration of mixing to impart energy).

Other ingredients The emulsions according to the invention are compositions which, in addition to the ingredients mentioned above, can comprise other ingredients. The nature and quantity of these other ingredients may depend on the destination or the use of the emulsion. These additional ingredients are known to those skilled in the art. For example, the emulsion may comprise additional emulsifying agents, known, in combination with the dendritic polymer, in particular surfactants, in particular nonionic or cationic surfactants, water-soluble amphiphilic polymers, comb polymers or block polymers. In the context of multiple emulsions, it is specified that each of the aqueous phases can comprise agents intended to control the osmotic pressure. It may, for example, be a salt chosen from alkali or alkaline earth metal halides ((such as sodium chloride, calcium chloride), or a sugar (such as gluocse) or a polysaccharide (such as dextran), or a mixture. In general, the emulsions can comprise nonionic, anionic, cationic or amphoteric surfactants (the zwitterionic surfactants being included in amphoterics). The emulsions can also include pH control agents, active ingredients, perfumes, etc.

Process The emulsions according to the invention can be prepared by the conventional processes of emulsification. These methods conventionally consist in mixing more or less vigorously the various ingredients: the immiscible phases, the emulsifying agent, and possibly other ingredients. For this mixture, some of the ingredients may have been mixed, dissolved or dispersed beforehand. Thus it may be advantageous to use an aqueous phase into which the dendritic polymer has been introduced beforehand, before mixing said aqueous phase with the immiscible phase. The mixing can be carried out with more or less strong stirring. In the case where the internal phase is of low viscosity (viscosity less than 1 Pa · s) can advantageously operate under vigorous stirring, for example using a device of Ultra-Turrax ^®, microfluidizer or other homogenizer high pressure. In the case where the internal phase is viscous (viscosity greater than 1 Pa.s, preferably greater than 5 Pa.s), it is advantageous to operate using a paddle frame. The temperature at which the emulsion is prepared can depend on the different phases implemented. Thus, one can choose to modulate the temperature in order to modulate the viscosity of the different phases implemented. Note that it may be practical to add a heat-thickening compound to the internal phase. The duration of agitation can be determined without difficulty by a person skilled in the art. It generally depends on the device used. In a rich diet, it can partly determine the size of the droplets. It is also mentioned that the emulsions can be produced according to a self-emulsification process. Under certain conditions, a mixture comprising the compound which will constitute the internal phase and the emulsifying agent or agents, can form an emulsion by simple addition in water, with very slight stirring. We speak for this mixture of self-emulsifiable compositions. Such compositions find utility in particular in the field of agriculture, for formulating liquid phytosanitary compounds insoluble in water directly on the farm ("tank mix"), and in the field of coatings and paints (in particular for isocyanate bases).

Applications The emulsions according to the invention can be used in numerous fields of application. Mention is made in particular of the fields of formulation of cometic products (skin, hair care, make-up), detergent products (cleaning of linen, dishes, or hard surfaces), paints or coatings. In the detergency or cosmetic field, the dendritic polymer according to the invention can be used as an emulsion vector or as a triggering agent for the deposition on an surface of an emulsion compound, for example a silicone. Thus, a stable emulsion of a compound to be deposited (for example a silicone) is prepared, and the deposition is triggered by modifying the external phase, for example by dilution or by change of pH, so as to modify the hydrophilicity of groups included. in the dendritic polymer (modification to make them more hydrophobic). The emulsion can then be destabilized, and the emulsified compound is deposited on a surface, for example a textile surface (detergency), or on the skin or hair (cosmetic, conditioner). The emulsified compound can also be brought to the surface by simple affinity of the dendritic polymer for the surface, by adsorption for example. Whatever the mechanism, destabilization of the emulsion, or affinity for a surface, the dendritic polymer can be considered as an emulsion vector. It is particularly useful in shampoos or in textile care compositions. These mechanisms can also be used for deposits or treatments on metals, glass, or clays. In the field of cosmetics, emulsions have the advantage of being substantially free of surfactant and of not foaming in the absence of a surfactant. The dendritic polymer can be combined with a surfactant. In this case, the dendritic polymer has an effect on the emulsification, without increasing the foaming linked to the presence of surfactant. In addition, in the absence of a surfactant, the dendritric polymer does not foam, and in the presence of a low-foaming surfactant, it improves the emulsification properties or emulsion stability, without increasing foaming. To totally avoid foaming, or not to increase it, avoids implementing restrictive emulsification processes. On the other hand, some products are not intended to foam. These are generally creams, milks or gels intended to be applied to the skin or the lips. As regards the field of paints and coatings, the emulsions according to the invention can for example be emulsions of alkyd or isocyanate type (emulsion in water of an alkyd or an isocyanate). The emulsion can also be an emulsion of monomers intended for the preparation of latex. The emulsion according to the invention can be used in paints, preferably aqueous, or itself constitute a preferably aqueous paint, and be used to transport in particular a hydrophobicizing agent on a surface of the building material type, plaster , cement, wood ..., with release of the hydrophobing agent by depositing and drying the paint on the surface. It can also be used for the treatment of metals. Likewise, it can be used in cosmetic compositions or itself constitute an aqueous cosmetic composition (moisturizing creams, sun creams, make-up products, styling gels, etc.); the hydrophobic phase can be or contain any hydrophobic active care material (such as conditioning agents, detangling agents, etc.), anti-UV agents, pigments, dyes, etc. It can also be used to impart to surfaces made of a woven or non-woven material of cellulosic and / or synthetic origin, for personal hygiene or cleaning the home, intended to come into contact with the skin, such as care and cleaning wipes or make-up removal ("wipes"), absorbent papers ("tissues"), feminine protections ("towels"), diapers ("Diapers") etc ..., intrinsic benefits to the hydrophobic non-aqueous phase and / or to active materials contained in the hydrophobic phase, and this during the preparation of said surfaces or by post-treatment of said surfaces. Can thus be given softening, anti-odor, perfuming, bactericidal, etc. properties. It can also be used during the manufacture or for the post-treatment of cartons or cardboard packaging, to provide hydrophobic, anti-odor properties, bactericides, fragrances ... The emulsion according to the invention (E) is particularly advantageous for conveying and depositing a hydrophobic active material (constituting the hydrophobic phase or included in the hydrophobic phase) on a hydroxyapatite surface or substrate (S) (tooth), a keratinous surface or substrate (skin, hair, leather) or a textile surface or substrate. When said substrate (S) is hydroxyapatite (teeth), the hydrophobic phase can contain hydrophobic agents having refreshing properties, agents making it possible to fight against dental plaque, antiseptic agents, etc. The emulsion (E) can be included or itself form a composition for dental or oral hygiene, composition intended to be rinsed or diluted. It can be toothpaste, mouthwash, etc. Said substrate (S) can in particular be a keratinous surface, such as the skin and the hair. The hydrophobic phase can be or contain any hydrophobic active care material (such as conditioning agents, detangling agents, etc.), anti-UV agents, pigments, dyes, etc .; the emulsion (E) can be included in or itself form a cosmetic composition intended to be rinsed or diluted; it may especially be a shampoo, a conditioner, a shower gel, etc. Said substrate (S) may be leather; the hydrophobic phase can be or contain any hydrophobic active material capable of providing the hydrophobic substrate, softness, flexibility, protection with respect to external agents, etc. In an interesting manner, said substrate (S) is in a textile material. The textile substrate may be in the form of textile fibers or of articles made from natural textile fibers (cotton, linen or other natural cellulosic material, wool ...), artificial (viscose, rayon ...) or synthetic ( polyamide, polyester ...) or mixtures thereof. Preferably, said substrate is a textile surface made of a cellulosic material, in particular cotton. The hydrophobic phase is preferably made of a material for textile care ("textile care agent"). The benefits brought by a hydrophobic lubricating phase to a textile substrate are in particular the contribution of properties of softness (softness), anti-creasing (anti-wrinkling), ease of ironing (easy-ironing), resistance to l abrasion (protection in particular against aging when wearing the garment or repeated washing operations), elasticity, color protection, retention of perfumes ... Among other active ingredients providing other benefits in the field of care of articles made of textile fibers, mention may in particular be made of perfumes; preferably, these are dissolved in the hydrophobic phase. The substrate or the surface (S) may be present in an aqueous bath (B). The aqueous bath (B) in which the textile substrate is present to acquire benefits, can be very varied. It may be, without limitation, a soaking bath, washing, rinsing, padding ... The emulsion according to the invention can in particular be used as an additive in a detergent composition for washing or rinsing articles in textile fibers, or as a detergent or rinsing composition for washing or rinsing articles in textile fibers, with the aim of conveying a hydrophobic care agent ("textile care agent") and / or any active material hydrophobic other useful, and to promote the deposition of this and / or the latter on an article made of textile fibers, cotton in particular, during the rinsing operation and / or during the subsequent drying operation ( s) during the main washing operation when it is a detergent composition for washing, or during the subsequent drying operation when it is a rinsing composition. The emulsion in the form of a multiple emulsion containing a hydrophobic care phase, as a detergent composition or in a detergent composition for washing laundry in a washing machine, used in the washing cycle, without adding liquid softening rinsing in the rinsing cycle, made it possible to provide the washed laundry with softness, flexibility, anti-wrinkling properties, easy ironing, abrasion resistance, elasticity, color protection, fragrance retention ... The emulsion (E) in the form of a multiple emulsion containing a hydrophobic care phase, as a rinsing composition or in a composition for rinsing laundry, allows to bring to the laundry, after drying, properties of softness, flexibility, anti-wrinkling, anti-ironing, easy-ironing, abrasion resistance, elasticity, color protection, fragrance retention

The deposition of the hydrophobic phase containing or consisting of an active material (A) on the substrate can be a deposition by adsorption, co-crystallization, trapping and / or adhesion. The amount of emulsion in the form of a multiple emulsion which may be present in a composition for washing textile fiber articles, according to the third subject of the invention, corresponds to an amount of hydrophobic phase representing from 0.0001% to 25 %, preferably from 0.0001% to 5% of the total weight of the composition, with relative amounts of emulsion, expressed in multiple emulsion, and of aqueous medium (B) equivalent to a dilution of 2 to 100 times the volume of said emulsion. The amount of emulsion in the form of a multiple emulsion which may be present in a composition for rinsing articles of textile fibers, according to the third object of the invention, corresponds to an amount of hydrophobic phase representing from 0.0001% to 25 %, preferably from 0.0001% to 5% of the total weight of the composition, with relative amounts of emulsion, expressed in multiple emulsion, and of aqueous medium (B) equivalent to a dilution of 2 to 100 times the volume of said emulsion. A washing composition, whether or not compacted or liquid powder, of articles made of textile fibers may contain at least one surfactant preferably chosen from anionic surfactants and nonionics or mixtures thereof. Among the anionic surfactants, mention may be made of alkyl (C ₈ -Cι ₅ ) benzene sulfonates (at a rate of 0-30%, preferably 1-25%, more preferably 2-15% by weight). In addition, primary or secondary alkyl sulfates can be mentioned, in particular primary (C ₈ -C ₁₅ ) alkyl sulfates; alkyl ether sulfates; olefin sulfonates; alkyl xylene sulfonates; dialkyl sulfosuccinates; fatty acid esters sulfonates; sodium salts are generally preferred. Among the nonionic surfactants, there may be mentioned the ethoxylates of primary or secondary alcohols, in particular the ethoxylates of C ₈ -C ₂₀ aliphatic alcohols having from 1 to 20 moles of ethylene oxide per mole of alcohol, and more particularly the ethoxylates of primary or secondary C ₁₀ -C ₁₅ aliphatic alcohols having from 1 to 10 moles of ethylene oxide per mole of alcohol; may also be mentioned non-ionic non-ethoxylated surfactants such as alkylpolyglucosides, glycerol monoethers, and polyhydroxyamides (glucamides). Preferably the level of nonionic surfactants is 0-30%, preferably 1-25%, more preferably 2-15% by weight. The choice and quantity of the surfactant depends on the desired use of the detergent composition. The surfactant systems to be chosen for washing textiles by hand or in the machine are well known to formulators.

Amounts of surfactants as high as 60% by weight may be present in the compositions for hand washing. Amounts of 5-40% by weight are generally suitable for washing textiles in the machine. Typically these compositions comprise at least 2% by weight, preferably from 2-60%, more preferably 15-40% and particularly 25-35% by weight.

It is also possible to include cationic mono-alkyl surfactants. Mention may be made of the quaternary ammonium salts of formula R ¹ R ² R ³ R ⁴ N ⁺ X ^′ where the R groups are long or short, alkyl, hydroalkyl or alkyl ethoxylated chains, X being a counterion (R ¹ is a C ₈ -C ₂₂ , preferably C ₈ -C ₁₀ , or C ₁₂ -C ₁ alkyl group, R ² is a methyl group, R ³ and R ^{4 being} similar or different being a methyl or hydroxymethyl group); as well as cationic esters, such as choline esters.

The detergent compositions for most washing machines, generally contain an anionic surfactant other than soaps, or a nonionic surfactant, or mixtures thereof, and optionally a soap. Detergent compositions for washing textiles generally contain at least one detergency builder; the total amount of detergency builder is typically 5-80%, preferably 10-60% by weight. Mention may be made of inorganic adjuvants such as sodium carbonate, crystalline or amorphous aluminosilicates (10-70%, preferably 25-50% dry), lamellar silicates, inorganic phosphates (Na orthophosphate, pyrophosphate and tripolyphosphate). Further details relating to particularly suitable aluminosilicates and zeolites are given in WO 03/020819. Mention may also be made of organic detergency builders, such as polymers of polyacrylate type, acrylic / maleic copolymers and acrylic phosphinates; polycarboxylate monomers such as citrates, gluconates, oxidisuccinates, mono-, di- and tri-succinates of glycerol, dipicolinates, hydroxyethyliminodiacetates, malonates or succinates of alkyl or alkenyl; fatty acid sulfonate salts .... Preferably, the organic detergency builders are citrates (5-30%, preferably 10-25% by weight), acrylic polymers, more particularly acrylic / maleic copolymers (0.5-10%, preferably 1- 10% by weight). When they are in compacted powder or not, the compositions may favorably contain a bleaching system, in particular peroxide compounds such as inorganic persalts (perborates, percarbonates, perphosphates, persilicates and persulfates, preferably sodium perborate monohydrate or tetrahydrate, and sodium percarbonate) or organic peroxyacids (urea peroxide), capable of releasing oxygen in solution. The bleaching peroxide compound is favorably present in an amount of 0.1-35%, preferably 0.5-25% by weight. It can be combined with a bleach activator to improve bleaching at low temperatures; it is present favorably in an amount of 0.1-8%, preferably 0.5-5% by weight. The preferred activators are peroxycarboxylic acids, especially peracetic and pernonanoic acids. Mention may very particularly be made of N, N, N ', N', - tetracetyl ethylenediamine (TAED) and sodium nonanoyloxybenzene sulfonate (SNOBS). The compositions also generally comprise one or more enzymes, in particular proteases, amylases, cellulases , oxidases, peroxidases and lipases (0.1- 3% by weight), perfumes, anti-redeposition agents, antifouling, anti-color transfer, non-ionic softening agents ... Detergent compositions for washing textiles may also be in the form of nonaqueous liquid tablets in an envelope made of a material dispersing in the washing medium such as polyvinyl alcohol for example. They comprise at least one water-miscible alcohol, such as in particular isopropyl alcohol, in an amount which can range from 5 to 20% by weight. .

They may contain at least one surfactant preferably chosen from anionic surfactants and nonionic surfactants or their mixtures, in an amount which can range from 20 to 75% by weight. They can also include organic detergency builders, such as sodium citrates, phopsphonates, etc., in amounts which can range from 5 to 20% by weight; they can also include perfumes, dyes, etc. The compositions for rinsing articles of textile fibers can contain cationic or non-ionic softening agents. They can represent from 0.5 to 35%, preferably from 1-30%, more preferably 3-25% by weight of the rinsing composition. Cationic softeners are substantially non-water-soluble quaternary ammonium compounds comprising a single alkyl or alkenyl chain containing at least 20 carbon atoms, or preferably compounds having two polar heads and two alkyl or alkenyl chains containing at least 14 carbon atoms . Most preferably, the softening compounds have two alkyl or alkenyl chains containing at least 16 carbon atoms, and particularly at least 50% of the alkyl or alkenyl groups have 18 or more carbon atoms. Most preferably the linear alkyl or alkenyl chains are predominant. In commercial softening rinse formulas, quaternary ammonium compounds having two long aliphatic chains, such as distearyl dimethyl ammonium chlorides, ditallow alkyl dimethyl ammonium chlorides, are very commonly used.

The rinse compositions may further include nonionic softeners such as lanolin; lecithins and other phospholipids are also suitable. The rinsing compositions may also contain nonionic stabilizing agents such as linear C ₈ -C ₂₂ alkoxylated alcohols containing 10 to 20 moles of alkylene oxide, Cι ₀ -C ₂₀ alcohols and their mixtures. The amount of non-ionic stabilizing agent represents 0.1-10%, preferably 0.5-5%, very particularly 1-4% by weight of the composition. The molar ratio of the quaternary ammonium compound and / or other softening cationic agent to the stabilizing agent is favorably 40 / 1-1 / 1, preferably 18 / 1-3 / 1.

The composition may also comprise fatty acids, in particular monocarboxylated (C ₈ -C ₂ ) alkyl or alkenyl acids or their polymers; preferably they are saturated and non-saponified, like oleic, lauric or tallow acids. They can be used in an amount of at least 0.1%, preferably at least 0.2% by weight. In concentrated compositions, they can be present in an amount of 0.5-20%, preferably 1-10% by weight. The molar ratio of the quaternary ammonium compound and / or other cationic softening agent to the fatty acid is favorably 10 / 1-1 / 10.

Other details or advantages of the invention will become apparent from the examples below, without limitation.

EXAMPLE 1 Synthesis of a Hyperbranched Copolyamide with Carboxylic Acid Terminations by Copolycondensation in the Molten Phase of 1,3,5-Benzene Tricarboxylic Acid (denoted BTC, core molecule of type R ¹ -B " ₃ , with B" = COOH ), 5-isophthalic acid (noted AIPA, AR- type branching molecule B ₂ , with A = NH ₂ and B = COOH), and ε-caprolactam (denoted CL, spacer of type A'-R'-B ', with A' = NH ₂ and B '= COOH). The respective overall composition is 1/6/6 in BTC / AIPA / CL. The reaction is carried out in a 500 ml glass reactor commonly used in the laboratory for the melt phase synthesis of polyesters or polyamides. The monomers are fully charged at the start of the test. The reactor is immersed in a metallic Wood alloy bath at 100 ° C. and maintained under mechanical stirring at 80 rpm. 72.7 g of ε-caprolactam (0.64 mol), 116.4 g of 5-aminoisophthalic acid (0.64 mol), 22.5 g of acid 1, 3 are successively introduced into the reactor. 5-benzene tricarboxylic (0.11 mol) and 0.53 g of a 50% aqueous solution (w / w) of hypophosphorous acid. The reactor is placed under a weak sweep of dry nitrogen. The stirring is then adjusted to 50 rpm and the reaction mass is gradually heated from 100 ° C to 250 ° C, in about 250 min. The temperature is then maintained at 250 ° C. in a tray.

After 60 minutes under these conditions, the reactor is put under progressive vacuum over 60 min. The minimum vacuum is then maintained for an additional 60 min. About 10.6 g of distillate is recovered. At the end of the cycle, the stirring is stopped and the reactor allowed to cool to room temperature under a stream of nitrogen. 182.5 g of polymer are collected. The hyperbranched copolyamide obtained is a whitish solid.

Example 2 Synthesis of a Hyperbranched Copolyamide with Carboxylic Acid Terminations by Copolycondensation in the Molten Phase of 1,3,5-Benzene Tricarboxylic Acid (denoted BTC, core molecule of type R ¹ -B " ₃ , with B" = COOH ), 5-amino isophthalic acid (noted AIPA, branching molecule type AR- B ₂ , with A = NH ₂ and B = COOH), and ε-caproiactam (noted CL, spacer type A '-R'-B', with A '= NH ₂ and B' = COOH). The respective overall composition is 1/25/25 in BTC / AIPA / CL.

The same reactor as that described in Example 1 is used. The monomers are fully charged at the start of the test. The reactor is immersed in a metallic Wood alloy bath at 100 ° C. and maintained under mechanical stirring at 80 rpm. 79.5 g of ε-caprolactam (0.70 mol), 127.2 g of 5-aminoisophthalic acid (0.70 mol), 5.9 g of acid 1, 3 are successively introduced into the reactor. 5-benzene tricarboxylic (0.03 mol) and 0.49 g of a 50% aqueous solution (w / w) of hypophosphorous acid. The reactor is placed under a weak sweep of dry nitrogen. The stirring is then adjusted to 50 rpm and the reaction mass is gradually heated from 100 ° C to 250 ° C, in about 250 min. The temperature is then maintained at 250 ° C. in a tray.

After 60 minutes under these conditions, the reactor is put under progressive vacuum over 60 min. The minimum vacuum is then maintained for an additional 60 min. About 11.3 g of distillate are recovered. At the end of the cycle, the stirring is stopped and the reactor allowed to cool to room temperature under a stream of nitrogen. 162.2 g of polymer are collected. The hyperbranched copolyamide obtained is a whitish solid.

Example 3 Neutralization with sodium hydroxide of a hyperbranched copolyamide with carboxylic acid terminations of global composition 1/25/25 respectively in BTC / AIPA / CL, synthesized in example 2. 50.0g of hyperbranched copolyamide obtained in example 2 are finely ground and dispersed in 300ml of water. The mixture is mechanically stirred using an anchor and gradually added with 35% by mass aqueous sodium hydroxide. The pH is checked regularly using pH paper and kept around 10. 22.12g of soda are necessary to reach a stable pH. The solution is then filtered, then lyophilized. 48.8 g of fine white powder are collected. Elemental analysis of sodium gives an average content of 9% by mass, ie a content of sodium carboxylate groups of 3480 meq / kg.

EXAMPLE 4 Synthesis of a Hyperbranched Copolyamide with Polyalkylene Oxide Terminations by Copolycondensation in the Molten Phase of 1,3,5-Benzene Tricarboxylic Acid (denoted BTC, core molecule of type R -B " ₃ , with B" = COOH), 5-amino isophthalic acid (denoted AIPA, branching molecule type AR- B ₂ , with A = NH ₂ and B = COOH), ε-caprolactam (denoted CL, spacer type A '- R'-B', with A '= NH ₂ and B' = COOH) and Jeffamine M1000 ® (noted M1000, blocker of type A "-R ² , with A" = NH ₂ ). The respective overall composition is 1/25/25/28 in BTC / AIPA / CL / M1000. The same reactor as that described in Example 1 is used. The monomers are fully charged at the start of the test. The reactor is immersed in a metallic Wood alloy bath at 100 ° C. and maintained under mechanical stirring at 80 rpm. 23.9 g of ε-caprolactam (0.21 mol), 236.2 g of Jeffamine M1000® (0.24 mol), 38.2 g of 5-aminoisophthalic acid (0.21) are successively introduced into the reactor. mol), 1.8 g 1,3,5-benzene tricarboxylic acid (0.008 mol) and 0.22 g of a 50% aqueous solution (w / w) of hypophosphorous acid. The reactor is placed under a weak sweep of dry nitrogen. The stirring is then adjusted to 50 rpm and the reaction mass is gradually heated from 100 ° C to 250 ° C, in about 250 min. The temperature is then maintained at 250 ° C. in a tray.

After 60 minutes under these conditions, the reactor is put under progressive vacuum over 60 min. The minimum vacuum is then maintained for an additional 60 min. About 7.0 g of distillate is recovered. At the end of the cycle, the stirring is stopped and the reactor allowed to cool to room temperature under a stream of nitrogen. 281.5 g of polymer are collected. The hyperbranched copolyamide obtained is a viscous translucent liquid.

EXAMPLE 5 Synthesis of a Hyperbranched Copolyamide with Polyalkylene Oxide and Carboxylic Acid Terminations by Copolycondensation in the Molten Phase of 1,3,5-Benzene Tricarboxylic Acid (denoted BTC, core molecule of type R ¹ -B " ₃ , with B "= COOH), 5-isophthalic acid (denoted AIPA, branching molecule of type ARB ₂ , with A = NH ₂ and B = COOH), ε-caprolactam (denoted CL, spacer of type A'-R'-B ', with A' = NH ₂ and B '= COOH) and Jeffamine M1000 ® (noted M1000, blocker of type A "-R ² , with A" = NH ₂ ) - La respective overall composition is 1/25/25/21 in BTC / AIPA / CL / M1000.

The same reactor as that described in Example 1 is used. The monomers are fully charged at the start of the test. The reactor is immersed in a metallic Wood alloy bath at 100 ° C. and maintained under mechanical stirring at 80 rpm. 29.3 g of ε-caprolactam (0.26 mol) are successively introduced into the reactor,

221.7g of Jeffamine M1000 ® (0.22 mol), 46.9 g of 5-aminoisophthalic acid (0.26 mol), 2.2 g of 1,3,5-benzene tricarboxylic acid (0.010 mol) and 0.24 g of a 50% (w / w) aqueous solution of hypophosphorous acid. The reactor is placed under a weak sweep of dry nitrogen. The stirring is then adjusted to 50 rpm and the reaction mass is gradually heated from 100 ° C to 250 ° C, in about 250 min. The temperature is then maintained at 250 ° C. in a tray.

After 60 minutes under these conditions, the reactor is put under progressive vacuum over 60 min. The minimum vacuum is then maintained for an additional 60 min. About 11.9 g of distillate are recovered. At the end of the cycle, the stirring is stopped and the reactor allowed to cool to room temperature under a stream of nitrogen. 285.8 g of polymer are collected. The hyperbranched copolyamide obtained is a viscous translucent liquid, which hardens into a wax at room temperature.

Examples 6 to 9: Preparation of direct water-in-oil emulsions, containing 20% by weight of oily phase and 80% of aqueous phase.

Hyperbranched copolyamides (PAHB) prepared according to the preceding examples are used as emulsifying agent. The quantity of PAHB retained for the preparation of the emulsion is previously dissolved in water to form the aqueous phase. This is adjusted to a desired pH by adding a solution of HCl or NaOH

1N.

The oil phase is added to the aqueous phase with stirring using a rotor / stator type agitator (Ultra-turrax) rotating at 9500 rpm. After addition, the stirring is extended for 2 min.

The emulsion thus obtained is then subjected to 3 passages under a pressure of 250 bars or 500 bars in a high pressure homogenizer (MICROFLUIDIZER M110

S). The particle size of the emulsion thus obtained is measured with a laser diffraction particle size analyzer (HORIBA LA-910 particle size analyzer) and the evolution of this particle size and the evolution of the macroscopic stability of the emulsion are followed over time. observe the instability phenomena that may occur (coalescence, Oswald ripening, creaming or sedimentation of the droplets due to the difference in oil and water densities).

Example 6: influence of the concentration of PAHB in the aqueous phase on the size of the emulsion.

Emulsions are prepared comprising from 0.25 to 5% by weight of PAHB relative to the oil. A PAHB is used according to Example 1, and a PAHB according to Example 2. The pH of the aqueous phase is adjusted to 6.0-6.5. The oil phase is hexadecane. The homogenization pressure is 500 bars.

The median radius (R) of the emulsion is measured as a function of the concentration of PAHB / oil. It shows that the definition of the poor (P) and rich (R) polymer domains and that the size of the emulsion for a given polymer concentration are relatively independent of the molecular weight of the dendritic polymer. The results are presented in Table I below.

Table I

Example 7: Emulsions prepared with a PAHB according to Example 2, and different oils

The emulsion contains 1% by weight of PAHB according to Example 2 relative to the oil (ie 0.2% o in the emulsion). The pH of the aqueous phase is adjusted to 6.0-6.5. 3 oils are studied: hexadecane, a polydimethylsiloxane silicone oil (Rhodorsil V100 from Rhodia), a rapeseed methyl ester (Phytorob 926-65 from Novance) The emulsions are subjected to 3 passages at 200 bars in the Microfluidizer. The results in terms of stability are presented in Table I below. Table I

* increase in drop size due to Oswald ripening caused by the relatively high solubility of rapeseed ester in water.

Example 8: Emulsions prepared with PAHBs according to examples 1 or 4. Influence of the nature of the chain ends.

The emulsions contain between 0.5 and 5% by weight of PAHB relative to the oil (0.1 to 1.0% in the emulsion) The oil phase is hexadecane. The emulsions are subjected to 3 passages at 200 bars in the Microfluidizer M110S (3 passages at 500 bars with the PAHB with amine termination). The results are presented in Table II below.

Table II

The creaming observed after 8 days is due to the significant difference in density between the hexadecane and the water which causes the gradual rise towards the upper part of the emulsion of the larger droplets.

Example 9: Emulsions prepared with a PAHB according to Example 1. Influence of the pH of the aqueous phase.

The emulsion contains 5% by weight of PAHB relative to the oil (ie 1% in the emulsion). 3 emulsions are prepared with an aqueous phase at three different pHs: 10.4 - 7.0 - 5.5. At pH 5.5 the Polymer is at the limit of solubility The oil used is a rapeseed methyl ester (Phytorob 926-65 from Novance). The emulsions are subjected to 3 passages at 200 bar in the Microfluidizer. The results are presented in Table III below.

At pH 5.5 the polymer is at the limit of solubility in water and it is in this pH zone that its affinity for the water / oil interface is the greatest, which explains the very good stability of the emulsions and the absence of coalescence. The solubility and the affinity of the polymer for water increases with pH and leads to a less good stability of the interfaces and the development of an increasing coalescence. The increase in median diameter observed even at pH 5.5 is due to the Oswald ripening caused by the solubility of the rapeseed ester in water.

Example 10 Synthesis of a Hyperbranched Copolyamide with Carboxylic and Octadecylene Terminations by Copolycondensation in the Molten Phase of Benzene-1,3,5 Tricarboxylic Acid (Denoted BTC, Core Molecule of Type R ¹ -B " ₃ , with B" = COOH), 5-amino isophthalic acid (noted AIPA, branching molecule of type ARB ₂ , with A = NH ₂ and B = COOH), of I 'ε -caprolactam (noted CL, spacer of type A'-R'-B', with A' = NH ₂ and B '= COOH) and octadecylamine (noted C18, blocker of type A "-R ² , with A" = NH ₂ ). The respective overall composition is 1/25/25/2 in BTC / AIPA / CUC18. The same reactor as that described in Example 1 is used. A metal bath of Wood alloy is used for heating the reaction mixture. 74.3 g of ε-caprolactam (0.656 mol) and 66.4 g of demineralized water are introduced into the reactor at ambient temperature. After dissolution, 118.9 g of 5-amino acid isophthalic (0.656 mol), 5.5 g of benzene-1 acid, 3.5 tricarboxylic acid (0.026 mol) and 0.476 g of a 50% aqueous solution (w / w) of hypophosphorous acid are added. The reaction mixture is then stirred mechanically at 50 rpm. A weak sweep of dry nitrogen is carried out and the heating to 100 ° C. is started. The reaction mass is then rapidly heated from 100 ° C to 165 ° C, in about 15 min. An isothermal plate is produced at this temperature for 150 min. After one hour of plateau, when the distillation of the bottom water is carried out, 14.1 g of octadecylamine (0.052 mol) are added to the reaction mixture. After the total 150 min, the temperature is increased to 250 ° C over approximately 15-20 min and is then maintained on a plateau until the end of the synthesis.

After 2 hours of plateau, the reactor is gradually put under vacuum over a period of 60 min, then maintained under partial vacuum in order to limit foaming (36 mBar) for an additional hour. At the end of the cycle, the stirring is stopped and the reactor allowed to cool to room temperature under a stream of nitrogen. 192.5 g of polymer are collected. The hyperbranched copolyamide obtained is a whitish solid and will be finely ground for its subsequent use.

Example 11: 50/50 reverse emulsion water in oil An aqueous solution comprising 10% by weight of hyperbranched copolyamide of Example 10 and 0.6% NaCl is prepared and brought to pH = 6.3 using NaOH. 10 g of this aqueous solution are gradually added to 10 g of the Rhodorsil Extrasoft silicone oil, sold by Rhodia. The mixture is sheared using a frame blade at 400 revolutions per minute for 1-5 minutes. Light microscopy shows that the droplet size of this emulsion is less than 1 μm.

Example 12: Multiple water in oil in water 45/45/10 emulsion

External aqueous phase: An aqueous solution comprising 10% by weight of Synperonic PE / F127, sold by Uniquema and 0.6% of NaCl is prepared.

Emulsification by phase inversion 90/10:

2 g of the external aqueous phase are added to 18 g of the reverse emulsion of example 11 (internal emulsion) and the whole is sheared using a frame blade at 100 revolutions per minute for 2.5 minutes. Example 13: 35/65 reverse emulsion water in oil

Internal aqueous phase: An aqueous solution comprising 10% by weight of hyperbranched copolyamide of Example 10 and 0.6% NaCl is prepared and brought to pH = 6.3 using NaOH (or HCl).

7 g of this aqueous solution are gradually added to 13 g of the silicone oil

Rhodorsil Extrasoft, marketed by Rhodia. The mixture is sheared using a frame blade at 400 revolutions per minute for 1-5 minutes.

Light microscopy shows that the droplet size of this emulsion is less than 1 μm.

Example 14: Multiple emulsion water in oil in water 28/52/20

External aqueous phase: An aqueous solution comprising 10% by weight of Synperonic PE / F127 marketed by Uniquema and 0.6% of NaCl is prepared. Emulsification by phase inversion 80/20:

4 g of the external aqueous phase are added to 16 g of the reverse emulsion of Example 13 and the whole is sheared using a frame blade at 100 rpm for 2.5 minutes.

Example 15: Multiple emulsion comprising a single emulsifying polymer for the internal emulsion and the reverse emulsion

The operation is carried out as indicated in Examples 11 and 12, with the difference that the Synperonic PE / F127 is replaced by the hyperbranched copolyamide of Example 10. A stable multiple emulsion is obtained.

Example 16: introduction of a multiple emulsion in a detergent medium

1 g of Ariel Regular detergent sold by Procter & Gamble, Tide sold by Procter & Gamble are introduced into 100 of water of hardness TH = 30 ° f, and 0.1 g of silicone oil equivalent of the multiple emulsion of Example 12. The mixture is stirred using a magnetic stirrer at 25-30 ° C. Samples are taken after 2, 20 and 120 minutes, and it is observed under the microscope that the emulsion structure is preserved.

Claims

1. Emulsion comprising an internal phase, an external phase, and an emulsifying polymer, one of the phases being an aqueous phase, characterized in that the emulsifying polymer is a dendritic polymer.

2. Emulsion according to the preceding claim, characterized in that the dendritic polymer is dispersible or soluble in water, at the pH of the emulsion.

3. Emulsion according to one of the preceding claims, characterized in that the dendritic polymer is a hyperbranched polymer, comprising hydrophobic groups, and hydrophilic or potentially hydrophilic groups.

4. Emulsion according to one of the preceding claims, characterized in that the emulsion is a direct emulsion, the aqueous phase being the external phase, and in that at least part of the hydrophilic or potentially hydrophilic groups are groups present in ends of polymer chains.

5. Emulsion according to one of claims 1 to 3, characterized in that the emulsion is a reverse emulsion, the aqueous phase being the phase being the internal phase, and in that at least part of the hydrophobic groups are groups present at the ends of polymer chains.

6. Emulsion according to one of the preceding claims, characterized in that the emulsion is a multiple emulsion comprising an internal aqueous phase, an intermediate phase, and an external aqueous phase, the internal phase and the intermediate phase constituting an internal reverse emulsion , the intermediate phase and the external phase constituting an external direct emulsion, and in that at least one of the emulsions chosen from the inverse internal emulsion and the external direct emulsion comprises the dendritic polymer.

7. Emulsion according to the preceding claim, characterized in that the direct external emulsion and the internal reverse emulsion comprise the dendritic polymer.

8. Emulsion according to one of the preceding claims, characterized in that the dendritic polymer is a hyperbranched polyamide or a hyperbranched polyester.

9. Emulsion according to one of claims 1 to 6, characterized in that the dendritic polymer is a hyperbranched polymer capable of being obtained by a process comprising the following steps: a) polycondensation, so as to obtain a polymer, of monomers comprising at least one multifunctional monomer comprising at least three reactive functions, of formula (I) below: AR- (B), (I) formula in which - f is an integer greater than or equal to 2, preferably goes from 2 to 10, very particularly is equal to 2 - the symbol A represents a reactive function or a group carrying a reactive function chosen from amino, carboxy, hydroxy, oxiranyl, halogen, isocyanato, or their precursors - the symbol B represents a reactive function or a group carrying a reactive function chosen from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato or their precursors, antagonist of A - the symbol R represents a linear or branched aliphatic, cycloaliphatic or aromatic polyvalent hydrocarbon residue containing from 1 to 50, preferably from 3 to 20 carbon atoms, optionally interrupted by one or more heteroatoms of oxygen, nitrogen, sulfur or phosphorus, said residue optionally carrying functions or functional groups which are not capable of reacting with functions A and B, Step b) optionally, at least partial hydrophilic functionalization of the polymer obtained in the polycondensation step.

10. Emulsion according to the preceding claim, characterized in that the monomers of step a) comprise:

• at least one bifunctional monomer in linear form of formula (II) in corresponding cyclic form, comprising two reactive polycondensation / polymerization functions A'-R'-B '(II) formula in which: - the symbol A', identical to or different from A, represents a reactive function chosen from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato, or their precursors, antagonist of B and B ' - the symbol B ', identical to or different from B, represents a reactive function chosen from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato, or their precursors, antagonist of A and A' - the symbol R ', identical with or different from R, represents a polyvalent hydrocarbon residue linear or branched aliphatic, cycloaliphatic or aromatic containing from 1 to 50, preferably from 3 to 20 carbon atoms, optionally interrupted by one or more heteroatoms of oxygen, nitrogen, of sulfur or phosphorus, said residue optionally carrying functions or functional groups which are not capable of reacting with functions A, A ', B and B' ^* the reactive function A ', being capable of reacting with function B and / or function B 'by condensation; * the reactive function B ', being capable of reacting with function A and / or function A' by condensation;

• and / or at least one “core” monomer of formula (III), comprising at least one function capable of reacting by condensation with the monomer of formula (I) and / or the monomer of formula (II) R ¹ - (B ") _n (III) formula in which - n is an integer greater than or equal to 1, preferably goes from 1 to 100, very particularly from 1 to 20 - the symbol B" represents a reactive function, identical or different from B or B ', chosen from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato, or their precursors, antagonist of A and A' - the symbol R ¹ represents a polyvalent linear or branched aliphatic hydrocarbon residue containing cycloaliphatic or aromatic 1 to 50, preferably from 3 to 20 carbon atoms, optionally interrupted by one or more heteroatoms of oxygen, nitrogen, sulfur or phosphorus, or an organosiloxane or polyorganosiloxane residue, said residue R ¹ optionally carrying functions or some functional groups not capable of reacting with functions A, A ', B, B' and B " ^* reactive function B", being capable of reacting with function A and / or function A 'by condensation;

• and / or at least one “chain-limiting” monofunctional monomer of formula (IV) A "-R ² (IV) formula in which - the symbol A "represents a reactive function, identical to or different from A or A ', chosen from amino, carboxy, hydroxy, oxiranyl, halogen, isocyanato, or their precursors, antagonist of B, B' and B" - the symbol R ² represents a polyvalent linear or branched aliphatic, cycloaliphatic or aromatic hydrocarbon residue containing from 1 to 50, preferably from 3 to 20 carbon atoms, optionally interrupted by one or more heteroatoms of oxygen, nitrogen, sulfur or of phosphorus, or an organosiloxane or polyorganosiloxane residue, said residue R ² optionally carrying functions or functional groups which are not capable of reacting with the functions A, A ', A ", B, B' and B" * the reactive function A ", being capable of reacting with function B and / or function B 'and / or function B" by condensation; • at least one of the reactive functions of at least one of the monomers of formula (II), (III) or (IV) being capable of reacting with an antagonistic function of the multifunctional monomer of formula (I).

1 1. Emulsion according to one of claims 9 or 10, characterized in that the functions A, A ', A ", and B, B', B" are chosen from reactive functions or groups carrying reactive functions chosen from amino, carboxy, hydroxy, oxiranyl functions, or their precursors.

12. Emulsion according to one of claims 9 to 11, characterized in that at least one chain-limiting monomer is used, said monomer being hydrophilic or potentially hydrophilic.

13. Emulsion according to one of the preceding claims, characterized in that it is a formulation of a cosmetic product, a detergent product, a paint or a coating.

14. Emulsion according to the preceding claim, characterized in that the formulation of cosmetic product is a product for the care of the skin or the hair.

15. Use of a dendritic polymer as defined in one of the preceding claims, as an emulsifying agent.

16. Use according to the preceding claim, in a formulation of a cosmetic product, a detergent product, a paint or a coating.

17. Use according to the preceding claim, characterized in that the formulation of cosmetic product is a product for the care of the skin or the hair.