EP1684894A1

EP1684894A1 - Emulsion for conveying an active hydrophobic material to a substrate in an aqueous medium

Info

Publication number: EP1684894A1
Application number: EP04805319A
Authority: EP
Inventors: Ian Harrison; Evelyne Prat; Hélène LANNIBOIS; Anne-Gaëlle DRENO
Original assignee: Rhodia Chimie SAS
Current assignee: Rhodia Chimie SAS
Priority date: 2003-11-13
Filing date: 2004-10-27
Publication date: 2006-08-02
Also published as: US20070128142A1; FR2862235B1; WO2005049189A1; FR2862235A1; JP2007519506A

Abstract

The inventive emulsion (E) comprises a hydrophobic phase (O) containing and/or consisting of an active hydrophobic material (A) embodied in the form of a multiple emulsion (Em) comprising: an internal invert emulsion (Ei) which comprises a continuous phase (O), an aqueous dispersed phase (Wi) and, at the interface of two phases, a stabilising agent (Di) in a hydrosoluble or hydrodispersible polysaccharide whose mean polymerisation degree is equal to or greater than 1.5, preferably equal to or greater than 20, whose Brookfield viscosity at 25 DEG C in a 1 % water solution is less than 20 000 mPa.s., which is devoid of lipophilic polyorganosiloxane substituting groups, and; an external aqueous or water mixable phase (We) in which the internal emulsion (Ei) is dispersed or in the solid form (Es) which is hydrodispersible in a multiple emulsion (Em). The emulsion (E) after being used in an aqueous medium (B) is capable of conveying the active hydrophobic material to a substrate arranged in or brought into contact with said aqueous medium (B).

Description

The present invention relates to an emulsion (E), in the form of a multiple emulsion (Em), the reverse internal emulsion of which comprises a hydrophobic active substance, or in the form of an emulsion (E). solid (Es) water-dispersible in a multiple emulsion of water-in-oil-in-water (Em) type. This emulsion can be used to convey said hydrophobic active material to a substrate in an aqueous medium. It can in particular be used in a detergent or rinsing composition or as a detergent or rinsing composition for washing or rinsing articles of textile fibers, with the aim of conveying and promoting the deposition of a hydrophobic active material such as a perfume, an agent hydrophobic care ..., on a textile article, in cotton in particular. It has been proposed to use a multiple water-in-oil-in-water (W / OW) type emulsion to transport hydrophilic active materials. Thus, EP-930 933-A- claims a process for the controlled release of an active principle contained in a multiple emulsion of water-in-oil-in-water type, characterized in that: - said multiple emulsion comprises a reverse emulsion Ei with an aqueous phase A1 which contains at least one hydrophilic active principle, said emulsion Ei being dispersed in the form of droplets of direct emulsion Ed, in an aqueous continuous phase A2, with the two emulsions Ed and Ei stabilized by at least one surfactant, present at level of their respective continuous phases and in that said multiple emulsion is brought into contact with a sufficient amount of an agent, so as to transform it into a direct emulsion and to induce the release of the active principle, contained in the aqueous phase A1 of the emulsion Ei, in the aqueous phase A2. The surfactant present in the aqueous continuous phase A2 of the Ed emulsion is preferably chosen from water-soluble lecithins, sucrose esters, esters of fatty acids, polyoxyethylenated alkylamides, triglyceride sulfates, alkyl sulfates, alkyl ether sulfates, alkyls sulfonates, alkylamine salts, fatty amines, lipoamino acids, alkylbetaines, alkylpolyglycol ethers, copolymers of alkylene oxides, modified polyesters, silicone polymeric surfactants. The surfactant present in the continuous phase of the Ei emulsion is preferably chosen from liposoluble lecithins, esters of sorbitan and of fatty acids, polyalkylene dipolyhydroxystearates, fatty acids, monoglycerides, polyglycerol esters, polyglycerol polyricinoleate, lactic and tartaric acid esters. The continuous phase of the Ei emulsion is an oily phase composed of at least one oil chosen from mineral, vegetable or animal oils. The direct emulsion Ed, preferably comprises by volume from 50 to 99% of an aqueous continuous phase A2 for i to 50% of reverse emulsion Ei The reverse emulsion Ei is preferably composed by volume of 50 to 99% d '' a continuous phase for 1 to 50% of aqueous phase A1. It is also known to prepare granules obtained by drying a multiple emulsion of water in oil in water (W / O / W) type, the internal aqueous phase of which comprises a hydrophilic active material. Thus WO 02/32563 claims granules capable of being obtained by drying a reverse emulsion, dispersed in an external aqueous phase,

(a) the reverse emulsion comprising an internal aqueous phase, comprising at least one hydrophilic active material, dispersed in an internal oily phase, said internal oily phase comprising at least one nonionic or cationic surfactant and / or at least nonionic amphiphilic polymer or cationic,

(b) the external aqueous phase comprising: - at least one nonionic polyoxyalkylenated surfactant and / or at least one nonionic polyoxyalkylenated amphiphilic polymer, - and at least one water-soluble or water-dispersible compound chosen from (i) the polymers obtained by polymerization of at least one carboxylic acid monomer, and at least one ethylenically unsaturated monomer, and / or at least one polyoxyalkylenated ester of ethylenically unsaturated carboxylic acid; (ii) polymers resulting from the polymerization of at least one carboxylic acid monomer and optionally comprising at least one hydrophobic graft; (iii) polypeptides of natural or synthetic origin, optionally comprising at least one hydrophobic graft; (iv) highly depolymerized polysaccharides optionally comprising at least one hydrophobic graft. These granules are redispersible in an aqueous medium in a multiple emulsion. The object of the invention is an emulsion in the form of a multiple emulsion or in a dry form redispersible in a multiple emulsion, the oil phase of which consists of or comprises a hydrophobic active material, emulsion which, after being used in an aqueous medium is capable of carrying said hydrophobic active material towards a substrate present in or in contact with said aqueous medium. A first object of the invention consists of an emulsion (E) comprising a liquid or fusible hydrophobic phase (O) containing and / or consisting of at least one hydrophobic active material (A), said emulsion (E) having: in the form of a multiple emulsion (Em) comprising: - an internal inverse emulsion (Ei) comprising said continuous hydrophobic liquid or fusible phase (O), an aqueous dispersed phase (Wi) and, at the interface of the two phases, at least one water-soluble or water-dispersible stabilizing agent (Di) - an aqueous or water-miscible external phase (We), in which the internal emulsion (Ei) is dispersed, using at least one dispersing agent and / or stabilizer (De) • or in solid form (Es), water-dispersible in a multiple emulsion (Em) in which the external phase (We) is aqueous, comprising - the reverse emulsion (Ei) dispersed in a matrix (M) water-soluble or water-dispersible solid - and the dispersing and / or stabilizing agent (De) located at the interface of the reverse emulsion (Ei) and the matrix (M) and optionally dispersed in the matrix (M) said emulsion being characterized in that the stabilizing agent (Di) at the interface of the two phases of the emulsion internal inverse (Ei) is made of a material chosen from water-soluble or water-dispersible polysaccharides (PSA): - whose average degree of polymerization (DP) is at least 1.5, preferably at least 20, very particularly at least 100 - whose Brookfield viscosity at 25 ° C in solution at 1% by mass in water is less than 20,000 mPa.s., preferably less than 5,000 mPa.s., very particularly ranging from 1 to 4,500 mPa.s., said polysaccharides (PSA) being also free of lipophilic polyorganosiloxane substituent groups. Inverse emulsion (Ei) According to the invention, the hydrophobic phase (O) contains and / or consists of at least one hydrophobic active material (A). The hydrophobic phase (O) and / or the active material (A) are made of at least one organic or organosilicon material or a mixture of at least one organic material and at least one organosilicon, liquid or fusible material which is insoluble in a aqueous phase. When the active material (A) is contained in the hydrophobic phase (O), it can also be in at least one solid or liquid inorganic material insoluble in an aqueous phase or in a mixture of at least one inorganic material and at least one organic material and / or at least one organosilicon material. According to the invention, the material constituting the hydrophobic phase (O) or the active material (A) is considered to be insoluble when less than 15%, preferably less than 10% of its weight, is soluble in the internal aqueous phase (Wi) and the external phase (We) if the latter is present, and this in a temperature range between 20 ° C. and the preparation temperature of the inverse emulsion (Ei) and of the multiple emulsion (Em) or of the emulsion in a solid form (Es).

Said hydrophobic phase (O) preferably has a melting point less than or equal to 100 ° C., more particularly less than or equal to 80 ° C. Said material constituting the hydrophobic phase (O), may be made of an organosilicon material (01).

It is in particular 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. These may include:

• 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 nonionic or amino polyorganosiloxane. As examples of polyorganosiloxanes, there may be mentioned: > linear, cyclic or crosslinked polyorganosiloxanes formed from nonionic organosiloxane units of general formula (R) a (X) bSKO) _[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 equal to 0, 1, 2 or 3 Preferably, said polyorganosiloxane is at least substantially linear, and very 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) _c Si (O) r ₄ _ _(a + _b + c)] / 2 (») formula in which • the symbols R are identical or different and represent a monovalent 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 ¹ function, where R ′ represents an alkyl group containing from 1 to 12 atoms carbon, 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 0, 1 or 2

• b is 0, 1 or 2

• c is equal to 1 or 2

• a + b + c is equal to 1, 2 or 3 By way of example of substituents corresponding to the symbol (B) in the formula (II) above, one can mention

- 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, per 100 total silicon atoms, from 0.1 to

50, preferably from 0.3 to 10, very particularly from 0.5 to 5 aminofunctionalized silicon atoms. sterically hindered piperidinyl groups of formula

OR * o R4 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 contains 2 to 12 carbon atoms and the cyclo-hexylene 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 which are} 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 Ov or the sterically hindered piperidinyl groups of formula IV

or * R ' ⁴ is chosen from a trivalent radical of formula: - (CH ₂ ) CH 'm \ co— OÙ _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 polyorganosiloxane with a sterically hindered amino function 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. Said material constituting the hydrophobic phase (O), may be made of an organic material (02). By way of example, there may be mentioned - the mono-, di- or triglycerides of C-ι-C ₃₀ carboxylic acids or their mixtures, such as vegetable oils (rapeseed, castor oil, sunflower oil, rapeseed oil erucic, linen ...)

- technical oils, such as cooked, blown or stand-up linseed oils marketed by NOVANCE - sucroesters, sucroglycerides

C ₁ -C ₃₀ alcohol esters of C ₁ -C ₃₀ carboxylic or C ₂ -C ₃₀ dicarboxylic acids,

- ethylene or propylene glycol monoesters or diesters of Cι.-C ₃ o carboxylic acids - propylene glycols of C -C ₂ alkyl ether

- di Cs-C ₃ o alkyl ethers

- mineral oils, such as naphthenic, paraffinic (petrolatum) oils, polybutenes

- organic waxes comprising alkyl chains containing from 4 to 40 carbon atoms. Among the waxes, we can mention in particular: • animal waxes (beeswax, lanolin, whale oil) • vegetable waxes (carnauba, candellila, sugar cane wax, jojoba) • fossil mineral waxes (montane, ozokerite, Utah wax) • hydrocarbon waxes comprising from 4 to 35 carbon atoms (mineral oils, paraffins, microcrystalline waxes) • synthetic waxes such as polyolefins (polyethylene, polypropylene), sterone, carbowax.

The active ingredient (A) can constitute the hydrophobic phase (O) or be contained in the hydrophobic phase (O); when it is contained in the hydrophobic phase (O), it can be soluble, partially soluble or insoluble in said hydrophobic phase (O). Mention may be made, as active materials (A) contained in the hydrophobic phase (O), of other hydrophobic materials such as in particular the perfume molecules, the organic or organosilicon anti-UV agents, the hydrophobic bactericidal agents, solid polyamide capsules, particles of silica or other oxides or inorganic compounds ...

Stabilizing agent (Di)

The stabilizing agent (Di) is made of a material chosen from water-soluble or water-dispersible polysaccharides (PSA): - whose average degree of polymerization (DP) is at least 1.5, preferably at least 20, very particularly at least 100 - whose Brookfield viscosity at 25 ° C in solution at 1% by mass in water is less than 20,000 mPa.s., preferably less than 5,000 mPa.s., very particularly ranging from 30 at 4500 mPa.s., said polysaccharides (PSA) being also free of lipophilic polyorganosiloxane substituent groups.

The expression “water-soluble or water-dispersible” means here that said polysaccharide (PSA) is not capable of forming a macroscopic two-phase solution at 25 ° C. in the internal aqueous phase (Wi). The expression "lipophilic" is used here as antonym of the term "hydrophilic"; that is, has no affinity for water; this means that the polyorganosiloxane groups, of which the polysaccharide (PSA) is free, would form, taken alone, at a concentration of 10% by weight, a macroscopic two-phase solution in distilled water at 25 ° C. According to the invention, the Brookfield viscosity at 25 ° C. of a 1% by mass solution of polysaccharide (PSA) in an aqueous HCl solution at 1% by volume can be determined as follows, after aging for 24 hours at 40 ° C. Equipment and Reagents Equipment • 800ml beaker, low form • 250ml bottle • Stirring motor allowing to obtain 500 rpm and equipped with a 65mm diameter Raeneri deflocculating paddle • Brookfield LVT viscometer equipped with a needle n ° 2 (planetary or disc type) • Oven set at 40 ° C Reagents • Distilled water • 10% hydrochloric acid solution by volume. In a 100 ml flask containing approximately 50 ml of distilled water, introduce 27.0 g of 37% hydrochloric acid (density = 1.19) grade analyzes. Make up to 100 ml with distilled water. Procedure • On a sheet of glossy paper, weigh 0.9 g of the polysaccharide • In the 800 ml beaker, weigh 269.1 g of water • Stir the water then add the powder in 20 to 30 seconds on the edges of the vortex. Shake for 30 minutes at 500 rpm. • While stirring, add 30g of the 10% hydrochloric acid solution to the solution in 5 to 10 seconds. Shake again for 5 minutes at 500 rpm. • Transfer the solution to the 250ml bottle and place it in the oven at 40 ° C. • After 24 hours, take the bottle out of the oven and reduce the temperature of the solution to that of room temperature (20 - 25 ° C). • Measure the viscosity of the solution with the Brookfield viscometer set at 3 rpm and equipped with needle No. 2 (planetary). Read after stabilization of the display (N).

Expression of results Apparent viscosity η of the 1% polysaccharide solution (PSA) in the 1% HCl solution η = 100 x N The term average degree of polymerization is understood to mean the average number of glycosyl units per mole of polysaccharide . Said polysaccharide (PSA) is a homopolysaccharide or a heteropolysaccharide; it can be linear or branched, non-ionic or ionic; it can optionally be substituted and / or modified by nonionic or ionic groups, other than lipophilic polyorganosiloxane groups.

Preferably, said polysaccharide (PSA), or its backbone, comprises similar or different glycosyl units joined by β (1-4) bonds. In addition to the β (1-4) bonds, it can also comprise other bonds, in particular β (1-3) and / or β (1-6). Said glycosyl units, similar or different, can in particular be hexose and / or pentose units. Among the hexose units (similar or different), mention may in particular be made of D-glucose, D- or L-galactose, D-mannose, D- or L-fucose, L-rhamnose units Among the pentose units (similar or different), there may be mentioned in particular the D-xylose, L- or D-arabinose units, etc. The hydroxyl functions or functions of the glycosyl units can be modified and / or substituted by nonionic groups. , ionic or ionizable.

When non-ionic modifying groups are concerned, these can in particular be linked to the carbon atoms of the sugar skeleton either directly or via —O— bonds. Among the nonionic groups, mention may be made of: • The alkyl groups comprising from 1 to 22 carbon atoms, optionally interrupted by one or more heteroatoms of oxygen and / or nitrogen,

• Aryl or arylalkyl groups comprising from 6 to 12 carbon atoms • Hydroxyalkyl or cyanoalkyl groups comprising from 1 to 6 carbon atoms

• The “ester” groups obtained by replacing hydrogen with a hydroxyl function -OH of the polysaccharide skeleton by a group comprising at least one acid unit containing in particular carbon, sulfur or phosphorus, such as in particular the carbonyl groups R- (CO) -, sulfonyl R-SO ₂ -, phosphorylated R ₂ P (O) -, hydroxyphosphorylated R- P (O) (OH) -, acid groups forming "ester" units with the residual oxygen atoms of the skeleton polysaccharide. The group R, alkyl, alkenyl, aryl, can comprise from 1 to 20 carbon atoms; it can also comprise a heteroatom, of nitrogen for example, linked directly to a carbonyl, sulfonyl unit, etc., and thus form urethane type bonds, etc. As an example, mention may be made of:

• The methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, dodecyl, octadecyl, phenyl groups linked to a carbon atom of the polysaccharide skeleton via an ether, ester, amide, urethane bond

• Cyanoethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl groups, linked to a carbon atom of the polysaccharide skeleton via an -O- bond

• The “ester” groups chosen from the acetate, propanoate, trifluoroacetate, 2- (2-hydroxy-1-oxopropoxy) propanoate, lactate, glycolate, pyruvate, crotonate, isovalerate, cinnamate, formate, salicylate, carbamate groups methylcarbamate, benzoate, gluconate, methanesulfonate, toluenesulfonate; the hemiesters groups of fumaric, malonic, itaconic, oxalic, maleic, succinic, tartaric, aspartic, glutamic, malic acids; there may be mentioned more particularly the substituent groups acetate, hemiacetate and 2- (2-hydroxy-1-oxopropoxy) propanoate. The rate of MS modification of a polysaccharide by a nonionic modifying group corresponds to the average number of moles of precursor of the nonionic modifying group which has reacted per glycosyl unit. The rate of modification MS can vary according to the nature of the precursor of said modifying group.

If said precursor is not capable of forming new reactive hydroxyl groups (alkylation precursor for example), the rate of modification by nonionic groups is less than 3 by definition. If said precursor is capable of forming new reactive hydroxyl groups (hydroxyalkylation precursor for example), the rate of modification MS is theoretically not limited; it can for example go up to 6, preferably up to 2. This rate is generally at least 0.001, preferably at least 0.01. Among the anionic or anionizable groups, mention may be made of those containing one or more carboxylate, sulfonate, sulfate, phosphate, phosphonate functions, etc.

Mention may in particular be made of those of formula. - [- CH2-CH (R) -O] _x - (CH ₂ ) y-COOH or • - [- CH ₂ -CH (R) -O] _x - (CH2) y-COOM, where R is an atom of hydrogen or an alkyl radical containing from 1 to 4 carbon atoms x is an integer ranging from 0 to 5 y is an integer ranging from 0 to 5 M represents an alkali metal

Mention may very particularly be made of the carboxy groups —COO ^′ Na * linked directly to a carbon atom of the sugar skeleton, methyl carboxy (sodium salt) —CH2-COO ^" Na ⁺ linked to a carbon atom of the sugar skeleton by the Intermediate of an —O— bond. Among the cationic or potentially cationic groups, mention may be made of those containing one or more amino, ammonium, phosphonium, pyridinium, etc. functions. Mention may in particular be made of the cationic or potentially cationic groups of formula -NH ₂ - [- CH ₂ -CH (R) -O] _x - (CH ₂ ) _y -COA-R'-N (R ") 2 - [ -CH ₂ -CH (R) -O] _x - (CH ₂ ) y-COA-R'-N ⁺ (R '") 3 X" - [- CH ₂ -CH (R) -O] _x - ( CH ₂ ) y-COA-R'-NH-R "" - N (R ") ₂ - [- CH ₂ -CH (R) -O] _x -R'-N (R") 2 - [- CH ₂ -CH (R) -O] _x -R'-N ⁺ (R '") 3 X" - [- CH ₂ -CH (R) -O] _x -R'-NH-R "" - N ( R ") ₂ • - [- CH ₂ -CH (R) -O] _x -YR" where. R is a hydrogen atom or an alkyl radical containing from 1 to 4 carbon atoms. X is an integer ranging from 0 to 5. y is an integer ranging from 0 to 5. R 'is an alkylene radical containing from 1 to 12 carbon atoms, optionally bearing one or more OH substituents. the radicals R ", which are similar or different, represent a hydrogen atom, an alkyl radical containing from 1 to 18 carbon atoms. the radicals R '", which are similar or different, represent an alkyl radical containing from 1 to 18 carbon atoms. R""is a linear, branched or cyclic alkylene radical containing from 1 to 6 carbon atoms. A represents O or NH. Y is a heterocyclic aliphatic group comprising from 5 to 20 carbon atoms and a nitrogen heteroatom X 'is a counterion, preferably halide (chloride, bromide, iodide in particular), as well as the N-alkylpyridinium-yl groups whose alkyl radical contains from 1 to 18 carbon atoms, with a counterion, preferably halide (chloride, bromide, iodide in particular).

Among the cationic or potentially cationic groups, there may be mentioned very particularly: - those of formula • -NH ₂

• -CH ₂ -CONH- (CH) ₂ -N (CH ₃ ) ₂

• -CH ₂ -COO- (CH ₂ ) ₂ -NH- (CH ₂ ) ₂ -N (CH3) ₂

. -CH ₂ -CONH- (CH) ₃ -NH- (CH ₂ ) ₂ -N (CH ₃ ) ₂ -CH ₂ -CONH- (CH ₂ ) ₂ -NH- (CH ₂ ) 2-N (CH ₃ ) 2 -CH2-CONH- (CH ₂ ) 2-N ⁺ (CH ₃ ) 3 Cl "-CH2-CONH - (CH2) 3-N ⁺ (CH3) 3 CI "- (CH ₂ ) ₂ -N (CH ₃ ) ₂ - (CH ₂ ) ₂ -NH- (CH ₂ ) 2-N (CH ₃ ) ₂ - ( CH ₂ ) 2-N ⁺ (CH ₃ ) ₃ Cif all preferably 2-hydroxypropyltrimethyl ammonium chloride -CH ₂ -CH (OH) -CH2-N ⁺ (CH ₃ ) 3 Cl "pyridinium-yl groups such as N-methyl pyridinium-yle, of formula

with a chloride counterion the hindered amino groups such as those derived from HALS amines, of general formula:

where R represents CH3 or H. Among the betaine groups, mention may be made of the functions of formula:

2-methyl (3-sulfopropyl) imidazolium function (2-sulfobenzyl) imidazolium function

(3-sulfopropyl) pyridinium function - (CH ₂ ) ₂ -N ⁺ (CH ₃ ) ₂ - (CH ₂ ) ₂ -COO ^" ethyl-dimethylammonium betaine function - (CH ₂ ) ₂ -N ⁺ (CH ₃ ) ₂ - (CH ₂ ) ₃ -SO ₃ ^" sulfo-propyl dimethylammonium function

The degree of substitution DS corresponds to the average number of hydroxyl functions of the glycosyl units substituted by the said ionic or ionizable group or groups, per glycosyl unit. It is generally less than 3, preferably less than 2. Among the polysaccharides (PSA) which can be used according to the invention, mention may be made of natural or synthetic polysaccharides, preferably modified and / or chemically substituted and / or degraded (depolymerized) by acid or basic hydrolysis, or by oxidative, thermal or enzymatic means. As examples we can mention:

Galactomannans (especially guar gum) depolymerized. in particular by an oxidative route, optionally modified or substituted by non-ionic groups (hydroxypropyl in particular), anionic (carboxymethyl in particular), cationic (hydroxypropyltrimethylammonium chloride for example), having a Brookfield viscosity (1% solution in water) which can range from 30 to 4500 mPa.s., preferably from 60 to 3500 mPa.s. We can cite in particular:

• Guars depolymerized by the oxidative route (having some COOH ⁺ functions resulting from depolymerization in an oxidizing medium), such as MEYPRO-GAT 7, MEYPRO-GAT 20, MEYPRO-GAT 30 marketed by Rhodia

• Hydropropopropylated depolymerized guars with a rate of modification of the order of 0.01 to 0.8, such as Rhodia's HMP-CON • Depolymerized carboxymethylated guars with a degree of substitution of the order of 0.05 to 1 , 6 like the MEYPRO-GUM R 600 marketed by Rhodia

• Cationized depolymerized guars with a degree of substitution of the order of 0.04 to 0.17, preferably 0.06 and 0.14, such as MEYPRO-COAT 21 marketed by Rhodia, AquaCat CG 518 marketed by Aqualon Modified celluloses, such as

• Cellulose monoacetates, having a degree of substitution from 0.3 to less than 1.2, preferably from 0.3 to 1. • Hydroxypropylated celluloses having a modification rate of the order of 0.2 to 1 , 5 like the Primaflo HP22 marketed by Aqualon

• Carboxymethylcelluloses with a degree of substitution of 0.05 to 1.2, preferably 0.05 to 1, such as Blanose Cellulose gum from Hercules and Liberty 3794 from Aqualon Dextrins possibly containing hydroxyethyl, hydroxypropyl groups or quaternized aminoalkyl (degradation of starches, optionally chemically modified by hydroxyethyl, hydroxypropyl or quaternized aminoalkyl groups).

- xyloqlvcanes like the tamarind gum Instasol 1200 from Saiguru Food, the MEYPRO-GUM T12 marketed by Rhodia.

- arabinoxylans

- alkylpolvglvcosides (APG) having a C4-C20 alkyl group _> preferably CS-C-JS. as well as an average number of glucose units of the order of 1.5 to 10, preferably of the order of 1.5 to 4, more generally of the order of 1.6 to 2.7 per mole of alkylpolyglycoside (APG), such as those mentioned in US 4,565,647.

Internal aqueous phase (Wi)

The average size of the aqueous droplets (Wi) of the internal inverse emulsion (Ei) can range up to 10 μm, preferably from 0.05 μm to 5 μm, and more preferably from 0.1 to 1 μm.

The average size corresponds to the median diameter in volume (d50), which represents the diameter of the particle equal to 50% of the distribution cumulative; it can for example be measured with a Horiba granulometer or optical microscope.

The dispersed aqueous phase (Wi) has a pH which can range from 0 to 14, preferably from 2 to 11, more preferably from 5 to 11. It can contain additives making it possible to adjust the osmotic pressure, such as salts (chloride or sulfate sodium, calcium chloride ...) or sugars (glucose) or polysaccharides (dextran ...). It can also contain buffering agents, hydrophilic active materials, in particular antibacterial agents such as methyl chloro isothiazolinone and methyl isothiazolinone (KATHON® CG marketed by

Rohm and Haas), other water-soluble or water-dispersible materials, as well as hydrophobic materials insoluble in the hydrophobic phase (O). For a good implementation of the invention, the mass ratio of the dispersed aqueous phase (Wi) to the hydrophobic phase (O) can range from 5/95 to 95/5, preferably from 3070 to 80/20.

The ratio of the mass of stabilizer (Di) to the mass of hydrophobic phase (O) can range from 0.1 / 100 to 500/100, preferably from 0.5 / 100 to 100/100, very particularly from 0, 5/100 to 50/100. The inverse emulsion (Ei) can be obtained in a conventional manner. For example, it can be obtained by dissolving and / or dispersing the polysaccharide (PSA) in water and then adding the aqueous solution and / or dispersion obtained to the hydrophobic phase (O), with stirring.

The stirring can advantageously be carried out by means of a frame blade, a planetary type mixer, a mixer having a scraping mobile and a blade rotating in opposite directions (counter-stirring).

The preparation of the reverse emulsion is generally carried out at a temperature higher than the melting temperature of the material used as the hydrophobic phase, but lower than that of degradation of the elements entering into the composition of the reverse emulsion. More particularly, this temperature is between 10 and 80 ° C.

The duration of the agitation can be determined without difficulty by those skilled in the art.

It is preferably sufficient to obtain an average size of aqueous droplets of the reverse emulsion of less than 10 μm, as mentioned above.

The amounts of the various constituents of the inverse emulsion (Ei) have already been defined above.

Multiple emulsion (Em) The multiple emulsion (Em) comprises the reverse emulsion above (Ei), as internal emulsion, dispersed in an external phase (We) aqueous or miscible with water, comprising at least one dispersing agent and / or stabilizer (De). Said dispersing and / or stabilizing agent (De) has a hydrophilic tendency. Preferably, said dispersing and / or stabilizing agent (De) is chosen from hydrophilic surfactants and / or hydrophilic polymers and / or hydrophilic amphiphilic polymers.

The term "hydrophilic" is used in its usual sense of "who has an affinity for water"; this means that the dispersing and / or stabilizing agent (De) is not capable of forming a macroscopic two-phase solution in distilled water at 25 ° C. Preferably, the external phase (We) is an aqueous phase. More particularly, the surfactants and / or polymers (De) satisfy the Bancroft rule and are preferably chosen from compounds which satisfy both of the two conditions below: - when they are mixed with the external aqueous phase at a concentration between 0.1 and 10% by weight of said phase and between 20 and 30 ° C, they are in the form of a solution in all or part of the concentration range indicated. - when mixed with the internal hydrophobic phase (O) at a concentration of between 0.1 and 10% by weight of said phase and between 20 and 30 ° C, they are found in the form of a dispersion throughout or part of the concentration range indicated. For a good implementation of the invention, said dispersing and / or stabilizing agent (De) can be formed (a) of at least one nonionic hydrophilic surfactant (b) of at least one anionic hydrophilic surfactant (c ) at least one cationic hydrophilic surfactant (d) at least one nonionic hydrophilic polymer (e) at least one nonionic hydrophilic amphiphilic polymer (f) at least one anionic hydrophilic polymer (g ) of at least one anionic hydrophilic amphiphilic polymer (h) of at least one cationic hydrophilic polymer (i) of at least one cationic hydrophilic amphiphilic polymer G) or of a mixture of at least two of said surfactants and / or polymers (a) to (d) above compatible. The term “compatible” means here that the surfactants in a mixture are not capable of causing the formation of aggregates in the non-dispersed state in the medium considered.

The total content of surfactant (s) and / or polymer (s) (De) present (s) in the external phase (We) can be between 0.01 and 50% by weight, preferably between 0.1 and 10%, more particularly between 0.5 and 5% by weight, relative to the inverse emulsion (Ei). Preferably, the nonionic hydrophilic surfactants have an HLB value at least equal to the required HLB of the hydrophobic phase (O); as an indication, this minimum value of HLB is most often at least 10. These are preferably polyalkoxylated.

Advantageously, the polyalkoxylated nonionic surfactant can be chosen from the following surfactants, alone or as a mixture:

- alkoxylated fatty alcohols - alkoxylated mono, di and triglycerides

- alkoxylated fatty acids

- alkoxylated sorbitan esters

- alkoxylated fatty amines

- the alkoxylated di (phenyl-1 ethyl) phenols - the alkoxylated tri (phenyl-ethyl) phenols

- Alkoxylated alkyl phenols, more particularly ethoxylated and / or propoxylated.

For purely illustrative purposes, the total number of ethoxylated and optionally propoxylated units is between 10 and 100. Among the anionic hydrophilic surfactants that may be mentioned:

- alkyl esters sulfonates,

- alkyl sulphates, as well as their polyalkoxylated derivatives (ethoxylated (OE), propoxylated (OP), or their combinations), such as for example sodium dodecyl sulphate; - alkyl ether sulfates, as well as their polyalkoxylated derivatives (ethoxylated (OE), propoxylated (OP), or their combinations), such as for example laurylethersulfate with n = 2.

- sulphate alkylamides, as well as their polyalkoxylated derivatives (ethoxylated (OE), propoxylated (OP), or their combinations); - salts of saturated or unsaturated fatty acids, and

- the alkyl and / or alkyl ether and / or alkylaryl ether ester phosphates. Among the cationic hydrophilic surfactants which may also be present in the dispersing and / or stabilizing agent (De), it is possible to mention the quaternary ammonium salts of formula R ¹ R ² R ³ R ⁴ N ⁺ X ^" where the groups R are long or short hydrocarbon chains, alkyl, hydroalkyl or alkyl ethoxylated, X being a counterion (R ¹ is a group C ₈ -C ₂₂ , preferably Cβ-C-10 or C12-C14 alkyl, R ² is a methyl group, R ³ and R ^{4 being} similar or different being a methyl or hydroxy methyl group); as well as Cationic esters, such as choline esters. With regard to the nonionic hydrophilic polymers which can be used, mention may be made of the water-soluble or water-dispersible nonionic polysaccharides (PSA) already mentioned above as stabilizing agent (Di), For example

• hydroxypropylated celluloses with a rate of modification of the order of 0.2 to 1.5, or

• cellulose monoacetates with a degree of substitution of 0.3 to less than 1.2. As regards nonionic hydrophilic amphiphilic polymers, the latter are preferably polyalkoxylated compounds, comprising at least two blocks, one of them being hydrophilic, the other hydrophobic, at least one of the blocks comprising polyalkoxylated, more particularly polyethoxylated and / or polypropoxylated patterns. More particularly, said nonionic polyalkoxylated hydrophilic amphiphilic polymers are chosen from polymers whose molar mass by weight is less than or equal to 100,000 g / mol (measured by GPC, polyethylene glycol standard), preferably between 1,000 and 50,000 g / mol, preferably between 1,000 and 20,000 g / mol. As examples of polymers of this type, mention may be made, inter alia, of polyethylene glycol / polypropylene glycol / polyethylene glycol triblock polymers. Such polymers are well known and are in particular marketed under the brands Pluronic (marketed by BASF), Arlatone (marketed by ICI). Said hydrophilic nonionic amphiphilic polymer can also be is a hydrophilic amphiphilic block polymer, obtained by polymerization of at least one hydrophilic nonionic monomer and at least one hydrophobic monomer, the proportion and nature of said monomers being such that the polymer resulting checks the conditions previously stated (Bancroft rule - two conditions). They comprise at least one hydrophobic block and at least one neutral (nonionic) hydrophilic block. In the case where said polymer comprises at least three blocks, and more particularly three blocks, the polymer is advantageously linear. In addition, the hydrophilic blocks are more particularly at the ends. In the case where the polymers comprise more than three blocks, the latter are preferably in the form of grafted or combed polymers.

Among the hydrophobic monomers from which the hydrophobic block (s) of the hydrophilic amphiphilic polymer may be mentioned, in particular:

- the 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;

- αβ-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,

- monomers of the cyclic siloxane type or not, chlorosilanes; - propylene oxide, butylene oxide; alone or in mixtures, as well as the macromonomers derived from such monomers.

As specific examples, we can cite:

- esters of (meth) acrylic acid with an alcohol comprising 1 to 12 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) n-butyl acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl 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; alone or in mixtures, as well as the macromonomers derived from such monomers.

The preferred monomers are the esters of acrylic acid with linear or branched Cι-C ₄ alcohols such as methyl, ethyl, propyl acrylate and butyl, vinyl esters such as vinyl acetate, styrene, α-methylstyrene.

As regards the nonionic hydrophilic monomers from which the hydrophilic amphiphilic block polymers can be obtained, mention may be made of ethylene oxide; amides of mono- or polycarboxylic acids, linear, branched, cyclic or aromatic, comprising at least one ethylenic unsaturation, or derivatives, such as (meth) acrylamide, N-methyloI (meth) acrylamide; hydrophilic esters derived from (meth) acrylic acid such as for example 2-hydroxyethyl (meth) acrylate; vinyl esters making it possible to obtain polyvinyl alcohol blocks after hydrolysis, such as vinyl acetate, vinyl Versatate®, vinyl propionate. These monomers can be used alone, in combination, as well as in the form of macromonomers. It is recalled that the term macromonomer designates a macromolecule carrying one or more functions which can be polymerized by the method used.

The preferred hydrophilic monomers are acrylamide and methacrylamide, alone or as a mixture, or in the form of macromonomers. Preferably, the nonionic hydrophilic amphiphilic polymers have an HLB value at least equal to the required HLB of the hydrophobic phase (O); As an indication, this minimum value of HLB is most often at least 10. Among the anionic hydrophilic polymers which may be used, mention may be made of the water-soluble or water-dispersible anionic polysaccharides (PSA) already mentioned above as stabilizing agent ( Di), such as

• Oxidically depolymerized guars (with some COOH ⁺ functions resulting from depolymerization in an oxidizing medium), such as MEYPRO-GAT 7, MEYPRO-GAT 20, MEYPRO-GAT 30 sold by Rhodia • Depolymerized hydroxypropylated guars with a change in the order of 0.01 to 0.8, such as Rhodia's HMP-CON

• Carboxymethylated depolymerized guars having a degree of substitution of the order of 0.05 to 1.6, such as MEYPRO-GUM R 600 sold by Rhodia. Among the anionic hydrophilic amphiphilic polymers which may be used, mention may be made particularly of block polymers, preferably diblocks or triblocks, obtained by polymerization of at least one anionic hydrophilic monomer, optionally at least one nonionic hydrophilic monomer, and at least one hydrophobic monomer. Again, the choice of monomers and their respective proportions are such that the resulting polymer satisfies the two conditions set out above (Bancroft rule).

As regards the anionic hydrophilic monomers from which the hydrophilic amphiphilic block polymers can be obtained, mention may be made

- linear, branched, cyclic or aromatic mono- or polycarboxylic acids, N-substituted derivatives of such acids; monoesters of polycarboxylic acids, comprising at least one ethylenic unsaturation;

- linear, branched, cyclic or aromatic vinyl carboxylic acids;

- amino acids comprising one or more ethylenic unsaturations; alone or as mixtures, their precursors, their sulfonic or phosphonic derivatives, as well as the macromonomers derived from such monomers; the monomers or macromonomers which may be in the form of salts. More particularly, we can cite:

- acrylic acid, methacrylic acid, fumaric acid, itaconic acid, citraconic acid, maleic acid, acrylamido glycolic acid, 2-propene 1-sulfonic acid, acid methallyl sulfonic, styrene sulfonic acid, α-acrylamido methylpropane sulfonic acid, 2-sulfoethylene methacylate, sulfopropyl acrylic acid, bis-sulfopropyl acrylic acid, bis-sulfopropyl methacrylic acid, sulfatoethyl acid methacrylic, hydroxyethyl methacrylic acid phosphate ester, as well as alkali metal salts, such as sodium, potassium, or ammonium;

- vinyl sulfonic acid, vinylbenzene sulfonic acid, vinyl phosphonic acid, vinylidene phosphoric acid, vinyl benzoic acid, as well as alkali metal salts, such as sodium, potassium, or ammonium ;

- N-methacryloyl alanine, N-acryloyl-hydroxy-glycine; alone or in mixtures, as well as the macromonomers derived from such monomers.

Examples of nonionic hydrophilic monomers and hydrophobic monomers have already been mentioned above. Among the cationic hydrophilic polymers which can be used, mention may be made of water-soluble polysaccharides (PSA) or cationic water dispersants already mentioned above as stabilizing agent (Di), such as for example

• Cationized depolymerized guars with a degree of substitution of the order of 0.04 to 0.17, preferably 0.06 and 0.14, such as MEYPRO-COAT 21 marketed by Rhodia, AquaCat CG 518 marketed by Aqualon According to a first preferred embodiment of the invention, the dispersing and / or stabilizing agent (De) is chosen from nonionic hydrophilic surfactants and / or nonionic hydrophilic (amphiphilic) polymers; more preferably, said nonionic hydrophilic surfactants and / or nonionic hydrophilic (amphiphilic) polymers have an HLB value at least equal to the required HLB of the hydrophobic phase (O); as an indication, this minimum value of HLB is most often at least 10. The hydrophilic amphiphilic hydrophilic agent (De) is very particularly a non-ionic hydrophilic amphiphilic polymer. According to a second preferred embodiment of the invention, the dispersing and / or stabilizing agent (De) is in a mixture of at least one nonionic hydrophilic surfactant and at least one anionic hydrophilic surfactant, optionally combined at least one nonionic hydrophilic (amphiphilic) polymer. According to a third embodiment of the invention, the dispersing and / or stabilizing agent (De) is chosen from cationic hydrophilic surfactants and / or cationic hydrophilic (amphiphilic) polymers, optionally mixed with at least one surfactant nonionic hydrophilic and / or at least one nonionic hydrophilic (amphiphilic) polymer. When a nonionic surfactant and / or a nonionic polymer is present, this can represent up to 50% of the weight of the cationic / nonionic mixture. According to a fourth embodiment, the dispersing and / or stabilizing agent (De) is chosen from stabilizing agents (Di) in at least one non-ionic, anionic or cationic water-soluble or water-dispersible polysaccharide (PSA), or their compatible mixtures . It may optionally be added with at least one other dispersing and / or stabilizing agent (De) other, compatible; preferably, the mass quantity of dispersing and / or stabilizing agent (De) other than water-soluble or water-dispersible polysaccharide (PSA), if any, is at most equal to the mass of water-soluble or water-dispersible polysaccharide (PSA) used as as a dispersing and / or stabilizing agent (De). The amount of external phase (We) of the multiple emulsion (Em) is a function of the desired concentration for the multiple emulsion (Em). The internal inverse emulsion mass ratio (external EiVphase (We) comprising the dispersing and / or stabilizing agent (De) can range from 50/50 to 99/1, preferably from 70/30 to 98/2, very particularly from 70 / 30 to 80/20.

The mass ratio, expressed in sec, of dispersing and / or stabilizing agent (De) / mass of the internal inverse emulsion (Ei), can range from 0.01 / 100 to 50/100, preferably 0.1 / 100 to 10/100, especially 0.5 / 100 to 5/100. The concentration of the external phase (We) in dispersing and / or stabilizing agent (De) can range from 1 to 50%. Preferably, the emulsion (E) is a multiple emulsion (Em) comprising at least 70% by weight of internal emulsion (Ei). The average size of the internal inverse emulsion globules (Ei) dispersed in the external phase (We) is preferably less than 200 μm; preferably it can range from 1 to 20 μm, more preferably from 5 to 15 μm.

For a good implementation of the invention, the average size of the internal inverse emulsion globules (Ei) dispersed in the external phase (We) is at least twice, preferably at least 5 times, very particularly d '' at least 10 times that of the average size of the droplets of the internal aqueous phase (Wi) dispersed in the hydrophobic phase. The external phase (We) can be aqueous or non-aqueous miscible with water. The term "miscible" with water means is not likely to form a macroscopic diphasic solution at 25 ° C. When the external phase (We) is a non-aqueous phase miscible with water, it is in particular an alcoholic or hydroalcoholic phase, in particular a phase based on isopropyl alcohol, ethanol. .

Preferably, the external phase (We) is an aqueous phase. The pH of the external aqueous phase is not limiting; it depends on the intended application of the invention. The pH can range from 0 to 14, preferably from 2 to 11, more preferably from 5 to 11.

As an indication, when it comes to implementing the emulsion (Em) to transport a hydrophobic active material towards the surface of a tissue present in a detergent bath, the pH of the external aqueous phase (We) of the concentrated multiple emulsion (Em) can range from 5 to 11, preferably from 6 to 8. The external phase (We), preferably aqueous, can also contain hydrophilic active materials, in particular antibacterial agents such as methyl chloro isothiazolinone and methyl isothiazolinone (KATHON® CG marketed by Rohm and Haas), as well as buffering agents for adjust the pH, additives to adjust the osmotic pressure, such as salts (sodium chloride or sulfate, calcium chloride ...) or sugars (glucose) or polysaccharides (dextran ...)

The concentrations] of salt, sugar and / or polysaccharide are such that the osmotic pressures of the external (We) and internal (Wi) phases are balanced. According to a first particular embodiment of the invention, the active material (A) contained in or constituting the hydrophobic phase (O), is a hydrophobic active material useful in the field of care or detergency of articles made of textile fibers, and the external phase (We) an aqueous liquid detergent formulation containing the dispersing and / or stabilizing agent (De) formed from a mixture of at least one nonionic hydrophilic surfactant and at least one anionic hydrophilic surfactant , optionally combined with at least one non-ionic hydrophilic (amphiphilic) polymer. The concentration of the aqueous external phase (We) in hydrophilic compound (De) can range from 10 to 60% by weight, preferably from 15 to 50% by weight; its pH can range from 6 to 8. The mass ratio, expressed in sec, of nonionic surfactant / anionic surfactant can range from 3/1 to 1/1. According to a second particular embodiment of the invention, the active material (A) is a hydrophobic active material useful in the field of care or detergency of articles made of textile fibers, and the external phase (We) a liquid detergent formulation non-aqueous miscible with water, containing the dispersing and / or stabilizing agent (De) formed from a mixture of at least one nonionic hydrophilic surfactant and at least one anionic hydrophilic surfactant, optionally combined with at least one nonionic hydrophilic (amphiphilic) polymer. The concentration of the non-aqueous external phase (We) in hydrophilic compound (De) can range from 10 to 60% by weight, preferably from 15 to 50% by weight. The mass ratio, expressed in sec, of nonionic surfactant / anionic surfactant can range from 3/1 to 1/1. According to a third particular embodiment of the invention, the active material (A) is a hydrophobic active material useful in the field of caring for articles made of textile fibers, and the external phase (We) an aqueous liquid rinsing formulation, containing the dispersing and / or stabilizing agent (De) formed from at least one cationic hydrophilic surfactant and / or from at least one cationic hydrophilic (amphiphilic) polymer, optionally in admixture with at least one nonionic hydrophilic surfactant and / or at least one nonionic hydrophilic (amphiphilic) polymer. When a nonionic surfactant and / or a nonionic polymer is present, this can represent up to 50% the weight of the cationic / nonionic mixture. The concentration of the aqueous external phase (We) in hydrophilic compound (De) can range from 3.5 to 20% by weight; its pH can range from 2.5 to 6. According to a fourth embodiment of the invention, the active material (A) is a hydrophobic active material useful in the field of paints, and the external phase (We) an aqueous formulation for paint. According to a fifth embodiment of the invention, the active material

(A) is a hydrophobic active material useful in the field of body or hair care or make-up, body, hair, dental or oral hygiene, and the external phase (We) an aqueous cosmetic formulation or a formulation for hygiene body, hair, tooth or mouth. The multiple emulsion (Em) according to the invention can be obtained by implementing techniques involving a single reactor or two reactors. A technique in a single reactor can be carried out by implementing the following steps: (a) preparing the reverse emulsion (Ei) (b) preparing the external phase containing the agent and / or stabilizer (De) ( c) the external phase is introduced into the reverse emulsion (Ei) without stirring (d) the whole is stirred. Step (a) of preparation of the reverse emulsion (Ei) can be carried out as described above.

Step (b) of preparation of the external phase (We) can be carried out by mixing the constituent of the external phase (We) (preferably water) and the dispersing and / or stabilizing agent (De ). The external phase (We) can also include adjuvants such as preservatives and additives regulating the osmotic pressure.

The preparation of the external phase can be carried out at room temperature.

However, it may be advantageous to prepare the external phase (We) at a temperature close to that at which the reverse emulsion (Ei) is prepared. Once the external phase (We) is obtained, it is added to the inverse emulsion

(Ei), during step (c), without stirring.

Then, after having introduced all of the external phase (We) into the reverse emulsion (Ei), the whole is agitated (step (d).

Advantageously, the stirring is carried out by means of moderately shearing mixers, as are, for example, the agitators provided with a frame blade, the planetary type mixers, or those having a scraping mobile and a blade rotating in opposite directions. (cons-stirring). This stirring operation preferably takes place at a temperature at which the hydrophobic phase (O) is in a liquid form, and more particularly is between 10 and 80 ° C. The average size of the internal inverse emulsion (Ei) globules advantageously varies between 1 and 100 μm, more particularly between 1 and 20 μm, advantageously between 5 and 15 μm. The average size of the globules, corresponding to the median diameter in volume (d50) which represents the diameter of the globule equal to 50% of the cumulative distribution, is measured with a Horiba device and, or with an optical microscope. The various constituents of the emulsion (Em) can be used according to the quantities mentioned above.

When (We) is an aqueous phase, although the pH value of the aqueous phase is not limiting, it may be advantageous to adjust the pH of the external aqueous phase by adding base (soda, potash) or hydrochloric acid). By way of illustration, the usual range of pH of the external aqueous phase is between 0 and 14, preferably between 2 and 11, more preferably between

5 and 11. At the end of this agitation step (d), a concentrated multiple emulsion is obtained, the inverse emulsion / external phase weight ratio (We) can range from 50/50 to 99/1, preferably 70 / 30 to 98/2, especially from

70/30 to 80/20. A technique in two reactors can be carried out by implementing the following steps: (a) preparing the external phase (We) containing the dispersing and / or stabilizing agent (De) as above (b) preparing l reverse emulsion (Ei) as above (c) gradually introducing the reverse emulsion (Ei) into the external phase (We), with stirring

Step (c) of preparation of the actual multiple emulsion is carried out with stirring; stirring can be done by means of a paddle frame.

Typically, the stirring speed is relatively slow, of the order of 400 revolutions / minute.

The multiple emulsion (Em) obtained is analogous to that obtained by the technique known as a single reactor. Another technique in two reactors, making it possible to prepare a similar multiple emulsion (Em), implements the following steps: (a) the reverse emulsion (Ei) is prepared as above; the amount of reverse emulsion (Ei) prepared is divided into two parts (b) the external phase (We) is prepared containing the dispersing and / or stabilizing agent (De) (c) the external phase (We) is introduced into the first part of the reverse emulsion (Ei) without stirring (d ) the whole is stirred (e) little by little the remaining part of the inverse emulsion (Ei) is introduced into the multiple emulsion obtained in step (d), with stirring When the dispersing and / or stabilizing agent (De) is in at least water-soluble or water-dispersible polysaccharide (PSA) constituting the stabilizing agent (Di), the multiple emulsion (Em) can be directly obtained by subjecting a mixture formed of the constituent (s) of the hydrophobic phase (O ), the stabilizing agent (Di) and the constituent (s) of the external phase (We) in a stirring operation under high shear.

Solid form (Es)

The emulsion in solid form (Es), according to the invention can be obtained by addition, to the external phase of the multiple emulsion (Em), of a matrix (M) - in a water-soluble or water-dispersible compound, capable of form, in the presence of the external phase of the multiple emulsion (Em), a solid shell, after drying and optionally crystallization - into a solid water-soluble or water-dispersible material capable of adsorbing and / or absorbing the multiple emulsion (Em) and / or to hydrate, while remaining in a solid form - or in an insoluble solid material, capable of adsorbing and / or absorbing the multiple emulsion (Em). Preferably, the external phase (We) of the multiple emulsion (Em) is aqueous.

Among the materials capable of forming the matrix (M), there may be mentioned: • the following water-soluble or water-dispersible organic and inorganic compounds: - polyethylene qlvcols (PEG) having a molecular weight of between 2,000 and 100,000 g / mole - co-polymers of ethylenically unsaturated carboxylic acid or anhydride and of non-ionic ethylenically unsaturated monomer - water-soluble or water-dispersible polypeptides (PP) of natural or synthetic origin - the polyelectrolytes (PE) in acid form, belonging to the family of weak polyacids, having a molecular mass of less than 20,000 g / mole, preferably between 1,000 and 5,000 g / mole - the polvvinylpyrrolidones (PVP) having a molecular weight less than 20,000 g / mole, preferably between 1,000 and 10,000 g / mole - polyvinyl alcohols (PVA) having a molecular weight less than 100,000 g / mole, and preferably having a deacetylation rate of 80 to 99 mol%, preferably 87 to 95 mol% - water-soluble or water-dispersible film-forming ampholytic polymers (PA) - water-soluble or water-dispersible oses, osides or polvholosides (Oz) - amino acids (AA) or water-soluble or water-dispersible salts amino acids - citric acid - fatty acids - urea - surfactants (TA) whose binary water-surfactant phase diagram includes a fluid isotropic phase at 25 ° C up to a concentration of at least 50% by weight of surfactant, followed by a rigid liquid crystal phase of hexagonal or cubic type at higher concentrations, stable at least up to 60 ° C. - the water-soluble or water-dispersible salts of alkali metals , like silicates (Sil). carbonates (Carb). phosphates (Phos). sulphates. phosphonates. acetates, citrates, salts of saturated or unsaturated fatty acids (stearates) of alkali metals, mixtures of sodium acetate and citric acid - or mixtures thereof.

• as well as insoluble porous materials such as carbonates of alkaline earth metals, clays. Among the copolymers of ethylenically unsaturated carboxylic acid or anhydride and of ethylenically unsaturated nonionic monomer, mention may be made of copolymers of linear or branched aliphatic, cycloaliphatic or aromatic aliphatic or monocarboxylic or polycarboxylic acid and of monoolefinic α containing from 2 to 20 carbon atoms.

Among the acid or anhydride monomers, mention may be made of those containing 3 to 10 carbon atoms, preferably those of formula (R ² ') (R ² ") C = C (R ^2, ") COOH where R ² ', (R ² ") and R ² " ¹ are identical or different and represent • a hydrogen atom, • a hydrocarbon radical containing from 1 to 4 carbon atoms, preferably methyl • a -COOH function • a radical -R-COOH, where R represents a hydrocarbon residue containing from 1 to 4 carbon atoms, preferably an alkylene residue containing 1 or 2 carbon atoms, especially methylene. Preferably, at least one of the radicals R ² 'or R ² "is hydrogen.

By way of example, mention may in particular be made of acrylic, methacrylic, crotonic, maleic, fumaric, citraconic, itaconic acids or anhydrides. Among the α monoolefin monomers, mention may especially be made of ethylene, propylene, butene-1, isobutylene, n-pentene-1, 2-methyl butene-1, n-hexene-1, methyl -2 pentene-1, methyl-4 pentene-1, ethyl-2 butene-1, diisobutylene (or -trimethyl-2,4,4 pentene-1), methyl-2 dimethyl-3,3 pentene -1. Preferably, the molar ratio between the two types of monomers can range from 30/70 to 70/30. Preferably, the copolymer of formula (i) results from the polymerization of maleic anhydride and 2,4,4-trimethyl 1-pentene.

This type of copolymer is well known to those skilled in the art. Mention may be made, as polymer of this type, of that marketed under the name Geropon® EGPM and T36 (maleic anhydride / diisobutylene), marketed by Rhodia Chimie, as well as Sokalan® CP9 (maleic anhydride / olefin) marketed by BASF. Among the water-soluble or water-dispersible synthetic polymers (PP), mention may be made of homopolymers or copolymers derived from the polycondensation of amino acids or of amino acid precursors, in particular aspartic and glutamic acid or their precursors, and hydrolysis . These polymers can be homopolymers derived from aspartic or glutamic acid as well as copolymers derived from aspartic acid and glutamic acid in any proportions, or copolymers derived from aspartic and / or glutamic acid and d other amino acids. Among the copolymerizable amino acids, there may be mentioned glycine, alanine, leucine, isoleucine, phenyl alanine, methionine, histidine, proline, lysine, serine, threonine, cysteine ... Among the polypeptides (PP) of plant origin, mention may be made of proteins of plant origin; these are preferably hydrolyzed, with a degree of hydrolysis less than or equal to 40%, for example from 5 to less than 40%. Among the proteins of vegetable origin, mention may be made, by way of indication, of the proteins originating from protein seeds, in particular those of peas, faba beans, lupins, beans, and lentils; proteins from cereal grains, especially those from wheat, barley, rye, corn, rice, oats, and millet; proteins from oil seeds, especially those from soybeans, peanuts, sunflowers, rapeseed, and coconuts; proteins from the leaves, especially alfalfa, and nettles; and proteins from plant organs from buried reserves, notably that of potatoes and beets.

Among the proteins of animal origin, mention may be made, for example, of muscle proteins, in particular stroma proteins, and gelatin; proteins originating from milk, in particular casein, lactoglobulin; and fish protein.

The protein is preferably of vegetable origin, and more particularly comes from soybeans or wheat. The polyelectrolyte (PE) can be chosen from those resulting from the polymerization of monomers which have the following general formula (R ¹ ) (R ² ) C = C (R ³ ) COOH formula in which R ¹ , R ² , and R ³ are the same or different and represent. a hydrogen atom,. a hydrocarbon radical containing from 1 to 4 carbon atoms, preferably methyl

. a -COOH function

. a radical -R-COOH, where R represents a hydrocarbon residue containing from 1 to 4 carbon atoms, preferably an alkylene residue containing 1 or 2 carbon atoms, methylene in particular. By way of nonlimiting examples, mention may be made of acrylic, methacrylic, maleic, fumaric, itaconic, crotonic acids. Also suitable are the copolymers obtained from the monomers corresponding to the preceding general formula and those obtained using these monomers and other monomers, in particular vinyl derivatives such as vinyl alcohols and copolymerizable amides such as acrylamide or methacrylamide. Mention may also be made of the copolymers obtained from vinyl ether alkyl and maleic acid as well as those obtained from vinyl styrene and maleic acid which are described in particular in the encyclopedia Kirk-Othmer entitled "ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY" - Volume 18 - 3 ^rd Edition - Wiley Interscience publication - 1982. The preferred polyelectrolytes have a low degree of polymerization. The molecular weight by weight of the polyelectrolytes is more particularly less than 20,000 g / mole. Preferably, it is between 1,000 and 5,000 g / mole. An ampholyte polymer (PA) is a polymer which comprises anionic or potentially anionic charges depending on the pH and cationic or potentially cationic charges depending on the pH, the potentially anionic or potentially cationic charges being taken into account for the calculation of the ratio of total number of anionic charges to the total number of cationic charges.

The film-forming ampholytic polymer (PA) generally has a molecular mass of less than 500,000 g / mol, determined by aqueous gel permeation chromatography (GPC).

The film-forming ampholytic polymer (PA) can be obtained from anionic and cationic ethylenically unsaturated monomers. It can also be obtained from a mixture of monomers additionally containing neutral monomers. The anionic ethylenically unsaturated monomers can be chosen from acrylic, methacrylic, fumaric, maleic, itaconic acids or anhydrides, N-methacroyl alanine, N-acryloyl-hydroxy-glycine ... or their water-soluble salts; water-soluble, sulfonated or phosphonated ethylenically unsaturated monomers, such as sulfopropyl acrylate or its water-soluble salts, water-soluble styrene sulfonates, vinylsulfonic acid and its water-soluble salts or vinylphosphonic acid and its water-soluble salts. The cationic ethylenically unsaturated monomers can be chosen from

* aminoacryloyl or acryloyloxy monomers such as trimethylaminopropylmethacrylate chloride, trimethylaminoethylacrylamide or methacrylamide chloride or bromide, trimethylaminobutylacrylamide or methacrylamide, trimethylaminopropylmethacrylamide () (3-acrylamidopropyl) trimethylammonium chloride (APTAC), methacryloyloxyethyl trimethylammonium chloride or methyl sulfate, acryloyloxyethyl trimethylammonium chloride;

* 1-ethyl 2-vinylpyridinium bromide, chloride or methyl sulfate; ^* N, N-dialkyldiallylamine monomers such as N, N-dimethyldiallylammonium chloride (DADMAC);

* polyquaternary monomers such as dimethylaminopropylmethacrylamide chloride, N- (3-chloro-2-hydroxypropyl) trimethylammonium (DIQUAT) ... The neutral ethylenically unsaturated monomers can be chosen from acrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, dimethylaminoethylmethacrylate (DMAEMA), dimethylaminopropyl methacrylamide, vinyl alcohol, alkyl or hydroxyalkyl acrylates or methacrylates, polyoxyalkylene glycol acrylates or methacrylates ... Mention may very particularly be made, as ampholyte polymer ( PA), copolymers or terpolymers

^* MAPTAC / acrylic or methacrylic acid; DIQUAT / acrylic or methacrylic acid; DADMAC / acrylic or methacrylic acid; * MES / acrylic or methacrylic acid / DMAEMA;

^* MAPTAC / acrylic acid / acrylamide; MAPTAC / maleic anhydride / acrylamide; MAPTAC / vinyl sulfonic acid / acrylamide;

* DADMAC / acrylic acid / acrylamide; DADMAC / maleic anhydride / acrylamide; DADMAC / vinyl sulfonic acid / acrylamide; * DIQUAT / acrylic acid / acrylamide; DIQUAT / maleic anhydride / acrylamide; DIQUAT / vinyl sulfonic acid / acrylamide; with a ratio of the total number of anionic charges to the total number of cationic charges which can range from 0.1 to 10. Among the dares (Oz) one can mention the aldoses such as glucose, mannose, galactose, ribose and ketoses such as fructose.

Osides are compounds which result from the condensation, with elimination of water, of daring molecules between them or even of daring molecules with non-carbohydrate molecules. among the osides, the holosides which are formed by the combination of exclusively carbohydrate units are preferred, and more particularly the oligoholosides (or oligosaccharides) which contain only a limited number of these units, that is to say a number which is generally lower. or equal to 10. As examples of oligoholosides, mention may be made of sucrose, lactose, cellobiose, maltose, sucrose and trehalose. The water-soluble or water-dispersible polyholosides (or polysaccharides) are highly depolymerized; they are described for example in the work of P. ARNAUD entitled "organic chemistry course", Gaultier-Villars éditeurs, 1987. More particularly, these polyholosides have a molecular mass by weight of less than 500,000 g / mole, preferably less at 20,000 g / mole. By way of nonlimiting example of polyholosides, mention may be made of celluloses and cellulose derivatives (carboxy methyl cellulose), carrageenans; among the highly depolymerized polyholosides, mention may be made of dextran, starch, xanthan gum and galactomannans such as guar or carob, these polysaccharides preferably having a melting point above 100 ° C. and a solubility in water between 5 and 500 g / l. Among the amino acids (AA). there may be mentioned monocarboxylated or dicarboxylated monoamine acids, monocarboxylated diamine acids and their water-soluble derivatives. Amino acids (AA) preferably have a side chain with acid-base properties; they are chosen in particular from arginine, lysine, histidine, aspartic, glutamic and hydroxyglutamic acids; they can also be in the form of derivatives, preferably water-soluble; it can be, for example, sodium, potassium or ammonium salts, such as sodium glutamate, aspartate or hydroxyglutamate. Regarding the surfactants (TA) likely to constitute the matrix (M), the description of the fluid isotropic phases and rigid liquid crystal of hexagonal or cubic type is given in the work of RG LAUGHLIN entitled "The AQUEOUS PHASE BEHAVIOR OF SURFACTANTS "- ACADEMIC PRESS - 1994. Their identification by diffusion of radiation (X and neutrons) is described in the work of V. LUZZATI entitled" BIOLOGICAL MEMBRANES, PHYSICAL FACT AND FUNCTION "- ACADEMIC PRESS - 1968. More particularly, the phase rigid liquid crystal is stable up to a temperature at least equal to 55 ° C. The fluid isotropic phase can be poured, while the rigid liquid crystal phase cannot.

Among the surfactants (TA), mention may be made of ionic glycolipid surfactants, in particular derivatives of uronic acids (galacturonic, glucuronic acids, D-mannuronic, L-iduronic, L-guluronic ...), having a substituted hydrocarbon chain or unsaturated or unsaturated comprising from 6 to 24 carbon atoms and preferably from 8 to 16 carbon atoms, or their salts. This type of product is described in particular in patent application EP 532,370.

Other examples of surfactant (TA) are amphoteric surfactants such as amphoteric derivatives of alkyl polyamines such as amphionic XL®, Mirataine H2C-HA® marketed by Rhône-Poulenc as well as Ampholac 7T / X® and Ampholac 7C / X® sold by Berol Nobel. Among the alkali metal silicates (Sil). mention may in particular be made of those having a SiO ₂ / M ₂ O molar ratio of 1.6 to 3.5 with M representing a sodium or potassium atom.

Among the alkali or alkaline earth metal phosphates (Phos). there may be mentioned in particular sodium hexametaphosphate, anhydrous sodium tripolyphosphates. Among the carbonates, mention may in particular be made of those of sodium or calcium. The amount of matrix (M) used is such that it represents from 20 to 80%, preferably from 30 to 70% of the weight of the emulsion in solid form (Es) expressed in dry form. The solid emulsion (Es) of the multiple emulsion (Em) can be carried out in different ways, depending on the nature of the matrix. When it is a meltable matrix at a temperature below 80 ° C. and crystallizable like polyethylene glycols of molecular mass ranging from 2000 to 100,000 g / mole, preferably from 3,000 to 50,000 g / mole, the solid emulsion of the multiple emulsion (Em) can be produced by adding to said multiple emulsion (Em) polyethylene glycol in the molten state at a temperature of the order of 60 to 80 ° C., or in solution aqueous, then crystallization by drying / cooling in thin film in a ventilated oven, and flaking.

A variant of this process consists in producing the multiple emulsion (Em) by dispersing the reverse emulsion (Ei) at a temperature of 60 to 80 ° C in molten polyethylene glycol added with (De) and then crystallization by drying. / thin film cooling in a ventilated oven, and flaking. When it is a matrix made of a material, preferably inorganic, porous anhydrous and / or hydratable, capable of remaining in the solid state after hydration, adsorption and / or absorption, such as sodium tripolyphosphates, carbonate sodium, the solid form can be achieved by placing on a support on said material and optionally moderate drying. According to a preferred mode of preparation of the emulsion (E) in a solid form (Es), the external aqueous phase of the multiple emulsion (Em) comprises at least one water-soluble or water-dispersible compound (M) which cannot be melted at a temperature below 100 ° C, as a drying additive for the multiple emulsion. Indeed, in the presence of these compounds, it becomes possible to dry the multiple emulsion (in other words to remove the external water from said emulsion) in order to obtain granules (or any other form). Preferably, the multiple emulsion (Em) is diluted with water preferably comprising dispersing and / or stabilizing agent (De) and introduced into the matrix (M), then dried.

The drying operation (consisting in removing water from the external aqueous phase) can be carried out by any means known to those skilled in the art.

Preferably, the drying is carried out so that at least 90% by weight of the external aqueous phase is eliminated.

Drying can be carried out in an oven, preferably in a thin layer. Usually the drying temperature is less than or equal to 100 ° C. More particularly, temperatures between 50 and 90 ° C are suitable for the implementation of this method.

Another method of drying the emulsion is a so-called rapid method. As such, spray drying, drying by using Duprat® drums, or lyophilization (freezing-sublimation) are suitable.

Spray drying can be carried out in the usual manner in any known device such as for example an atomization tower associating a spraying carried out by a nozzle or a turbine with a stream of hot gas. The inlet temperature of the gases is of the order of 100 ° C. to 200 ° C. and that of the outlet of the atomizing gases is preferably between 55 and 100 ° C. These temperatures are given for information only, and depend on the thermal stability of the various elements. In addition, it is defined according to the desired final water content in the granule. Advantageously, the desired average size of the granules (d50) is between 100 μm and a few millimeters (Sympatec), preferably between 100 and 800 μm. Such granules can be obtained directly using a double-effect atomizer (drying / granulation). They can also be obtained using a single-effect atomizer (drying) associated with a granulation device (fluidized bed) with spraying of water, optionally additive with matrix material (M).

In the case of drying operations for the multiple emulsion carried out by means of a Duprat® drum, or any means allowing a dry film to be obtained quickly which is separated from the drying support by a scraping operation for example, scales or powder that can possibly be ground. If necessary, these scales can be the subject of a subsequent implementation, such as an agglomeration step, so as to obtain agglomerated granules. Advantageously, the average size of the granules (d50) obtained directly after drying is between 100 μm and a few millimeters (Sympatec), preferably between 100 and 800 μm.

It should be noted that additives, such as anti-caking agents, fillers (such as silica, kaolin, titanium dioxide, etc.) can be incorporated into the granules. These additives can be introduced during drying or in post addition. A second object of the invention consists in the use of an emulsion (E) comprising a hydrophobic liquid or fusible phase (O) containing and / or consisting of at least one hydrophobic active material (A), said emulsion (E ) being: • in the form of a multiple emulsion (Em) comprising: - an internal inverse emulsion (Ei) comprising said continuous hydrophobic liquid or fusible phase (O), an aqueous dispersed phase (Wi) and, with interface of the two phases, at least one water-soluble or water-dispersible stabilizing agent (Di) - an aqueous or water-miscible external phase (We), in which the internal emulsion (Ei) is dispersed, using at least one dispersing and / or stabilizing agent (De) • or in solid form (Es), hydrodispersible in a moon multiple emulsion (Em) in which the external phase (We) is aqueous, comprising - the reverse emulsion (Ei) dispersed in a water-soluble or water-dispersible solid matrix (M) - and the dispersing and / or stabilizing agent t (De) located at the interface of the inverse emulsion (Ei) and the matrix (M) and optionally dispersed in the matrix (M) emulsion (E) in which the stabilizing agent (Di) at the interface of the two phases of the internal inverse emulsion (Ei) is made of a material chosen from water-soluble or water-dispersible polysaccharides (PSA), free from lipophilic polyorganosiloxane substituent groups: - whose average degree of polymerization (DP) is at least 1 , Preferably at least 20?, Most particularly at least 100 - whose Brookfield viscosity at 25 ° C in 1% solution by mass in water is less than 20,000 mPa.s., preferably less than 5000 mPa.s., especially ranging from 1 to 4500 mPa.s., for conveying, in an aqueous medium (B) in contact with a substrate (S), the hydrophobic phase (O) containing and / or consisting of at least one hydrophobic active material (A), to said substrate (S). Said substrate (S) can be of any material, in particular a metal or any natural, artificial or synthetic material, or a mixture of these materials. Said hydrophobic phase (O) is preferably made of an active material capable of bringing its intrinsic properties or the benefits which result therefrom, to said substrate. The aqueous external phase (We) can itself constitute the aqueous medium (B), with release of the hydrophobic phase and of the hydrophobic active material by deposition or application and drying of the emulsion on the substrate (S). 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, plaster, cement, wood ..., with release of the hydrophobicizing 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 paper ("tissues"), feminine protections ("towels"), diapers (diapers) etc ..., intrinsic benefits in the hydrophobic phase (O) and / or the active materials (A) 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, bactericidal, perfuming properties ... The second object of the invention consists in particular in use of an emulsion (E) comprising a liquid or fusible hydrophobic phase (O) containing and / or consisting of at least one hydrophobic active material (A), said emulsion (E) being: • in the form of a multiple emulsion (Em) comprising: - an internal inverse emulsion (Ei) comprising said continuous hydrophobic liquid or fusible phase (O), an aqueous dispersed phase (Wi) and, at the interface of the two phases, at least one water-soluble stabilizing agent or water-dispersible (Di) - an aqueous or water-miscible external phase (We), in which the internal emulsion (Ei) is dispersed, using at least one dispersing and / or stabilizing agent (De) • or in solid form (Es), water-dispersible in Mon e multiple emulsion (Em) in which the external phase (We) is aqueous, comprising - the inverse emulsion (Ei) dispersed in a solid matrix (M) water-soluble or water-dispersible - and the dispersing and / or stabilizing agent (De) located at the interface of the inverse emulsion (Ei) and the matrix (M) and optionally dispersed in the matrix (M) emulsion (E) in which the stabilizing agent (Di) at the interface of the two phases of the internal inverse emulsion (Ei) is made of a material chosen from water-soluble or water-dispersible polysaccharides (PSA), free from lipophilic polyorganosiloxane substituent groups: - the average degree of polymerization (DP) of which is preferably at least 1.5 at least 20?, especially at least 100? whose Brookfield viscosity at 25 ° C in solution at 1% by mass in water is less than 20,000 mPa.s., preferably less than 5,000 mPa .s., particularly ranging from 1 to 4500 mPa.s., to transport, in mili eu aqueous (B) brought into contact with a substrate (S), the hydrophobic phase (O) containing and / or consisting of at least one hydrophobic active material (A), towards said substrate (S), the volume of said aqueous medium being sufficient to cause destabilization and / or rupture of the emulsion

(E) by dilution of said emulsion (E) and / or drying subsequent to dilution of said emulsion (E), and the provision and / or release of the material active (A) contained or constituent of the hydrophobic phase (O), on the substrate (S). Preferably, the emulsion (E) is a multiple emulsion

(Em) comprising at least 70% by weight of internal emulsion (Ei). For a good implementation of the invention, relative amounts of emulsion (Em) and aqueous medium (B) equivalent to a dilution of 2 to 100 times the volume of said emulsion (Em) can be used. The emulsion according to the invention is particularly advantageous for conveying and depositing a hydrophobic active material on a hydroxyapatite surface (tooth), a keratin surface (skin, hair, leather) or a textile surface. 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 may be toothpaste, mouthwash, etc. Said substrate (S) may 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 in particular 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 a very preferred manner, said substrate (S) is made of 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.

Said hydrophobic phase (O) is preferably made of a material for textile care ("textile care agent"). The particular examples of organosilicon (01) and organic (02) materials mentioned above are particularly well suited, very particularly organosilicon materials, especially amines. The benefits brought by a hydrophobic lubricating phase (01) or (02) to a textile substrate are in particular the contribution of properties of softness (softness), anti-creasing (anti-wrinkling), ease of ironing (easy- ironing), abrasion resistance (especially protection against aging when wearing the garment or repeated washing operations), elasticity, color protection, retention of perfumes ... Among the 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 (O), in particular in organosilicon (01) or organic (02) materials. 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 (E) according to the invention, can in particular be used as an additive in a detergent composition for washing or rinsing articles made of textile fibers, or as a detergent or rinsing composition for washing or rinsing articles made of textile fibers, with the aim of conveying a hydrophobic care agent ("textile care agent") and / or any other useful hydrophobic active material, and to promote the deposition thereof and / or thereof on an article made of textile fibers, in particular cotton, during the rinsing operation and / or during the subsequent drying (s) to the main washing operation in the case of a detergent composition for washing, or in the subsequent drying operation in the case of a rinsing composition. It has indeed been observed that the use of the emulsion (E) in the form of a multiple emulsion (Em) or in the form of a water-dispersible solid (Es) containing a hydrophobic phase (O) of care, as composition detergent or in a detergent composition for washing clothes in a washing machine, used in the washing cycle, without adding softening rinsing liquid to the rinsing cycle, made it possible to provide the washed laundry with softness properties, flexibility, anti-wrinkling, easy-ironing, abrasion resistance, elasticity, color protection, retention of perfumes ... It has also been found that the use of the emulsion (E) in the form of a multiple emulsion (Em) or in the form of a water-dispersible solid (Es) containing a hydrophobic phase (O) of care, as composition of rinsing or in a composition for rinsing the laundry, made it possible to bring to the laundry, after drying, properties of softness, flexibility, anti-wrinkling (anti-wrinkling), ease of ironing (easy-ironing), abrasion resistance, elasticity, color protection, fragrance retention ... The deposition of the hydrophobic phase (O) containing or consisting of the active material (A) on the substrate can be a deposition by adsorption , co-crystallization, trapping and / or adhesion. The amount of emulsion (E) in the form of a multiple emulsion (Em) or in the form of a water-dispersible solid (Es) which may be present in a composition for washing textile fiber articles, according to the third object of the invention, corresponds to an amount of hydrophobic phase (O) 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 as an emulsion multiple (Em), and aqueous medium (B) equivalent to a dilution of 2 to 100 times the volume of said emulsion (Em). The amount of emulsion (E) in the form of a multiple emulsion (Em) 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 (O ) 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 (Em), and of aqueous medium (B ) equivalent to a dilution of 2 to 100 times the volume of said emulsion (Em). 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 -Cι ₅ ) 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 alcohols aliphatic C ₈ -C ₂ o having from 1 to 20 moles of ethylene oxide per mole of alcohol, and more particularly the ethoxylates of primary or secondary aliphatic alcohols C ₁ 0-C ₁₅ 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 amount 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 groups R 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 C1 ₂ -C ₁ 4 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. 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 builder, the total amount of 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 at 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, in particular 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, anti-fouling, 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 from 3 to 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 are very commonly used, such as distearyl dimethyl ammonium chlorides; ditallow alkyl dimethyl ammonium.

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 from 10 to 20 moles of alkylene oxide, C ₁₀ -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 fatty acid softening cationic agent is favorably 10 / 1-1 / 10. A final object of the invention consists in a method for conveying, to a substrate (S) in contact with an aqueous medium (B), at least one active material contained in or constituting a hydrophobic phase (O) liquid or fusible of an emulsion (E), said emulsion being • in the form of a multiple emulsion (Em) comprising: - an internal inverse emulsion (Ei) comprising said continuous hydrophobic liquid or fusible phase (O), an aqueous dispersed phase (Wi) and, at the interface of the two phases, at least one water-soluble or water-dispersible stabilizing agent (Di) - an aqueous or water-miscible external phase (We), in which the internal emulsion (Ei) is dispersed , using at least one dispersing and / or stabilizing agent (De) • or in solid form (Es), water-dispersible in a multiple emulsion (Em), comprising - the reverse emulsion (Ei) dispersed in a matrix (M) water-soluble or water-dispersible solid - and the dispersing and / or stabilizing agent (De) located at the interface of the inverse emulsion (Ei) and the matrix (M) and optionally dispersed in the matrix (M) emulsion (E) in which the stabilizing agent (Di) at the interface of the two phases of the internal inverse emulsion (Ei) is made of a material chosen from water-soluble or water-dispersible polysaccharides (PSA), free from lipophilic polyorganosiloxane substituent groups: - the average degree of polymerization (DP) of which is preferably at least 1.5 at least 20, especially at least 100 - whose Brookfield viscosity at 25 ° C in solution at 1% by mass in water is less than 20,000 mPa.s., preferably less than 5,000 mPa. s., especially ranging from 1 to 4500 mPa.s., by bringing the emulsion (E) into contact with the substrate (S) in contact with the aqueous medium (B). The last object of the invention relates in particular to a method for conveying, to a substrate (S) in contact with an aqueous medium (B), at least one active material contained in or constituting a hydrophobic phase (O) liquid or fuse of an emulsion (E), said emulsion being in the form of a multiple emulsion (Em) comprising: an internal inverse emulsion (Ei) comprising said continuous hydrophobic liquid or fusible phase (O), an aqueous dispersed phase (Wi) and, at the interface of the two phases, at least one water-soluble or water-dispersible stabilizing agent (Di) - a aqueous or water-miscible external phase (We), in which the internal emulsion (Ei) is dispersed, using at least one dispersing and / or stabilizing agent (De) • or in solid form (Es ), water-dispersible in a multiple emulsion (Em), comprising - the inverse emulsion (Ei) dispersed in a solid matrix (M) water-soluble or water-dispersible - and the dispersing and / or stabilizing agent (De) located at the interface of the reverse emulsion (Ei) and the matrix (M) and optionally dispersed in the matrix (M) emulsion (E) in which the stabilizing agent (Di) at the interface of the two phases of the internal reverse emulsion ( Ei) is made of a material chosen from water-soluble or water-dispersible polysaccharides (PSA), free of gro upophilic polyorganosiloxane substituents: - whose average degree of polymerization (DP) is at least 1.5, preferably at least 20, very particularly at least 100 - whose Brookfield viscosity at 25 ° C in solution 1% by mass in water is less than 20,000 mPa.s., preferably less than 5,000 mPa.s., very particularly ranging from 1 to 4,500 mPa.s., by bringing the emulsion into contact (E ) with the substrate (S) in contact with the aqueous medium (B), the volume of said aqueous medium (B) being sufficient to cause destabilization and / or rupture of the emulsion (E) by dilution of said emulsion (E ) and / or drying subsequent to the dilution of said emulsion (E), and the provision and / or release of the active material (A) contained or constituting the hydrophobic phase (O), on the substrate (S). Preferably, the emulsion (E) is a multiple emulsion (Em) comprising at least 70% by weight of internal emulsion (Ei). The conditions for carrying out said process have already been described above.

The following examples are given as an indication. In the following examples are implemented

• As hydrophobic phase (O) and active material (A) the amino silicone oil RHODORSIL® EXTRASOFT marketed by Rhodia.

• As stabilizing agent (Di) - MEYPROGAT® 7 depolymerized guar marketed by Rhodia, with a molecular weight of about 47,000, a degree of polymerization of about 300, and having a Brookfield viscosity of 1-5 mPa.s at 1% in water at 25 ° C - A cellulose monoacetate with a degree of polymerization of around 300, a degree of substitution of 0.67 and having a Brookfield viscosity of 1-5 mPa.s at 1% in the water at 25 ° C

• As dispersing and / or stabilizing agent (De), Arlatone® F 127G, of formula HO (CH ₂ CH2θ) χ (CH (CH3) CH ₂ θ) y (CH ₂ CH ₂ O) _z H marketed by ICI -Uniquema

Example 1: Multiple emulsion Composition of the inverse emulsion (Ei):

• 50% by weight of internal aqueous phase consisting of: Water 90 parts by weight Meyprogat® 7 10 parts by weight

• 50% by weight of amino silicone oil phase (O) Rhodorsil® Extrasoft oil 100 parts by weight

Preparation of the reverse emulsion (Ei):

Preparation of the internal aqueous phase Water is introduced into a 1 I reactor fitted with a paddle-type stirring.

(diameter 54 mm, speed 400 rpm), at room temperature.

The Meyprogat® 7 powder is then gradually introduced with stirring at room temperature.

The mixture is stirred for two hours at ambient temperature so as to disperse the gel particles of Meyprogat® 7 in a homogeneous manner. Optionally, the dispersion is sheared using a rotor-stator type tool

(Ultra-turrax type GT45).

The pH of the internal aqueous solution / dispersion is 5 to 7.5

Preparation of the reverse emulsion In a 2 I reactor fitted with a paddle-type stirring (diameter 90 mm, speed 400 revolutions / minute), the Rhodorsil® Extrasoft oil is introduced.

The internal aqueous phase is then introduced over 45 minutes at room temperature. Stirring is continued for 15 minutes to refine the emulsion. An inverse emulsion (Ei) is obtained, the drops of dispersed aqueous phase (Wi) having a particle size of 1 μm (observation made under optical microscopy on a sample without and with prior dilution in Extrasoft oil).

Composition of the multiple emulsion:

• 91% by weight of inverse emulsion (Ei) above

• 9% by weight of external aqueous phase (We), obtained from 9 parts by weight of an aqueous solution at 10% by weight of Arlatone F 127G® which corresponds to - 10% of dry Arlatone® F127G - 90% water

Preparation of the multiple emulsion:

Preparation of the external aqueous phase In a 0.5 I beaker fitted with magnetic bar stirring, water is introduced and gradually the Arlatone F 127G powder with stirring at room temperature.

The mixture is stirred for 15 minutes at room temperature, so as to obtain a homogeneous solution (10% solution of Arlatone F 127G). Preparation of the double emulsion

The external aqueous phase prepared above is added, without stirring and quickly at room temperature, to the reverse emulsion (Ei) obtained above contained in the 2 I reactor fitted with stirring of the pale frame type (diameter

90 mm). The whole is then agitated (blade type agitation - diameter 90 mm, speed

200 rpm). A multiple emulsion is quickly obtained; this emulsion is kept under stirring for refining for 10 minutes.

A concentrated multiple emulsion (Em) is obtained, which is in the form of a viscous non-pourable cream; the average droplet size (d50) of internal reverse emulsion is close to 10 μm, with a low polydispersity index.

Example 2: multiple emulsion A multiple emulsion is prepared according to the procedure of Example 1, replacing the 10 parts by weight of Meyprogat® 7 with 10 parts of cellulose monoacetate. EXAMPLE 3 Depositing Rhodorsil® Extrasoft Oil on Detergent Bath on Cotton

Test The test is carried out in a Tergotometer laboratory apparatus, well known to formulators of detergent compositions. The device simulates the mechanical and thermal effects of washing machines of the American type with pulsator; thanks to the presence of 6 washing pots, it makes it possible to carry out series of simultaneous tests with appreciable time savings. Preparation

The pots are heated to 40 ° C.

500ml of water with a hardness of 30 ° HT (diluted Contrexéville® mineral water) are introduced into each jar

5g of a powdered detergent composition for washing machine in the machine are introduced into each jar (i.e. 10g / I) the Tergotometer is started (100 cycles / minute for 5 minutes) to dissolve the detergent.

Wash cycle

A quantity of double emulsion prepared in Example 1 or in Example 2 corresponding to 0.5 g of Rhodorsil® Extrasoft oil is introduced into each pot.

We introduce into each jar 3 Terry terry cotton test tubes

(10cmx10cm).

Wash at 100 cycles / minute for 20 minutes.

Rinsing cycle The tissue squares are then rinsed 3 times for 5 minutes (each time) with cold water.

Drying

The fabric squares are taken out and allowed to air dry. An assessment of softness performance is given by a jury of trained experts, in a blind test.

The performance obtained is given in the table below (“Emulsion”) and compared to that obtained with:

• Washing with a Tergotometer without adding the multiple emulsion from Example 1 or 2 (“Reference 1”) • Washing with a Tergotometer without adding the multiple emulsion from Example 1 or 2, followed by rinsing with the addition of 5g of a commercial softening formulation on the 3rd rinse ("Reference 2"). The results obtained are shown in the following table

Claims

1) Emulsion (E) comprising a liquid or fusible hydrophobic phase (O) containing and / or consisting of at least one hydrophobic active material (A), said emulsion (E) being: • in the form of a multiple emulsion (Em) comprising: - an internal inverse emulsion (Ei) comprising said continuous hydrophobic liquid or fusible phase (O), an aqueous dispersed phase (Wi) and, at the interface of the two phases, at least one water-soluble or water-dispersible stabilizing agent (Di) - an aqueous or water-miscible external phase (We), in which the internal emulsion (Ei) is dispersed, using at least one dispersing and / or stabilizing agent (De) • or in solid form (Es), water-dispersible in a multiple emulsion (Em) in which the external phase (We) is aqueous, comprising - the inverse emulsion (Ei) dispersed in a matrix (M) solid water-soluble or water-dispersible - and dispersing and / or stabilizing agent (De) located at the interface of the reverse emulsion (Ei) and the matrix (M) and optionally dispersed in the matrix (M) said emulsion being characterized in that the stabilizing agent (Di) at the interface of the two phases of the internal inverse emulsion (Ei) is made of a material chosen from water-soluble or water-dispersible polysaccharides (PSA): - whose average degree of polymerization (DP) is at least 1.5, preferably at least 20, most particularly at least 100 - whose Brookfield viscosity at 25 ° C in solution at 1% by mass in water is less than 20,000 mPa.s., preferably less than 5,000 mPa.s., very particularly ranging from 1 to 4,500 mPa.s., said polysaccharides (PSA) being also free of lipophilic polyorganosiloxane substituent groups.

2) Emulsion according to claim 1), characterized in that the hydrophobic phase (O) is in at least one organic or organosilicon material or in a mixture of at least one organic material and at least one organosilicon, liquid or fuse insoluble in an aqueous phase. 3) Emulsion according to claim 1) or 2), characterized in that the active material (A) is in at least one organic or organosilicon material, in a mixture of at least one organic material and at least one organosilicon material , liquid or fuse insoluble in an aqueous phase, in at least one solid inorganic material or liquid insoluble in an aqueous phase or in a mixture of at least one of said inorganic materials and at least one of said organic materials and / or at least one of said organosilicon materials. 4) Emulsion according to any one of claims 1) to 3), characterized in that said hydrophobic phase (O) and / or said active material (A) is an oil, a wax or a resin in a linear, cyclic polyorganosiloxane , branched or crosslinked. 5) Emulsion according to claim 4), characterized in that said polyorganosiloxane is a nonionic or amino polyorganosiloxane.

6) Emulsion according to any one of Claims 1) to 3), characterized in that said hydrophobic phase (O) and / or said active material (A) is made of an organic material chosen from

• mono-, di- or triglycerides of Cι-C ₃₀ carboxylic acid or mixtures thereof, in particular vegetable oils

• technical oils, in particular boiled, blown or standolized linseed oils • sucroesters, sucroglycerides

• the alcoolesters C-ι-C ₃ o carboxylic acids, C-ι-C ₃ o or dicarboxylic C ₂ -C ₃ o,

• ethylene or propylene glycol monoesters or diesters of Cι-C ₃₀ carboxylic acids • propylene glycols of C ₄ -C ₂ alkyl ether

• di C ₈ -C ₃ o alkyl ethers

• mineral oils, in particular naphthenic, paraffinic oils, polybutenes

• organic waxes comprising alkyl chains containing from 4 to 40 carbon atoms, in particular animal waxes, vegetable waxes, mineral waxes, hydrocarbon waxes comprising from 4 to 35 carbon atoms, synthetic waxes. 7) Emulsion according to any one of claims 1) to 3), characterized in that the active material (A) is contained in the hydrophobic phase (O), and is in one or more perfume molecules, an anti-UV agent organic or organosilicon, a hydrophobic bactericidal agent, solid polyamide capsules, particles of silica or other oxide or inorganic compound.

8) Emulsion according to any one of claims 1) to 7), characterized in that said polysaccharide (PSA) or its backbone is a homopolysaccharide or a linear or branched heteropolysaccharide, nonionic or ionic, comprising similar glycosyl units or different joined by β (1-4) bonds, and possibly other bonds, in particular β (1-3) and / or β (1-6). 9) Emulsion according to claim 8), characterized in that the hydroxyl functions of the glycosyl units are substituted and / or modified by nonionic or ionic groups other than lipophilic polyorganosiloxane groups. 10) Emulsion according to claim 8) or 9), characterized in that said polysaccharide (PSA) is chosen from:

• galactomannans, preferably guar gum, depolymerized, optionally modified or substituted by nonionic groups, preferably hydroxypropyl, anionic, preferably carboxymethyl, cationic, preferably hydroxypropyltrimethylammonium chloride;

The cellulose monoacetates, having a degree of substitution of 0.3 to less than 1.2, preferably of 0.3 to 1,

• hydroxypropylated celluloses exhibiting a rate of modification of the order of 0.2 to 1.5 • carboxymethylcelluloses exhibiting a degree of substitution of 0.05 to 1.2, preferably of 0.05 to 1,

• dextrins optionally containing quaternized hydroxyethyl, hydroxypropyl or aminoalkyl groups

• xyloglycans such as tamarind gum • arabinoxylans

• alkylpolyglycosides 11) Emulsion according to any one of claims 1) to 10), characterized in that the mass ratio of the dispersed aqueous phase (Wi) to the hydrophobic phase (O) ranges from 5/95 to 95/5, preferably from 30/70 to 80/20.

12) Emulsion according to any one of claims 1) to 11), characterized in that the ratio of the mass of stabilizer (Di) to the mass of hydrophobic phase (O) ranges from 0.1 / 100 to 500/100 , preferably from 0.5 / 100 to 100/100, very particularly from 0.5 / 100 to 50/100.

13) Emulsion according to any one of claims 1) to 12), characterized in that said dispersing and / or stabilizing agent (De) is chosen from hydrophilic surfactants and / or hydrophilic polymers and / or hydrophilic amphiphilic polymers .

14) Emulsion according to claim 13), characterized in that said dispersing and / or stabilizing agent (De) is formed (a) of at least one nonionic hydrophilic surfactant (b) of at least one hydrophilic surfactant anionic (c) of at least one cationic hydrophilic surfactant (d) of at least one nonionic hydrophilic polymer (e) of at least one nonionic hydrophilic amphiphilic polymer (f) of at least one hydrophilic polymer anionic (g) of at least one hydrophilic amphiphilic polymer anionic (h) of at least one cationic hydrophilic polymer (i) of at least one cationic hydrophilic amphiphilic polymer G) or of a mixture of at least two of said surfactants and / or polymers (a) to (d) above compatible. 15) Emulsion according to claim 13) or 14), characterized in that the total content of surfactant (s) and / or polymer (s) (De) present (s) in the external phase (We) is between 0 , 01 and 50% by weight, preferably between 0.1 and 10%, more particularly between 0.5 and 5% by weight, relative to the inverse emulsion (Ei).

16) Emulsion according to any one of Claims 13) to 15), characterized in that said hydrophilic polymer (De) is in at least one or comprises at least one water-soluble or water-dispersible polysaccharide (PSA) (Di).

17) Emulsion according to any one of Claims 1) to 16), characterized in that the internal inverse emulsion mass ratio

(Ei) / external phase (We) comprising the dispersing and / or stabilizing agent (De) ranges from 50/50 to 99/1, preferably from 70/30 to 98/2, very particularly from

70/30 to 80/20. 18) An emulsion according to any one of claims 1) to 17), characterized in that the mass ratio, expressed in sec, of dispersing and / or stabilizing agent (De) / mass of the internal inverse emulsion (Ei) , ranges from 0.01 / 100 to 50/100, preferably from 0.1 / 100 to 10/100, very particularly from 0.5 / 100 to 5/100.

19) Emulsion according to any one of claims 1) to 18), characterized in that the concentration of the external phase (We) in dispersing and / or stabilizing agent (De) ranges from 1 to 50%. 20) Emulsion according to any one of claims 1) to 19), characterized in that the external phase (We) is an aqueous phase.

21) Emulsion according to any one of claims 1) to 19), characterized in that the external phase (We) is an alcoholic or hydroalcoholic phase, preferably isopropanol or ethanol.

22) Emulsion according to any one of claims 1) to 20), characterized in that the active material (A) contained in or constituting the hydrophobic phase (O) is chosen from care or detergency agents for fiber articles textiles, and in that the external phase (We) is an aqueous liquid detergent formulation containing the dispersing and / or stabilizing agent (De) formed from a mixture of at least one nonionic hydrophilic surfactant and of at least one anionic hydrophilic surfactant, optionally combined with at least one nonionic hydrophilic (amphiphilic) polymer.

23) Emulsion according to any one of claims 1) to 19) and 21), characterized in that the active material (A) contained in or constituting the hydrophobic phase (O) is chosen from care or detergency agents for articles made of textile fibers, and in that the external phase (We) is a non-aqueous liquid detergent formulation miscible with water, containing the dispersing agent and / or stabilizer (De) formed from a mixture of at least one nonionic hydrophilic surfactant and at least one anionic hydrophilic surfactant, optionally combined with at least one nonionic hydrophilic (amphiphilic) polymer.

24) Emulsion according to any one of claims 1) to 20), characterized in that the active material (A) contained in or constituting the hydrophobic phase (O) is chosen from agents for caring for articles of textile fibers, and in that the external phase (We) is an aqueous liquid rinsing formulation, containing the dispersing and / or stabilizing agent (De) formed of at least one cationic hydrophilic surfactant and / or at least one polymer (amphiphilic) cationic hydrophilic, optionally in admixture with at least one nonionic hydrophilic surfactant and / or at least one nonionic hydrophilic (amphiphilic) polymer.

25) Emulsion according to any one of claims 1) to 20), characterized in that the active material (A) contained in or constituting the hydrophobic phase (O) is chosen from agents in the field of paints, and in that the external phase (We) is an aqueous paint.

26) Emulsion according to any one of claims 1) to 20), characterized in that the active material (A) contained in or constituting the hydrophobic phase (O) is chosen from agents in the cosmetic or body care field, and in that the external phase (We) is an aqueous cosmetic composition. 27) Emulsion according to any one of Claims 1) to 16), characterized in that it is in the form (Es) and in that the solid matrix (M) is made of materials chosen from - polyethylene glycols having a molecular weight between 2,000 and 100,000 g / mole - copolymers of ethylenically unsaturated carboxylic acid or anhydride and ethylenically unsaturated nonionic monomer - polypeptides of natural or synthetic origin, water-soluble or water-dispersible - polyelectrolytes in acid form, belonging to the family of weak polyacids, having a molecular weight of less than 20,000 g / mole, preferably between 1,000 and 5,000 g / mole - polyvinylpyrrolidones having a molecular weight of less than 20,000 g / mole, preferably between 1,000 and 10,000 g / mole - polyvinyl alcohols having a molecular weight of less than 100,000 g / mole, and preferably having a deacetylation rate of 80 to 99 mol%, preferably 87 95% molar - water-soluble or water-dispersible film-forming ampholyte polymers - water-soluble or water-dispersible oses, osides or polyholosides - amino acids or water-soluble or water-dispersible salts of amino acids - citric acid - fatty acids - urea - surfactants whose binary water-surfactant phase diagram includes an isotropic fluid phase at 25 ° C up to a concentration of at least 50% by weight of surfactant, followed by a rigid liquid crystal phase of hexagonal or cubic type at higher concentrations, stable at least up to 60 ° C. - the water-soluble or water-dispersible salts of alkali metals, such as silicates, carbonates, phosphates, sulfates, phosphonates, acetates, citrates, alkali metal saturated or unsaturated fatty acid salts, mixtures of sodium acetate and citric acid - or mixtures thereof.

28) Use of the emulsion (E) forming the subject of any one of claims 1) to 27), for conveying, in aqueous medium (B) in contact with a substrate (S), the hydrophobic phase (O ) containing and / or consisting of at least one hydrophobic active material (A), towards said substrate (S).

29) Use according to claim 28), characterized in that said substrate (S) is of any material, in particular a metal or any natural, artificial or synthetic material, or a mixture of these materials.

30) Use according to claim 28) or 29), in paints for conveying a hydrophobing agent on a surface made of a material of construction, plaster, cement, or wood, with release of the hydrophobicizing agent by depositing and drying the paint on the surface.

31) Use according to claim 28) or 29), in cosmetic compositions for conveying a hydrophobic cosmetic or body care or hair care active material, with release of the hydrophobic agent by deposition or application and drying on the skin or hair .

32) Use according to claim 28) or 29) in formulations for the treatment of metals.

33) Use according to claim 28) or 29), for the preparation or post-treatment of a surface of a woven or non-woven material of cellulosic and / or synthetic origin, for personal hygiene or the cleaning of the house, intended to be brought into contact with the skin.

34) Use according to claim 28) or 29), for the preparation or post-treatment of cardboard boxes or cardboard packaging 35) Use according to claim 28) or 29), to convey, in aqueous medium (B) brought into contact with a substrate (S), the hydrophobic phase (O) containing and / or consisting of at least one hydrophobic active material (A), towards said substrate (S), the volume of said aqueous medium being sufficient to cause destabilization and / or the rupture of the emulsion (E) by dilution of said emulsion (E) and / or drying subsequent to the dilution of said emulsion (E), and the provision and / or release of the active material (A) contained or constituent of the hydrophobic phase (O), on the substrate (S).

36) Use according to claim 35), characterized in that the multiple emulsion (Em) comprises at least 70% by weight of internal emulsion

(Ei).

37) Use according to claim 35) or 36), characterized in that the relative amounts of emulsion (Em) and aqueous medium (B) are equivalent to a dilution of 2 to 100 times the volume of said emulsion (Em) . 38) Use according to any one of claims 35) to 37), for conveying and depositing a hydrophobic active material on a hydroxyapatite surface, a keratin surface or a textile surface. 39) Use according to claim 38), in a formulation for dental or oral hygiene, intended to be rinsed or diluted.

40) Use according to claim 38, in a cosmetic formulation for the care of hair and / or skin, intended to be rinsed or diluted.

41) Use according to any one of claims 35) to 38), characterized in that the hydrophobic phase (O) and / or the active material (A) is chosen from care or detergency agents for articles of textile fibers .

42) Use of the emulsion (E) according to claim 38) or 41), as an additive in a detergent composition for washing or rinsing articles of textile fibers, or as a detergent or rinsing composition for washing or rinsing articles of textile fibers, with the aim of conveying a hydrophobic care agent and / or any other useful hydrophobic active material, and of promoting the deposition of the latter and / or of this on an article of textile fibers, cotton in particular, during the rinsing operation and / or during the drying operation subsequent to the main washing operation when it is a detergent composition for washing, or during the subsequent drying operation in the case of a rinsing composition.

43) Method for conveying, to a substrate (S) in contact with an aqueous medium (B), at least one active material (A) contained in or constituting a hydrophobic phase (O) liquid or fuse of the emulsion ( E) forming the subject of any one of claims 1) to 27), by bringing said emulsion (E) into contact with the substrate (S) in contact with the aqueous medium (B).

44) Method according to claim 43), characterized in that the volume of said aqueous medium (B) is sufficient to cause destabilization and / or rupture of the emulsion (E) by dilution of said emulsion (E) and / or drying subsequent to the dilution of said emulsion (E), and the provision and / or release of the active material (A) contained or constituting the hydrophobic phase (O), on the substrate (S). 45) Method according to claim 44), characterized in that the emulsion

(E) is a multiple emulsion (Em) comprising at least 70% by weight of internal emulsion (Ei).