FR2833185A1 - MULTIPLE EMULSIONS INCLUDING AN INTERNAL GELIFIED OIL PHASE - Google Patents

Abstract

The invention concerns multiple emulsions A/B/C comprising a dispersed phase A in a continuous phase B, the whole of phase B comprising phase A, constituting a dispersed phase in a continuous phase C; phases A and B and phase B and C being mutually non-miscible; the multiple emulsions A/B/C being of the type water/oil//water, oil/water/oil, silicone/oil/water or oil/silicone/water, characterized in that the internal oil phase A or B comprises at least a gelling polymer substantially insoluble in aqueous medium, having at least three identical or different branches, each branch consisting: of an internal sequence comprising repeating oxypropylene and/or oxybutylene, and optionally oxyethylene units; an external sequence comprising a linear or branched, saturated or unsaturated hydrocarbon chain, comprising at least 18 carbon atoms in the longest chain, and optionally interrupted by one or several aromatic rings; the two sequences being mutually linked via a spacer segment of formula: XCOX'r-[{R<sp>1</sp>-XCOX'r}p-R<sp>2</sp>-XCOX'r]q, wherein: X, X', identical or different, represent -O-, -NH-, -NHCO-; R<sp>1</sp>, R<sp>2</sp>, identical or different, represent an alkyl or aryl radical; p is an integer ranging between 0 and 9; q is equal to 0 or 1; r is equal to 0 or 1.

Description

<Desc / Clms Page number 1>

La présente invention a pour objet des émulsions multiples du type eau 1 huile 1 eau, hui) e/eau/huiie, siticone/hui) e/eau ou huile 1 silicone 1 eau, dans lesquelles la phase huile interne est gélifiée. MULTIPLE EMULSIONS INCLUDING
A GELIFIED INTERNAL OIL PHASE

The present invention relates to multiple emulsions of the type water 1 oil 1 water, oil) e / water / oil, siticone / oil) e / water or oil 1 silicone 1 water, in which the internal oil phase is gelled.

Multiple emulsion systems are often used to limit the exchanges of active materials with the external medium and they represent a definite improvement over systems comprising only a single emulsion.

It may however be advantageous to improve multiple emulsion systems, so as to further limit the possible exchanges with the external medium.

It has been thought to replace the oil constituting the organic phase in contact with the external aqueous medium, with an organic compound which is solid at room temperature, such as waxes for example. One of the limitations of such systems lies in the fact that the rapid release of the active material which is encapsulated in the droplets of wax depends on the rise in temperature beyond the melting point of said wax. However, in certain applications, such a rise in temperature cannot be reasonably implemented.

Furthermore, it may be advantageous in certain cases to dissolve a hydrophobic active material in the organic phase. However, there are fewer organic compounds of the wax type than there are compounds of the oil type. Thus, it is possible to encounter more difficulties in finding waxes compatible with the active material used than in the case of oils.

The object of the present invention is therefore to provide systems of the multiple emulsion type, compatible with the use of organic phases which are liquid at room temperature, and which limit the exchanges of active material from one phase to another.

These aims and others are achieved by the present invention which therefore relates to multiple A / B / C emulsions comprising a dispersed phase A in a continuous phase B, the whole of phase B comprising phase A, constituting a phase dispersed in a continuous phase C; phases A and B on the one hand, and phases B and C on the other hand, being immiscible with one another; the multiple emulsions A / B / C being of the water / water / water, oil / water / oil / water, silicone / oil / water or oil 1 silicone 1 water type, characterized in that the internal oil phase A or B comprises at least least one gelling polymer which is substantially insoluble in aqueous medium, having at least three identical or different branches, each branch consisting of:

<Desc / Clms Page number 2>

- of an internal block comprising repeating units oxypropylene and / or oxybutylene, and optionally oxyethylene, - of an external block comprising a hydrocarbon chain, linear or branched, saturated or not, comprising at least 18 carbon atoms in the chain the longest, and optionally interrupted by one or more aromatic rings; the two sequences being linked together via a spacer segment of formula: - XCOX'r- [<! R1-XCOX'ri-p-R2-XCOX'r] q; formula in which: - X, X ', which may or may not be identical, represent -O-; -NH-; -NHCO-; - R1, R2, identical or not, represent a divalent alkyl radical, linear or branched, comprising 1 to 18 carbon atoms in the longest chain, or a divalent aryl radical comprising one or more aromatic rings, optionally substituted, - p is an integer between 0 and 9; - q is equal to 0 or 1; - r is equal to 0 or 1.

It should be noted, and this represents an advantage of the present invention, that the active material encapsulated by means of the gelled oil phase can be released easily and quickly, by applying a simple shear to the multiple emulsion.

According to the present invention, any mixture will be qualified as a gel which, placed in a glass tube comprising the oil and the gelling polymer at a concentration of between 0.5 and 10% by weight of oil, does not flow for a long time. minute after inverting the tube to 1800; the test being carried out at 20 ° C., in a glass tube 10 cm long, 1.8 cm in diameter, the oil mixture 1 gelling polymer representing 5 cm of the height of the tube.

Furthermore, the term polymer will be used to denote homopolymers and copolymers indifferently.

In addition, the term macromonomer denotes a macromolecule carrying one or more functions capable of being polymerized, depending on the polymerization method adopted.
Before describing the multiple emulsion, the gelling polymer will first be described.

As has been indicated previously, the gelling polymer is a polymer which is substantially insoluble in aqueous medium. The term “substantially insoluble” is intended to denote polymers which, when introduced into water, at a temperature of 20 ° C. and at a concentration of 1% by weight, form a precipitate.

<Desc / Clms Page number 3>

The gelling polymers also preferably have a molar mass by weight of less than or equal to 100,000 g / mol, more particularly between 1,000 and 10,000 g / mol. It should be noted that the molar masses by weight of the polymers correspond to relative values which were evaluated by size exclusion chromatography, by comparing with linear polystyrene standards of low polydispersity and by using dichloromethane (CH2Cl2) as eluent.

Furthermore, the gelling polymer is chosen from branched polymers, that is to say polymers comprising at least three branches.

Each of the branches, which may or may not be identical, comprises an internal sequence and an external sequence, possibly linked together by a spacer segment.

The internal block comprises oxypropylene and / or oxybutylene repeat units, and optionally oxyethylene.

More particularly, the total number of oxypropylene and / or oxybutylene repeat units is between 1 and 10, advantageously between 3 and 9.

Moreover, if one or more of the blocks comprises oxyethylene repeating units, the total number of these repeating units in the polymer is such that the polymer remains substantially insoluble in water, in the sense indicated above. Preferably, if they are present, the total number of oxyethylene repeat units in the polymer represents less than 10% of the total number of oxypropylene and / or oxybutylene units.

The external sequence comprises a hydrocarbon chain, linear or branched, saturated or not, comprising at least 18 carbon atoms in the longest chain, and optionally interrupted by one or more aromatic rings, more particularly rings comprising 6 carbon atoms.

According to a more particular embodiment of the invention, the hydrocarbon chain comprises 18 to 40 carbon atoms.

Preferably, the hydrocarbon chain is saturated.

Furthermore, the hydrocarbon chain is advantageously linear, or, if it comprises one or more branches, the latter do not contain more than four carbon atoms.

The spacer, by means of which are connected the internal and external sequences of each branch, identical or different from one branch to another, has the following formula: - XCOX'r- [Ri-XCOX'r! -P- R2-XCOX'r] q; formula in which: - X, X ', which may or may not be identical, represent -O-; -NH-; -NHCO-;

<Desc / Clms Page number 4>

- R1, R2, identical or not, represent an alkyl radical, linear or branched, comprising 1 to 18 carbon atoms, preferably 4 to 12 carbon atoms in the longest chain, or an aryl radical comprising one or more rings aromatic, optionally substituted, - p is an integer between 0 and 9, preferably between 0 and 3; q is 0 or 1; r is equal to 0 or 1.

More particularly, in the above formula, R1, R2, which may or may not be identical, correspond to the following formula: - (CH2) n- (CH (CH3)) n'-; in which n, n ', identical or not, are integers varying from 0 to 12, on the condition that at least one of the two coefficients is not zero and that n + n is at most 12, preferably at most 10. Preferably, R1, R2, which are identical or different, correspond to the following formula: - (CH2) n-; formula in which n is an integer equal to 5.

Preferably, X represents -O- or -NH- and r is equal to 0.

According to another possibility, the radicals R1, R2, which may or may not be identical, represent aryl radicals comprising one or more aromatic rings, optionally substituted. The radicals can comprise a single aromatic ring, preferably with 6 carbon atoms, or else consist of several aromatic rings, preferably two aromatic rings, pericondensed or linked by inert groups, such as single valential bonds, an alkyl radical. comprising 1 to 4 carbon atoms.

According to one embodiment of the invention, the polymers which have just been described are obtained by implementing polyaddition and / or polycondensation reactions during which water or carbon dioxide molecules are released, and / or cycle opening.

In particular, the reactions involved are of the carboxylic acid type with alcohol, carboxylic acid with amine, carboxylic acid with isocyanate, amine with isocyanate, alcohol with isocyanate, lactam ring opening by an amine, lactone ring opening by an alcohol .

As the first type of reagent used in the preparation of the polymer, more particularly those from which the internal blocks are derived, mention may be made of polyoxypropylenated and / or polyoxybutylenated polyamines comprising at least three amine functions, polyoxypropylenated and / or polyoxybutylenated polyols comprising at least three alcohol functions, the polyoxypropylenated and / or polyoxybutylenated polyisocyanates comprising at least three isocyanate functions.

As a second type of reagents, those from which the external sequences are derived, mention may in particular be made of monocarboxylic acids, monoisocyanates, monoalcohols and monoamines having a hydrocarbon chain.

According to a first variant, the first and second reagents have antagonist functions (reacting with each other).

<Desc / Clms Page number 5>

A first embodiment of this variant consists in bringing these two reagents into contact only (q = 0).

A second embodiment of this variant consists in bringing the two reagents into contact in the presence of a third, difunctional reagent, itself also possessing the functions antagonistic to those of the first and second reagents.

It should be noted that this third reagent can also be a compound of the amino acid type, masked or not. The masked amino acids are more particularly chosen from lactams.

The third reagent can be a compound of the hydroxy acid type, masked or not.

The masked hydroxy acids are more particularly chosen from lactones.

This third reagent can also be a macromonomer, that is to say consist of several units linked together by —XCO— functions; X representing -NH- or -O- (pO); the two reactive functions of this macromonomer being functions antagonistic to those of the first and second reactants. In this scenario, and depending on the nature of the reactive functions of the first and second reactants, the -XCO functions may or may not be identical.

It should also be noted that in the case of macromonomers, the latter can be prepared during the polycondensation itself, or else be the subject of a separate synthesis.

According to a second variant, the first and second reagents have functions of the same type (which do not react with each other).

In such a case, the presence of a third type of reagent is necessary. The latter is a difunctional compound having two functions antagonistic to those of the two aforementioned reagents.

This third reagent can be chosen from compounds of the dicarboxylic acid type, diisocyanates, diamines or diols.

It can likewise be a macromonomer, that is to say it may consist of several units linked together by —XCO— functions; X representing -NH- or -0-; the two reactive functions of this macromonomer being functions antagonistic to those of the first and second reactants. Here again, the functions-XCO-may or may not be identical.

Finally, as previously, the macromonomers can be synthesized during the polycondensation or else separately.

Advantageously, and whatever the variants used, the nature and the respective amounts of the reactants are chosen such that the molar ratio between reactive functions is stoichiometric.

The procedure is carried out by bringing the various reagents into contact, preferably in the absence of solvent.

<Desc / Clms Page number 6>

This first step is generally carried out at a temperature such that the reagents are in liquid form. Thus, the reaction is usually carried out at a temperature greater than or equal to the melting point of the reactants.

The various reagents are used in adequate amounts to obtain a polymer as defined above.

The reagents can be introduced successively, or else they can be present simultaneously.

Once the contact has been made, the actual polymerization reaction is carried out. To do this, the temperature is brought to a value generally between 100 C and 300 C. During this step, water or carbon dioxide may be released.

The pressure conditions during the polymerization reaction can be determined without difficulty by a person skilled in the art. For example, the removal of water can take place under vacuum.

Furthermore, it is preferable that the reaction, when it is carried out at atmospheric pressure, is carried out under an inert atmosphere, in particular under a nitrogen purge.

The operation takes place with stirring.

phénylphosphinique, l'acide phénylphosphonique ou le phosphite de tris (nonyl phényle). A catalyst can optionally be used to promote the polyamide reaction, such as, for example, hypophosphorous acid, acid

phenylphosphinic, phenylphosphonic acid or tris (nonyl phenyl) phosphite.

de titane, le tétrabutylorthozirconate, l'octoate d'étain, le dilaurate de dibutylétain. It is also possible to use a catalyst which promotes the polyesterification if necessary. Among the catalysts that can be used, mention may be made of catalysts based on titanium, zirconium, tin among others, such as for example tetrabutylorthotitanate.

titanium, tetrabutylorthozirconate, tin octoate, dibutyltin dilaurate.

It is also possible to use an isocyanate reaction catalyst if necessary. Among the catalysts that can be used, mention may be made of tertiary amines, among others, such as, for example, triethylene diamine, N, N'-dimethylpiperazine, triethylamine.

The catalyst may represent a content less than or equal to 1% by weight relative to the total weight of the various monomers, more particularly less than or equal to 0.5%, and preferably between a few tens and a few hundreds of parts per million.

Once the reaction is complete, the polymer is recovered in a conventional manner by expelling the melt through a drain port.

According to an advantageous embodiment of the present invention, the content of gelling polymer represents 0.5 to 10% by weight of the internal oil phase A or B, preferably 1 to 5% by weight of the internal oil phase A or B .

<Desc / Clms Page number 7>

Multiple emulsions will now be described.

As has been indicated previously, the multiple emulsions comprise a phase A dispersed in a phase B, the whole being dispersed in a phase C. Furthermore, phases A and B are immiscible with one another; phases B and C also.

More particularly, phases A on the one hand, and B on the other hand, are said to be immiscible respectively in phases B and C, when their solubility in the phase concerned does not exceed 10% by weight, in a temperature range. between 20 C and the preparation temperature of the multiple emulsion.

According to an essential characteristic of the invention, the internal oil phase of the multiple emulsion comprises the gelling polymer described above. More particularly, it may be phase A or phase B of the multiple emulsion, depending on the case.

It is indicated that in the remainder of the text, phase A may be qualified as dispersed internal phase, phase B as continuous internal phase, phase C as continuous external phase.

It should be noted more particularly that at least one of the phases of the multiple emulsion comprises at least one active material. It should be noted that said active material may be different from the phase in which it is present, or else it may constitute the phase itself. If the active material is different from the phase in which it is present, it is in a form soluble in the phase concerned or in a form dissolved in a solvent miscible with said phase, or in the form of a solid suspended in said phase. Moreover, and always in the case where the active material and the phase concerned are different, the content of active material is more particularly between 0.1 and 50% by weight of said phase, and preferably between 0.1 and 20% by weight of said phase.

In the case where the phase can be considered as an active material as such, then it is chosen from the compounds which are in liquid form at room temperature.

A first category of multiple emulsions according to the invention consists of multiple emulsions of the water / oil / water type or of the oil / water / oil type.

As indicated above, the aqueous phase (s) of these two systems may optionally comprise at least one hydrophilic active material which may be in a soluble form or dissolved in a water-miscible solvent (such as, for example, methanol, ethanol. , propylene glycol, glycerol, or mixtures thereof), or in the form of a solid in suspension; the amount of active material, if present, falling within the ranges mentioned above.

<Desc / Clms Page number 8>

Given the large number of fields in which the multiple emulsions according to the invention are capable of being used, numerous active materials may be suitable for the implementation of the invention.

By way of example of active materials which can be used in the field of cosmetics, mention may be made of substances which have a cosmetic effect, a therapeutic effect or any other substance which can be used for the treatment of the skin and the hair.

Thus, it is possible to use, as active material, conditioning agents for the skin and / or the hair, such as in particular polymers comprising quaternary ammoniums which can optionally be used in heterocycles (compounds of the quaternium, polyquaternium, etc. type. ). , humectants; fixing agents (styling) which are more particularly chosen from polymers (homo-, co-or ter-polymers, for example acrylamide, acrylamide / sodium acrylate, polystyrene sulfonate, etc.), cationic polymers, polyvinyl pyrrol id one, polyvinyl acetate, etc.

It is also possible to use coloring agents; astringent agents which can be used in deodorants and which are more particularly aluminum or zirconium salts; antibacterial agents; anti-inflammatory agents, anesthetic agents, sun filters, etc.

Mention may also be made of α- and p-hydroxy acids, such as citric, lactic, glycolic or salicylic acids; dicarboxylic acids, preferably unsaturated, comprising 9 to 16 carbon atoms, such as azelaic acid; vitamin C and its derivatives, in particular glycosylated and phosphate derivatives; biocides, in particular cationic (in particular Glokill PQ, Rhodoquat RP50, marketed by Rhodia Chimie).

In the food industry, mention may be made, for example, of divalent calcium salts (phosphates, chlorides, etc.) used as a crosslinking agent for texturizing polymers such as alginates, carrageenans; sodium bicarbonate, among others.

In the field of phytosanitary active materials, it is possible to use hydrophilic pesticides or hydrophilic nutrients which promote the growth and development of plants.

Bentazon, Bialaphos, Bispyribac, Bromacil, Bromoxynil, Chloramben, Clopyralid, 2, 4-D, 2,4-Db, Dalapon, Dicamba, Dichlorprop, Diclofop, Difenzoquat, Diquat, Endothall, Fenac, Fenoxaprop, Flamprop, Fluazifop, Fluoroglycofen, Fluroxypyr, Fomesafen, Among the suitable active materials, mention may in particular be made of the following herbicidal active materials, in the form or not of organic or inorganic salts: aminophosphate or aminophosphonate derivatives, Acifluorfen, Asulam, Benazolin,

Bentazon, Bialaphos, Bispyribac, Bromacil, Bromoxynil, Chloramben, Clopyralid, 2, 4-D, 2,4-Db, Dalapon, Dicamba, Dichlorprop, Diclofop, Difenzoquat, Diquat, Endothall, Fenac, Fenoxaprop, Flamprop, Fluazifopen, Fluoroglycofen, Fluroxypyr, Fomesafen,

<Desc / Clms Page number 9>

Fosamine, Haloxyfop, loxynil, Mcpa, Mcpb, Mecoprop, Methylarsonic Acid, Naptalam, Nonanoic Acid, Paraquat, Picloram, Sulfamic Acid, or mixtures thereof.

Preferably, the active material is chosen from aminophosphate or aminophosphonate derivatives, in the form of organic or inorganic salts, such as glyphosate, sulphosate or glufosinate.

As regards the field of the operation or construction of oil or gas field wells, the present invention can be implemented for hydrophilic active materials which can be used in particular during cementation, completion, drilling and stimulation operations. wells (eg fracking). As examples of active materials which can be used in this field, mention may be made of catalysts for the crosslinking of cementitious compositions, such as, for example, lithium salts, such as chloride or acetate. Mention may also be made of compounds capable, inter alia, of degrading polysaccharides, such as, for example, carboxylic acids (in particular citric acid), enzymes (in particular cellulases), oxidants.

In the field of silicones, mention may be made, for example, of calcium salts and potassium hydroxide, usually used as crosslinking agents.

As suitable active materials in the field of papermaking, mention may in particular be made of calcium chloride and hydrochloric acid.

As regards the oil phase (s) of this first category of multiple emulsions, they consist of compounds immiscible in water, in the sense indicated above, in liquid form at room temperature (20- 30 C).

More particularly, the oil phase intended to comprise the gelling polymer is chosen from the following compounds: organic oils of animal or plant origin; - products resulting from the alcoholysis of the aforementioned oils; - essential oils ; - mono-, di- and tri-glycerides - esters of fatty acids, saturated or not, comprising 10 to 40 carbon atoms and alcohols comprising 1 to 6 carbon atoms; - alcohols, saturated or not, comprising 4 to 40 carbon atoms, and optionally comprising several hydroxyl groups; these compounds being used alone or as a mixture.

As organic oils of animal origin, mention may be made, among others, of sperm whale oil, whale oil, seal oil, shark oil, cod liver oil, alone or as a mixture. .

As examples of organic oils of vegetable origin, mention may be made, among others, of rapeseed oil, sunflower oil, peanut oil, olive oil, oil.

<Desc / Clms Page number 10>

walnut, corn oil, soybean oil, avocado oil, linseed oil, hemp oil, grapeseed oil, coconut oil, palm oil, cottonseed oil, babassu oil, jojoba oil, sesame oil, castor oil, macadamia oil, sweet almond oil, alone or as a mixture.

The products resulting from the alcoholysis of the aforementioned oils can also be used.

Among the essential oils, there may be mentioned without intention to be limited thereto, the oils and / or essences of mint, spearmint, peppermint, menthol, vanilla, cinnamon, bay leaf, anise, 'eucalyptus, thyme, sage, cedar leaf, nutmeg, citrus (lemon, lime, grapefruit, orange), fruit (apple, pear, peach, cherry, plum, strawberry, raspberry, apricot , pineapple, grape, etc.), alone or in mixtures.

Regarding fatty acid esters, these can advantageously be obtained from fatty acids, saturated or not, comprising 10 to 40 carbon atoms, more particularly 18 to 40 carbon atoms, and which may comprise one or more unsaturations ethylenic, conjugated or not. It should be noted that said acids can comprise one or more hydroxyl groups.

As examples of saturated fatty acids, mention may be made of palmitic, stearic and behenic acids.

As examples of unsaturated fatty acids, mention may be made of myristoleic, palmitoleic, oleic, erucic, linoleic, linolenic, arachidonic and ricinoleic acids, as well as their mixtures.

As for the alcohols from which these esters are prepared, they more particularly comprise 1 to 6 carbon atoms. Preferably, they are methyl, ethyl, propyl or isopropyl esters.

The oil phase can likewise be chosen from mono-, di- and tri-glycerides.

The alcohols more particularly comprise 4 to 40 carbon atoms, preferably 10 to 40 carbon atoms, optionally one or more ethylenic unsaturations, conjugated or not, and optionally several hydroxyl groups.

Polymers comprising several hydroxyl groups may likewise be suitable, such as, for example, polypropylene glycols.

Finally, it is specified that it is not excluded that the oil phase comprises a quantity of water which does not exceed the limit of solubility of water in said oil phase (at a temperature between 20 and 30 C) .

As oil phase intended not to include the gelling polymer, mention may in particular be made of: organic oils of animal or plant origin; - mineral oils, such as for example naphthenic, paraffinic (petrolatum), isoparaffinic oils, alone or as a mixture.

<Desc / Clms Page number 11>

- products resulting from the alcoholysis of the aforementioned oils; - essential oils ; - mono-, di- and tri-glycerides - esters of fatty acids, saturated or not, comprising 10 to 40 carbon atoms and alcohols comprising 1 to 6 carbon atoms; - alcohols, saturated or not, comprising 4 to 40 carbon atoms, and optionally comprising several hydroxyl groups; these compounds being used alone or as a mixture.

As regards the possible choices of compounds appearing in the above list, reference may be made to the details indicated above in the context of the choice of the oil phase intended to comprise the gelling polymer.

The oil phase, with or without a gelling polymer, may optionally comprise an active material, which may be in liquid form, in a form soluble in said oil phase or dissolved in a solvent miscible with the oil phase or else in the form of a solid suspended in said oil phase. Furthermore, the amount of hydrophobic active material, if it is present and if it is different from the oil phase, is more particularly within the ranges indicated above.

Finally, it is recalled that in the case where the oil phase is considered as an active material as such, then it is chosen from the compounds which are in liquid form at room temperature.

The active material is obviously chosen according to the field of application of the multiple emulsion according to the invention.

By way of example of active materials in the field of food, mention may be made of mono-, di- and triglycerides, essential oils, flavors and colorings.

By way of example of active materials in the field of cosmetics, mention may be made of silicone oils belonging, for example, to the family of dimethicones; lipophilic vitamins, such as vitamin A, D, E; UV absorbers (aminobenzoate derivatives of the PABA and PARA type, dibenzoylmethanes, etc.); anti-aging agents (retinoids, vitamin C derivatives such as esters of the acetate, propionate or palmitat type; ceramides and pseudo-ceramides, phospholipids, etc.); anti-cellulite agents (isobutylmethylxanthine, theophyline); anti-acne agents (resorcinol and its derivatives, etc.); bactericides; anti-microbial agents (thymol, menthol, triclosan, etc.); aromas, perfumes, essential oils or even aldehydes and esters.

By way of example of active materials suitable for carrying out the invention, in the field of paints, mention may be made of alkyd resins, epoxy resins, masked or unmasked (poly) isocyanates.

<Desc / Clms Page number 12>

In the field of paper, examples that may be mentioned are sizing and water-repellent resins, such as alkyl ketene dimer (AKD) or alkenyl succinic anhydride (ASA).

In the field of agrochemistry, the plant protection active materials can be chosen from the family of α-cyano-phenoxybenzyl carboxylates or α-cyanohalogenophenoxy-carboxylates, the family of N-methylcarbonates comprising aromatic substituents, active materials such as Aldrin , Azinphos-methyl, Benfluralin, Bifenthrin, Chlorphoxim, Chlorpyrifos, Fluchloralin, Fluroxypyr, Dichlorvos, Malathion, Molinate, Parathion, Permethrin, Profenofos, Propiconazole, Prothiofos, Pyrifenox, Butachlor, Metonimephosargil, Dichlorvos, , Mecarbam, Propargite, Prosulfocarb, Bromophos-ethyl, Carbophenothion, Cyhalothrin.

It is likewise possible to use active materials such as those entering into the composition of lubricants for working or deforming materials. The active material is usually an oil, a derivative of an oil or a fatty acid ester.

The active material can also be chosen from organic solvents or mixtures of such solvents which are not or only slightly miscible in water in the sense indicated above, such as in particular those used for cleaning or pickling, such as aromatic petroleum fractions, terpene compounds such as D- or L-limonenes, as well as solvents such as Solvessoo.

méthyle et éthyle, mais pouvant être également propyle, isopropyle, butyle, n-butyle et isobutyle ; l'anisol ; la n-méthylpyrrolidone ; le diméthylsulfoxyde ; les cétones comme la cyclopentanone, la méthylisobutylcétone ; les polyalkylène glycols, comme le polyéthylène glycol 400, le polypropylène glycol 400. Also suitable as solvents are hydrocarbon-based oils such as petrolatum oil, and chlorinated solvents, C1-C4 alkyl diesters of at least one C4-C6 aliphatic diacid. Mixtures of diacid esters are used more particularly which are esters derived essentially from adipic, glutaric and succinic acids, the alkyl groups of the ester part being chosen above all from the groups.

methyl and ethyl, but can also be propyl, isopropyl, butyl, n-butyl and isobutyl; anisol; n-methylpyrrolidone; dimethyl sulfoxide; ketones such as cyclopentanone, methyl isobutyl ketone; polyalkylene glycols, such as polyethylene glycol 400, polypropylene glycol 400.

Multiple emulsions further comprise surfactants and / or polymers chosen according to the nature of the interface to be stabilized, in other words according to the nature of the continuous phase and of the dispersed phase.

According to a first advantageous embodiment of the invention, the surfactants and / or polymers are chosen from compounds satisfying the Bancroft rule. In other words, the fraction of the soluble polymer in the continuous phase is greater than the fraction of the soluble polymer in the dispersed phase.

<Desc / Clms Page number 13>

Preferably, the inverse emulsion comprises at least one surfactant and / or at least one polymer, chosen from those which satisfy both the two conditions below: - when they are mixed with phase B, at a concentration between 0 , 1 and
10% by weight of phase B and at a temperature between 20 C and the preparation temperature of emulsion A / B, are in the form of a solution in phase B, in all or part of the range of indicated concentration; - when mixed with phase A, at a concentration between 0.1 and
10% by weight of phase A and at a temperature between 20 C and the preparation temperature of emulsion A / B, are in the form of a dispersion in phase A, in all or part of the range of indicated concentration.

Moreover, at least one of the phases of the multiple emulsion comprises at least one surfactant and / or at least one polymer, preferably chosen from those which satisfy both the two conditions below: - when they are mixed with phase C, at a concentration between 0.1 and
10% by weight of phase C and at a temperature between 20 C and the preparation temperature of the A / B / C emulsion, are in the form of a solution in phase C, in all or part of the indicated concentration range; - when they are mixed with phase B, at a concentration between 0.1 and
10% by weight of phase B and at a temperature between 20 C and the temperature for preparing the A / B / C emulsion, are in the form of a dispersion in phase B, in all or part of the indicated concentration range.

Thus, according to a first variant of this embodiment, when phase A is an aqueous phase (dispersed) and B an oil phase (continuous), or when phase B is an aqueous phase (dispersed) and phase C is an oil phase (continuous), respectively phase B (continuous) or phase C (continuous), comprises at least one nonionic surfactant and / or at least one amphiphilic block polymer comprising at least one hydrophobic block and at least one hydrophilic block neutral, anionic or cationic. It is recalled that the surfactant and the polymer satisfy the Bancroft rule stated above.

In addition, the total content of nonionic surfactant (s) and / or amphiphilic block polymer (s) being between 0.1 and 10% by weight, preferably between 2 and 10% by weight. weight relative to phase A (dispersed) or phase B (dispersed), respectively.

<Desc / Clms Page number 14>

As regards the nonionic surfactants, the latter are advantageously chosen from surfactants having an HLB (hydrophilic / lipophilic balance) value of less than or equal to 8.

As examples of suitable surfactants, mention may be made, alone or as a mixture: - alkoxylated fatty alcohols - alkoxylated mono, di or triglycerides - alkoxylated fatty acids - optionally alkoxylated sorbitan esters - alkoxylated fatty amines - alkoxylated di (1-phenyl ethyl) phenols - alkoxylated tri (1-phenyl ethyl) phenols - alkoxylated alkylphenols the number of alkoxylated units (ethoxylated, propoxylated, butoxylated) is such that the HLB value is less than or equal to 8.

Alkoxylated fatty alcohols generally contain from 6 to 22 carbon atoms, the alkoxylated units being excluded from these numbers.

The alkoxylated mono, di or triglycerides can be triglycerides of plant or animal origin.

The optionally alkoxylated sorbitan esters are more especially cyclized fatty acid sorbitol esters comprising from 10 to 20 carbon atoms such as auric acid, stearic acid or oleic acid.

Alkoxylated fatty amines generally have 10 to 22 carbon atoms, alkoxylated units being excluded from these numbers.

Alkoxylated alkylphenols generally have one or two alkyl groups, linear or branched, having 4 to 12 carbon atoms. By way of example, mention may in particular be made of octyl, nonyl or dodecyl groups.

As for the block amphiphilic polymer, this comprises at least two blocks.

These amphiphilic polymers, satisfying Bancroft's rule and the two conditions stated above, more particularly comprise at least one hydrophobic block and at least one neutral, anionic or cationic hydrophilic block.

In the case where the amphiphilic polymer comprises at least three blocks, and more particularly three blocks, the polymer is preferably linear. In addition, the hydrophobic blocks are preferably found at the ends.

In the event that the polymers comprise more than three blocks, the latter are preferably in the form of graft or comb polymers.

<Desc / Clms Page number 15>

In what follows, even if this constitutes a misnomer, the term amphiphilic block polymer will be used interchangeably for linear block polymers and graft or comb polymers.

Said amphiphilic polymers can advantageously be obtained by so-called living or controlled radical polymerization. By way of nonlimiting examples of so-called living or controlled polymerization processes, reference may in particular be made to applications WO 98/58974 (xanthate), WO 97/01478 (dithioesters), WO 99/03894 (nitroxides); WO 99/31144 (dithiocarbamates).

The amphiphilic polymers can also be obtained by cationic or anionic polymerization.

They can likewise be prepared by bringing into play polymerizations by ring opening (in particular anionic or cationic), or by chemical modification of the polymer.

The graft polymers or combs can also be obtained by so-called direct grafting and copolymerization methods.

Direct grafting consists in polymerizing the chosen monomer (s) by a radical route, in the presence of the selected polymer to form the backbone of the final product. If the monomer / backbone pair as well as the operating conditions are judiciously chosen, then there may be a transfer reaction between the growing macroradical and the backbone. This reaction produces a radical on the backbone and it is from this radical that the graft grows. The primary radical from the initiator can also contribute to transfer reactions.

As regards the copolymerization, it firstly implements the grafting at the end of the future pendant segment, of a radical polymerizable function. This grafting can be carried out by usual methods of organic chemistry. Then, in a second step, the macromonomer thus obtained is polymerized with the monomer chosen to form the backbone and a so-called “comb” polymer is obtained.

Among the hydrophobic monomers from which the hydrophobic block (s) of the amphiphilic polymer can be prepared, there may be mentioned in particular: - esters of mono-or poly-carboxylic acids, linear, branched, cyclic or aromatic, comprising at least one ethylenic unsaturation , - esters of saturated carboxylic acids comprising more particularly 8 to 30 carbon atoms, and optionally carrying a hydroxyl group; - ap-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,

<Desc / Clms Page number 16>

- cyclic or non-cyclic siloxane type monomers, chlorosilanes; propylene oxide, butylene oxide; alone or in mixtures, as well as the macromonomers derived from such monomers.

As specific examples of hydrophobic monomers capable of entering into the preparation of the hydrophobic block (s) of the amphiphilic block polymer, there may be mentioned: - esters of (meth) acrylic acid with an alcohol comprising 1 to 12 atoms of carbon such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) acrylate ) isobutyl acrylate, 2-ethylhexyl acrylate; - vinyl acetate, Versatate &commat; vinyl, vinyl propionate, vinyl chloride, vinylidene chloride, methyl vinyl ether, ethyl vinyl ether; - vinyl nitriles include more particularly those having from 3 to 12 carbon atoms, such as in particular acrylonitril and methacrylonitrile; - styrene,) 'a-methylstyrene, vinyltoluene, butadiene, chloroprene, isoprene; alone or in mixtures, as well as the macromonomers derived from such monomers.

The preferred monomers are the esters of acrylic acid and methacrylic acid with linear or branched C1-C4 alcohols such as methyl, ethyl, propyl and butyl acrylate or methacrylate, the esters vinyls such as vinyl acetate, styrene, α-methylstyrene.

With regard to the nonionic hydrophilic monomers from which the amphiphilic block polymers can be obtained, there may be mentioned, without intending to be limited thereto, ethylene oxide, the amides of mono-or polycarboxylic acids, linear , branched, cyclic or aromatic, comprising at least one ethylenic unsaturation or derivatives, such as (meth) acrylamide, N-methylol (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, Versatate &commat; vinyl, vinyl propionate, alone, in combination, as well as the macromonomers derived from such monomers.

However, the preferred hydrophilic monomers are acrylamide and methacrylamide, alone or as a mixture, or in the form of macromonomers.

As regards the anionic hydrophilic monomers from which the amphiphilic block polymers can be obtained, there may be mentioned, for example, the monomers comprising at least one carboxylic, sulphonic, sulfuric, phosphonic, phosphoric or sulphosuccinic function, or the corresponding salts.

<Desc / Clms Page number 17>

It is specified that under the pH conditions of use of the amphiphilic block polymer, the functions of the anionic block (s) of the polymer are in an at least partially ionized (dissociated) form. More particularly, at least 10 mol% of the functions of the block (s) are in ionized form. The determination of this value does not pose a problem to those skilled in the art; it is in particular a function of the pKa of the ionizable functions of the units of the polymer and of the number of these functions (ie the number of moles of monomers bearing ionizable functions used during the preparation of the polymer).

More particularly, the monomers are chosen from: - linear, branched, cyclic or aromatic mono-or poly-carboxylic 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; it being possible for the monomers or macromonomers to be in the form of salts.

- l'acide acrylique, l'acide méthacrylique, l'acide fumarique, l'acide itaconique, l'acide citraconique, l'acide maléique, l'acide acrylamido glycolique, l'acide 2-propène 1sulfonique, l'acide méthallyl sulfonique, l'acide styrène sulfonique, l'acide a- acrylamido méthylpropane sulfonique, le 2-sulfoéthylène méthacylate, l'acide sulfopropyl acrylique, l'acide bis-sulfopropyl acrylique, l'acide bis-sulfopropyl méthacrylique, l'acide sulfatoéthyl méthacrylique, le monoester phosphate d'acide hydroxyéthyl méthacrylique, ainsi que les sels de métal alcalin, comme le sodium, le potassium, ou d'ammonium ; t'acide vinyt sutfonique, t'acide vinytbenzène sutfonique, t'acide vinyt phosphonique, l'acide vinylidène phosphorique, l'acide vinyl benzoïque, ainsi que les sels de métal

alcalin, comme le sodium, le potassium, ou d'ammonium ; te N-méthacrytoyt a ! anine, te N-acrytoyt-hydroxy-gtycine ; seuls ou en mélanges, ainsi que les macromonomères dérivant de tels monomères. By way of examples of anionic monomers, mention may be made without intention of being limited to:

- acrylic acid, methacrylic acid, fumaric acid, itaconic acid, citraconic acid, maleic acid, acrylamido glycolic acid, 2-propene 1sulfonic acid, methallyl sulfonic acid , styrene sulfonic acid, α-acrylamido methylpropane sulfonic acid, 2-sulfoethylene methacylate, sulfopropyl acrylic acid, bis-sulfopropyl acrylic acid, bis-sulfopropyl methacrylic acid, sulfatoethyl methacrylic acid, hydroxyethyl methacrylic acid monoester phosphate, as well as alkali metal salts, such as sodium, potassium, or ammonium; vinyt sutfonic acid, vinytbenzene sutfonic acid, vinyt phosphonic acid, vinylidene phosphoric acid, vinyl benzoic acid, as well as metal salts

alkaline, such as sodium, potassium, or ammonium; te N-methacrytoyt a! anine, te N-acrytoyt-hydroxy-gtycine; alone or in mixtures, as well as the macromonomers derived from such monomers.

It would not be departing from the scope of the present invention to use precursor monomers of those which have just been mentioned. In other words, these monomers have units which, once incorporated into the polymer chain, can be transformed, in particular by a chemical treatment such as hydrolysis, to restore the aforementioned anionic species. For example, the monomers

<Desc / Clms Page number 18>

totally or partially esterified of the abovementioned monomers can be used to be, subsequently, totally or partially hydrolyzed.

As cationic hydrophilic monomers from which the block amphiphilic polymers can be obtained, there may be mentioned in particular: - aminoalkyl (meth) acrylates, aminoalkyl (meth) acrylamides; - monomers comprising at least one secondary, tertiary or quaternary amine function, or a heterocyclic group containing a nitrogen atom, vinylamine, ethylene imine; - ammonium salts of diallyldialkyl; alone or as mixtures, or the corresponding salts, as well as the macromonomers derived from such monomers.

Said monomers can have a counterion chosen from halides such as, for example, chlorine, sulphates, hydrosulphates, alkylsulphates (for example comprising 1 to 6 carbon atoms), phosphates, citrates, formates, acetates.

Examples of suitable cationic monomers include the following monomers, among others: - dimethyl amino ethyl (meth) acrylate, dimethyl amino propyl (meth) acrylate, ditertiobutyl aminoethyl (meth) acrylate, dimethyl amino methyl (meth) acrylamide, dimethyl amino propyl (meth) acrylamide; - ethylene imine, vinylamine, 2-vinylpyridine, 4-vinylpyridin; - trimethylammonium ethyl (meth) acrylate chloride, trimethylammonium ethyl acrylate methyl sulfate, benzyl dimethylammonium ethyl (meth) acrylate chloride, 4-benzoylbenzyl dimethyl ammonium ethyl acrylate, trimethyl ammonium ethyl (meth) chloride acrylamido, vinylbenzyl trimethyl ammonium chloride; - diallyldimethyl ammonium chloride; alone or as mixtures, or their corresponding salts, as well as the macromonomers derived from such monomers.

Preferably, the amphiphilic block polymers have a molar mass by weight of less than or equal to 100,000 g / mol, more particularly between 1,000 and 50,000 g / mol, preferably between 1,000 and 20,000 g / mol. It is specified that the molar masses by weight indicated above are theoretical molar masses, evaluated as a function of the respective amounts of the monomers introduced during the preparation of said polymers.

Preferably, an amphiphilic block polymer of nonionic type is used.

<Desc / Clms Page number 19>

As an example of an amphiphilic block polymer suitable for the implementation of the invention, mention may be made of triblock polymers polyhyd roxystéa rate-polyethylene glycol-polyhydroxystearate (the products of the Arlacel range from ICI are an example), polymers containing polydimethylsiloxane blocks grafted to polyether polyalkyl (such as the products of the Tegopren brand sold by Goldschmidt).

According to a second variant of the invention, when phase A is an aqueous phase and B an oil phase, said phase A (which represents the dispersed internal phase) comprises, associated with one or more nonionic surfactants and / or amphiphilic polymers with blocks which have just been described, at least one cationic surfactant; the total content of cationic surfactant (s) and of nonionic surfactant (s) and / or of block amphiphilic polymer (s) is between 0.1 and 10% by weight, preferably between 2 and 10% by weight relative to phase A.

In the case of this variant, it is indicated that the cationic surfactant does not satisfy the Bancroft rule stated previously. Indeed, the cationic surfactant is soluble in the dispersed phase and not in the continuous phase of the reverse emulsion.

Among the cationic surfactants, use may in particular be made of aliphatic or aromatic fatty amines, aliphatic fatty amides, quaternary ammonium derivatives (Rhodoquat RP50 from Rhodia Chimie).

According to another variant of the invention, when phase A is an aqueous phase and B an oil phase, said phase A (dispersed internal phase) comprises, instead of the nonionic surfactant (s) and / or of the amphiphilic polymer (s) with blocks detailed above, at least one cationic surfactant. In this case, the total content of cationic surfactant (s) is between 0.1 and 10% by weight, preferably between 2 and 10% by weight relative to phase A.

According to a particularly advantageous embodiment, one or more nonionic surfactants and / or one or more amphiphilic block polymers are used.

Preferably, an amphiphilic polymer containing nonionic blocks or a mixture of several of them is used.

In the case where phase A or B is an oil phase and phase B or C an aqueous phase, respectively, said phase B or C (continuous phase) comprises: at least one nonionic surfactant and / or at least one amphiphilic polymer nonionic optionally combined with at least one anionic surfactant and / or at least one anionic amphiphilic polymer; the total content of nonionic and anionic amphiphilic surfactant (s) and / or polymer (s) is between 0.5 and
10% by weight, preferably between 1 and 5% by weight, relative to phase A or to phase B; the amount of anionic amphiphilic surfactant (s) and / or polymer (s) represents 0.5 to 10% by weight, preferably 0.5 to 2% by weight, relative to the weight of surfactant ( s) and / or nonionic amphiphilic polymer (s); or

<Desc / Clms Page number 20>

at least one anionic amphiphilic polymer optionally combined with at least one anionic surfactant; the total content of amphiphilic polymer (s) and / or anionic surfactant (s) is between 0.5 and 10% by weight, preferably between 1 and 5% by weight, relative to the phase A or phase B.

As regards the nonionic surfactants, use is preferably made of polyalkoxylated nonionic surfactants.

le nombre de motifs alcoxylés, plus particulièrement éthoxylés et/ou propoxylés, est tel que la valeur de HLB soit supérieure ou égale à 10. Advantageously, said nonionic surfactant is chosen from the following surfactants, alone or as a mixture: - alkoxylated fatty alcohols - alkoxylated mono, di or triglycerides - alkoxylated fatty acids - alkoxylated sorbitan esters - alkoxylated fatty amines - alkoxylated di (phenyl-1ethyl) phenols - alkoxylated tri (1-phenylethyl) phenols - alkoxylated alkyl phenols

the number of alkoxylated units, more particularly ethoxylated and / or propoxylated, is such that the value of HLB is greater than or equal to 10.

As regards the nonionic amphiphilic polymer, the latter can be chosen from polyalkoxylated polymers such as, for example, polyethylene glycol / polypropylene glycol / polyethylene glycol triblock polymers. Such polymers are well known and are marketed in particular under the brand Pluronic (marketed by the company BASF), or under the brand Arlatone (marketed by ICI).

According to another embodiment, the nonionic amphiphilic polymer is an amphiphilic block polymer, preferably diblock or triblock, obtained by polymerization of at least one nonionic hydrophilic monomer and at least one hydrophobic monomer, the proportion and the quantity. the nature of said monomers being such that the resulting polymer satisfies the conditions stated above (Bancroft rule).

The lists of nonionic hydrophilic monomers, as well as of nonionic hydrophobic monomers, cited in the context of the description of amphiphilic block polymers entering into the composition of emulsions in which the continuous phase is an oil phase, can be used in the case of polymers according to this variant.

However, the preferred hydrophilic monomers are acrylamide and methacrylamide, alone or as a mixture, or in the form of macromonomers; the preferred hydrophobic monomers are the esters of acrylic or methacrylic acid with linear or branched C1-C4 alcohols such as acrylate or methacrylate of

<Desc / Clms Page number 21>

methyl, ethyl, propyl and butyl, vinyl esters such as vinyl acetate, styrene, &alpha; -methylstyrene.

(monoéthanolamine, diéthanolamine, triéthanolamine...). On peut citer tout particulièrement les méthyl ester sulfonates dont le radical R est en C14-C16 ; les alkylbenzènesulfonates, plus particulièrement en &num;9-020, tes a ! ky ! su) fonates primaires ou secondaires, notamment en C8-C22, les alkylglycérol sulfonates, les acides polycarboxyliques sulfonés, comme par exemple ceux décrits dans
GB 1082179, les sulfonates de paraffine ; tes alkylsulfates, par exemple de formule ROS03M, où R représente un radical alkyle ou hydroxyalkyle en C1O-CZ4, de préférence en C1z-CZO ; M représentant un atome d'hydrogène ou un cation de même définition que ci-dessus, ainsi que leurs dérivés polyalcoxylés (éthoxylés, propoxylés, ou leurs combinaisons), comme par exemple le dodécylsulfate de sodium ; - tes atkytéthersutfates, par exemple de formule RO (CH2CH20) nSO3M où R représente un radical alkyle ou hydroxyalkyle en C10-CZ4, de préférence en C12-C20 ;
M représentant un atome d'hydrogène ou un cation de même définition que ci- dessus, n variant généralement de 1 à 4, ainsi que leurs dérivés polyalcoxylés (éthoxylés, propoxylés, ou leurs combinaisons), comme par exemple le laurylethersulfate avec n = 2. Among the suitable anionic surfactants, there may be mentioned inter alia, alone or as mixtures: - alkyl ester sulphonates, for example of formula R-CH (SO3M) -COOR ', where R represents an alkyl radical in Cs-CZo, preferably in Cio-Cie, R ′ a C 1 -C 6 alkyl radical, preferably C 1 -C 3 and M an alkali cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derivative of an alkanolamine

(monoethanolamine, diethanolamine, triethanolamine ...). Mention may very particularly be made of methyl ester sulfonates in which the R radical is C14-C16; alkylbenzenesulfonates, more particularly in &num; 9-020, your a! ky! su) primary or secondary fonates, in particular C8-C22, alkylglycerol sulfonates, sulfonated polycarboxylic acids, such as for example those described in
GB 1082179, paraffin sulfonates; your alkyl sulphates, for example of formula ROS03M, where R represents an alkyl or hydroxyalkyl radical in C1O-CZ4, preferably in C1z-CZO; M representing a hydrogen atom or a cation of the same definition as above, as well as their polyalkoxylated derivatives (ethoxylated, propoxylated, or their combinations), such as for example sodium dodecylsulfate; - your atkytethersutfates, for example of formula RO (CH2CH20) nSO3M where R represents an alkyl or hydroxyalkyl radical in C10-CZ4, preferably in C12-C20;
M representing a hydrogen atom or a cation of the same definition as above, n generally varying from 1 to 4, as well as their polyalkoxylated derivatives (ethoxylated, propoxylated, or their combinations), such as for example laurylethersulfate with n = 2 .

sulfosuccinates, les N-acyl sarcosinates, les polyéthoxycarboxylates ; et - les phosphates esters d'alkyle et/ou d'alkyléther et/ou d'alkylaryléther. - alkyl amide sulfates, for example of formula RCONHR'OS03M where R represents a C2-C22, preferably C6-CZO, alkyl radical, R'a C2-C3 alkyl radical, M representing a hydrogen atom or a cation of the same definition as above, as well as their polyalkoxylated derivatives (ethoxylated, propoxylated, or their combinations); - salts of saturated or unsaturated fatty acids, for example such as C8-C24, preferably C14-C20, N-acyl N-alkyltaurates, alkylisethionates, alkylsuccinamates and alkylsulfosuccinates, monoesters or diesters of

sulfosuccinates, N-acyl sarcosinates, polyethoxycarboxylates; and - alkyl and / or alkyl ether and / or alkylaryl ether ester phosphates.

Among the anionic polymers which may be used, there may be mentioned most particularly the block polymers, preferably diblock or triblock, obtained by

<Desc / Clms Page number 22>

polymerization of at least one anionic hydrophilic monomer, optionally of at least one nonionic hydrophilic monomer, and of at least one hydrophobic monomer.

Here again, the choice of monomers and their respective proportions are such that the resulting polymer satisfies the two conditions stated above (Bancroft rule).

The nonionic and anionic hydrophilic monomers, as well as the hydrophobic monomers mentioned in the context of the description of the amphiphilic polymers entering into the composition of emulsions for which the continuous phase is an oil phase, can be used to obtain the polymers according to this variant. We can therefore refer to it.

The emulsions can also include conventional additives.

For example, in the case where the emulsion is of the water / oil / water type, the internal aqueous phase can comprise at least one additive chosen from salts. According to this first possibility, the salt is chosen from alkali or alkaline earth metal halides (such as sodium chloride, calcium chloride), or alkali or alkaline earth metal sulphates (such as sodium sulphate), or their mixtures.

According to another possibility, the internal aqueous phase can comprise as additive, at least one sugar, such as glucose for example, or also at least one polysaccharide, such as in particular dextran, or their mixtures. These two possibilities can be combined.

The salt concentration in the internal aqueous phase, when the latter is present, is more particularly between 0.05 and 1 moli, preferably 0.1 to 0.4 mol.

The concentration of sugar and / or polysaccharide is such that the osmotic pressure of the internal aqueous phase comprising the sugar and / or polysaccharide corresponds to the osmotic pressure of an internal aqueous phase comprising 0.05 to
1 molli of salt.

Still in the case where the emulsion is of the water / oil / water type, it may likewise be advantageous to incorporate into the external aqueous phase, at least one additive (salt and / or a sugar and / or a polysaccharide) such as as defined above, in order to balance the osmotic pressures of the two aqueous phases.

Therefore, and if necessary, the external aqueous phase can comprise at least one salt with a concentration in the external aqueous phase of between 0.05 and 1 moli, preferably 0.1 to 0.4 moli. It may optionally comprise at least one polysaccharide sugar 1, or their mixtures with a concentration such that the osmotic pressure of the external aqueous phase comprising the sugar and / or polysaccharide corresponds to the osmotic pressure of an internal aqueous phase comprising 0.05 to 1 molli of salt.

<Desc / Clms Page number 23>

It should be noted that the aqueous phase, preferably the external aqueous phase, can also comprise at least one thickening agent.

The thickening agent is chosen more particularly from polysaccharides such as xanthan gum and guar, alone or as mixtures.

Furthermore, the thickening agent content, if it is present, is usually between 0.1 and 2% by weight of the multiple emulsion.

Finally, the phase A / phase B weight ratio is advantageously between 10/90 and 90/10. Preferably, the phase A / phase B weight ratio is between 30/70 and 80/20.

In addition, preferably, the weight ratio of the whole phase A and phase B 1 phase C is between 30/70 and 90/10, preferably between 50/50 and 90/10.

A second category of multiple emulsions according to the invention consists of multiple emulsions of the silicone / oil / water type or of the oil / silicone / water type.

It is recalled that the internal oil phase, which is not a silicone, of each of the aforementioned two systems comprises the gelling polymer.

In this category, one of the internal phases is a silicone phase.

Preferably, the silicone is chosen from those which are in liquid form at room temperature (20-30 C).

Are likely to be suitable for the implementation of the invention, alone or in mixtures, silicones constituted in whole or in part of units of formula: R'3-aRaSiOi / 2 (unit M) and / or RzSiO (unit D) formulas where: - a is an integer from 0 to 3; - the R radicals are identical or different and represent: - a saturated or unsaturated aliphatic hydrocarbon group containing from 1 to 10 carbon atoms; - an aromatic hydrocarbon group containing from 6 to 13 carbon atoms; a polar organic group bonded to silicon via an Si-C or Si-O-C bond; - the radicals R 'are identical or different and represent: - a saturated or unsaturated aliphatic hydrocarbon group containing from 1 to 10 carbon atoms; - an aromatic hydrocarbon group containing from 6 to 13 carbon atoms; - an -OH function; - an amino- or amido-functional group containing from 1 to 6 carbon atoms, bonded to silicon by an Si-N bond.

Preferably at least 80% of the radicals R represent a methyl group.

These silicones can optionally comprise, preferably less than 5 mol%, units of formulas T and / or Q:

<Desc / Clms Page number 24>

RSi03 / 2 (unit T) and / or SiO2 (unit Q) formula in which R has the definition given above.

As examples of aliphatic or aromatic hydrocarbon radicals R, there may be mentioned the groups: - alkyl, preferably C1-C10 alkyl optionally halogenated, such as methyl, ethyl, octyl, trifluoropropyl; - alkoxyalkylene, more particularly C2-C10, preferably Cz-Ce, such as -CH2-CH2-O-CH3; - Alkenyls, preferably Cs-Cio alkenyl, such as vinyl, allyl, hexenyl, decenyl, decadienyl; - alkenyloxyalkylene such as - (CH2) 3-O-CH2-CH = CH2, or alkenyloxyalkoxy alkyl such as - (CH2) 3-OCH2-CH2-O-CH = CH2 in which the alkyl parts are preferably from Cl-Clo and the alkenyl moieties are preferably C2-Clo-aryls, preferably C6-C13, such as phenyl.

As examples of polar organic groups R, there may be mentioned: - hydroxyfunctional groups such as alkyl groups substituted with one or more hydroxy or di (hydroxyalkyl) amino groups and optionally interrupted by one or more divalent hydroxyalkylamino groups. By alkyl is meant a hydrocarbon chain preferably of C1-C10, better still of C1-C6; examples of these groups are - (CH2h-OH; - (CH2) 4N (CH2CH20H) 2 ;-( cl2) 3-
N (CH2CH2OH) -CH2-CH2-N (CH2CH2OH) 2: - aminofunctional such as alkyl substituted with one or more amino or aminoalkylamino groups where alkyl is as defined above; examples are- (CH2) 3-NH2; (CH2) 3-NH- (CH2) 2NH2; -amidofunctionals such as alkyl substituted with one or more acylamino groups and optionally interrupted by one or more divalent alkyl-CO-N <groups where alkyl is as defined above and acyl represents alkylcarbonyl; an example is the group - (CH2) 3-N (COCH3) - (CH2) 2NH (COCH3); - carboxyfunctionals such as carboxyalkyl optionally interrupted by one or more oxygen or sulfur atoms where alkyl is as defined above; an example is the group -CH2-CH2-S-CH2-COOH.

As examples of R ′ radicals, mention may be made of the groups: - alkyl, preferably optionally halogenated C1-C10 alkyl, such as methyl, ethyl, octyl, trifluoropropyl; - Aryls, preferably C6-Cis, tets than phenyl; - aminofunctionals such as alkyl or aryl substituted by amino, alkyl preferably being C 1 -C 6 and aryl denoting a cyclic aromatic group

<Desc / Clms Page number 25>

preferably C-C13 hydrocarbon such as phenyl; examples are ethylamino, phenylamino; - amidofunctionals such as alkylcarbonylamino where alkyl is preferably
Here-This; examples are methylacetamido.

As concrete examples of "D units", mention may be made of: (CH3hSiO; CH3 (CH = CH2) SiO; CH3 (CeH5) SiO; (C6Hs) 2SiO; CH3 (CH2-CH2-CH20H) SiO.

As concrete examples of “M units”, mention may be made of: (CH3) 3SiOi / 2; (CH3) 2 (OH) SiOl / 2; (CH3) (CH = CH2) Si01 / 2; (OCH3) 3SiO1 / 2: [OC (CH3) = CH2] 3SiO1 / 2: [ON = C (CH3)] 3SiO / 2; (NH-CH3) 3SiO1 / 2; (NH-CO-CH3hSi01 / 2 '
As concrete examples of “T units”, mention may be made of: CH3Si03 / 2; (CH = CH2) SiO3 / 2.

When the silicones contain reactive and / or polar R radicals (such as OH, vinyl, allyl, hexenyl, aminoalkyls, etc.), the latter generally do not represent more than 5% of the weight of the silicone, and preferably not more than 1% of the weight of the silicone.

siloxane ;l'heptaméthyl-3 [ (triméthyl-silyl) oxy] trisiloxane, l'hexaméthyl-3, 3 bis[ (triméthylsilyl) oxy] trisiloxane ;l'hexaméthylcyclotrisiloxane, l'octaméthylcyclotétrasiloxane, le décaméthylcyclopentasiloxane, le dodécaméthylcyclohexasiloxane, le pentaméthyl[ (tri- méthylsilyl) oxy] cyclotrisiloxane. Can be suitably used volatile oils such as hexamethyldisiloxane, octamethyldisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadecamethylhexa

siloxane; heptamethyl-3 [(trimethyl-silyl) oxy] trisiloxane, hexamethyl-3, 3 bis [(trimethylsilyl) oxy] trisiloxane; hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclotetrasiloxane, decamethylcyclopentasiloxamethylcyloxane, dododecyclo-cyclo-cyclo-cyclo-cyclo-cyclo-cycloxane (tri-methylsilyl) oxy] cyclotrisiloxane.

It is also possible to use non-volatile silicones such as polydimethylsiloxane and α, to-bis (hydroxy) polydimethylsiloxane oils and gums, as well as polydimethylsiloxane, polyphenylmethylsiloxane and α, # -bis (hydroxy) poly dimethylsiloxane gums can likewise be used. .

A, co-bis (trimethyl) polydimethyl siloxane oils, and a, m-bis (hydroxy) polydimethyl siloxane oils are more particularly preferred.

By way of representative of silicones which are most particularly suitable for the present invention, mention may in particular be made of silicones of the polydimethylsiloxane (dimethicone) and diphenyldimethicone type.

As regards the other internal phase of the multiple emulsion according to this second category, this is an oil, which is not a silicone, chosen more particularly from the following compounds: organic oils of animal origin or vegetable; - products resulting from the alcoholysis of the aforementioned oils; - essential oils ; - mono-, di- and tri-glycerides;

<Desc / Clms Page number 26>

- esters of fatty acids, saturated or not, comprising 10 to 40 carbon atoms and alcohols comprising 1 to 6 carbon atoms; - alcohols, saturated or not, comprising 4 to 40 carbon atoms, and optionally comprising several hydroxyl groups; these compounds being used alone or as a mixture.

Reference may be made to the list of oils comprising the gelling polymer, given in the context of the first category of multiple emulsions according to the invention.

One and / or the other of the internal phases of the multiple emulsion (silicone, oil), can comprise at least one active material which can be present in a liquid form, in a form soluble in the oil phase concerned or solubilized. in a solvent miscible with this oil phase or else in the form of a solid suspended in the oil phase concerned. Furthermore, the amount of hydrophobic active material, if it is present and if it is different from the oil or silicone phase, is more particularly within the ranges indicated above.

Finally, it is recalled that in the case where the oil or silicone phase is considered as an active material as such, then it is chosen from the compounds which are in liquid form at room temperature.

Here again, reference can be made to the list of hydrophobic active materials listed above.

The external aqueous phase of the multiple emulsion of this second category can optionally comprise a hydrophilic active material. What has been indicated previously with regard to the nature of the active material when describing the aqueous phases of the emulsions of the first category remains valid in this case.

Multiple emulsions further comprise surfactants and / or polymers chosen according to the nature of the interface to be stabilized, in other words according to the nature of the continuous phase and of the dispersed phase.

Note that Bancroft's rule can be applied to the polymer used.

Thus, the fraction soluble in the continuous phase is greater than the fraction soluble in the dispersed phase.

Thus, the inverse emulsion comprises at least one surfactant / polymer, preferably chosen from those which satisfy both the two conditions below: - when they are mixed with phase B, at a concentration of between 0.1 and
10% by weight of phase B and at a temperature between 200C and the preparation temperature of emulsion A / B, are in the form of a solution in phase B, in all or part of the range of indicated concentration; - when mixed with phase A, at a concentration between 0.1 and
10% by weight of phase A and at a temperature between 200C and

<Desc / Clms Page number 27>

temperature of preparation of emulsion A / B, are in the form of a dispersion in phase A, in all or part of the concentration range indicated.

Moreover, the multiple emulsion comprises at least one surfactant / polymer, chosen more particularly from those which satisfy both the two conditions below: when they are mixed with phase C, at a concentration of between 0.1 and
10% by weight of phase C and at a temperature between 20 C and the preparation temperature of the A / B / C emulsion, are in the form of a solution in phase C, in all or part of the indicated concentration range; - when they are mixed with phase B, at a concentration between 0.1 and
10% by weight of phase B and at a temperature between 20 C and the temperature for preparing the A / B / C emulsion, are in the form of a dispersion in phase B, in all or part of the indicated concentration range.

In the case where the continuous phase is an oil and the dispersed phase a silicone, the oil phase comprises at least one comb or block polymer.

It is specified, purely as an indication, that the polymer has a number molar mass of less than or equal to 100,000 g / mol, more particularly between 1,000 and 50,000 g / mol.

The molar mass in number is given here with an absolute value, and can be advantageously determined by size exclusion chromatography coupled to the MALLS method (light scattering - multi-angle laser light scattering). Note that this method is particularly suitable for polymers of any mass.

For polymers of low masses, in particular less than or equal to approximately 20,000 g / mol, it is also possible to use NMR, which also gives an absolute value for the masses of copolymer.

la phase silicone (pour le polymère dérivant des blocs solubles dans la phase silicone). Advantageously, if each of the blocks of the polymer represented a polymer (same size and composition as the blocks), then the monomers constituting each of the blocks would be chosen such that each polymer is soluble, under the conditions of temperature and concentrations mentioned. above, either in the oil phase (for the polymer derived from soluble blocks in the oil phase) or in

the silicone phase (for the polymer derived from blocks soluble in the silicone phase).

More particularly, the fraction of the polymer which is soluble in the silicone phase derives from a polysiloxane which can be chosen from the silicones listed above.

<Desc / Clms Page number 28>

Preferably, the polysiloxane carries reactive functions, such as -OH and -NH2 functions, among others.

As regards the fraction soluble in the oil phase, this is preferably derived from the polymerization of at least one monomer chosen from the following monomers: - esters of mono-or poly-carboxylic acids, linear, branched , cyclic or aromatic, comprising at least one ethylenic unsaturation; - ap-ethylenically unsaturated nitriles, vinyl ethers, vinyl esters, vinyl aromatic monomers, vinyl or vinylidene halides; - hydrocarbon-based monomers, linear or branched, aromatic or not, comprising at least one ethylenic unsaturation; alone or in mixtures, as well as the macromonomers derived from such monomers.

totalement désacétylé), le Versatate&commat; de vinyle, le propionate de vinyle, le chlorure de vinyle, le chlorure de vinylidène, le méthyl vinyléther, l'methyl vinyléther, le (méth) acrylonitrile, la N-vinylpyrrolidone, le vinylformamide, le vinylacétamide, la vinylamine ; - les N-alkyl (méth) acrylamide comme l'isopropyl acrylamide ; - le styrène, l'a-méthylstyrène, le vinyltoluène, le butadiène, le chloroprène, l'isoprène ; seuls ou en mélanges, ainsi que les macromonomères dérivant de tels monomères. More precisely, said monomers can be chosen from: - 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, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethyl acrylate, hexyl d (meth) acrylate 'hydroxyethyl; - vinyl acetate (making it possible to obtain polyvinyl alcohol partially or

completely deacetylated), Versatate &commat; vinyl, vinyl propionate, vinyl chloride, vinylidene chloride, methyl vinylether, methyl vinylether, (meth) acrylonitrile, N-vinylpyrrolidone, vinylformamide, vinylacetamide, vinylamine; - N-alkyl (meth) acrylamides such as isopropyl acrylamide; - styrene, α-methylstyrene, vinyltoluene, butadiene, chloroprene, isoprene; alone or in mixtures, as well as the macromonomers derived from such monomers.

It should be noted that the fraction of the polymer soluble in the oil phase can be obtained from the abovementioned monomers, combined with monomers of a different chemical nature, such as, for example, hydrophilic, nonionic or ionic monomers.

As examples of ionic hydrophilic monomers, more particularly anionic or potentially anionic depending on the pH conditions, there may be mentioned in particular: - linear, branched, cyclic or aromatic mono-or poly-carboxylic acids, N-substituted derivatives of such acids, polycarboxylic acid monoesters, comprising at least one ethylenic unsaturation;

<Desc / Clms Page number 29>

- linear, branched, cyclic or aromatic vinyl carboxylic acids; - amino acids comprising one or more ethylenic unsaturations; alone or as mixtures, their sulfonic or phosphonic derivatives, the macromonomers derived from such monomers, as well as the corresponding salts.

As examples of monomers of this type, the following may be suitable, in acid form or in the form of an alkali metal salt (sodium, potassium), or of ammonium: - (meth) acrylic acid, acid 2 -propene 1-sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, a-acrylamido methylpropane sulfonic acid, 2-sulfoethylene methacylate, sulfopropyl (meth) acrylic acid, bis-sulfopropyl (meth) acid ) acrylic, hydroxyethyl methacrylic acid monoester phosphate; - vinyl sulfonic acid, vinylbenzene sulfonic acid, vinyl phosphonic acid, vinyl benzoic acid; - N-methacryloyl alanine, N-acryloyl-hydroxy-glycine; alone or in mixtures, as well as the macromonomers derived from such monomers.

Among the nonionic hydrophilic monomers, there are among others the amides of mono-or poly-carboxylic acids, linear, branched, cyclic or aromatic, comprising at least one ethylenic unsaturation, or derivatives, such as (meth) acrylamide, N-methylol (meth) acrylamide; certain 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 or vinyl propionate.

If the copolymer is obtained in part from hydrophilic monomers, it is specified that their content is such that the polymer meets the criteria stated above (Bancroft rule).

According to a preferred embodiment of the present invention, the polymer entering into the composition of the emulsion is a linear block polymer. Preferably, said polymer comprises at least three blocks.

The polymers which can be used in the context of the present invention can be obtained, advantageously, by the radical route, preferably controlled.

dans lesquels :

- x est égal à 0, 1, 2 ou 3, y est égal à 0, 1, 2 ou 3 avec 2 < (x+y) < 3 et y est différent de 0 pour au moins un des motifs du copolymère hybride, 'tes symboles R, identiques ou différents, représentent : Preferably, such polymers can be obtained by implementing a process for the preparation by thermal activation of silicone and organic hybrid polymers comprising units (1):

wherein :

- x is equal to 0, 1, 2 or 3, y is equal to 0, 1, 2 or 3 with 2 <(x + y) <3 and y is different from 0 for at least one of the units of the hybrid copolymer, 'your R symbols, identical or different, represent:

<Desc / Clms Page number 30>

dans lequel : - x'= 1,2, 3 ou 4 en fonction de la valence de Z, - Z, identiques ou différents, représentent un atome de carbone, soufre, oxygène, phosphore, azote et/ou une valence libre, - rut, identiques ou différents, représentent : - un groupe (i) alkyle, acyle, aryle, alcène ou alcyne éventuellement substitué, - un cycle (ii) carboné, saturé ou non, éventuellement substitué et/ou aromatique, et/ou - un hétérocycle (iii), saturé ou non, éventuellement substitué, - ces radicaux (i), (ii) et (iii) pouvant être substitués avantageusement par : des groupes phényles substitués, des groupes aromatiques substitués, ou des groupes : alkoxycarbonyle, aryloxycarbonyle (-COOR5), carboxy (-COOH), acyloxy (-02CR5), carbamoy ! e (-CONRS), cyano (-CN), alkylcarbonyle,

alkylarylcarbonyle, arylcarbonyle, arylalkylcarbonyle, phtalimido, maleïmido, succinimido, amidino, guanidimo, hydroxy (-OH), amino (-NR52)'halogène, allyle, époxy, alkoxy (-OR5), S-alkyle, S-aryle, des groupes présentant un caractère hydrophile ou ionique tels que les sels alcalins d'acides carboxyliques, les sels alcalins d'acide suifonique, les chaînes polyoxyde d'alkylène (POE, POP), les substituants cationiques (sels d'ammonium a linear or branched alkyl radical containing 1 to 8 carbon atoms, optionally substituted by at least one halogen, preferably fluorine, the alkyl radicals preferably being methyl, ethyl, propyl, octyl and 3,3, 3-trifluoropropyl, - a cycloalkyl radical containing between 5 and 8 cyclic carbon atoms, optionally substituted, - an aryl radical containing between 6 and 12 carbon atoms which may be substituted, preferably phenyl or dichlorophenyl, - an aralkyl part having an alkyl part containing between 5 and 14 carbon atoms and an aryl part containing between 6 and 12 carbon atoms, optionally substituted on the aryl part by halogens, alkyls and / or alkoxyls containing 1 to 3 carbon atoms, the U symbols, which are identical or different, represent (ll):

in which: - x '= 1,2, 3 or 4 depending on the valence of Z, - Z, identical or different, represent a carbon atom, sulfur, oxygen, phosphorus, nitrogen and / or a free valence, - rut, identical or different, represent: - an optionally substituted alkyl, acyl, aryl, alkene or alkyne group, - a saturated or unsaturated carbon ring (ii), optionally substituted and / or aromatic, and / or - a heterocycle (iii), saturated or unsaturated, optionally substituted, - these radicals (i), (ii) and (iii) possibly being substituted advantageously by: substituted phenyl groups, substituted aromatic groups, or groups: alkoxycarbonyl, aryloxycarbonyl ( -COOR5), carboxy (-COOH), acyloxy (-02CR5), carbamoy! e (-CONRS), cyano (-CN), alkylcarbonyl,

alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidimo, hydroxy (-OH), amino (-NR52) 'halogen, allyl, epoxy, alkoxy (-OR5), S-alkyl, S-aryl, groups having a hydrophilic or ionic character such as alkali metal salts of carboxylic acids, alkali metal salts of sulfonic acid, polyalkylene oxide chains (POE, POP), cationic substituents (ammonium salts

<Desc / Clms Page number 31>

- un groupement (iv) de formute-CnF (zni) avec n compris entre 1 et 20, - un groupement (v) de formule suivante :

dans laquelle : - R6, R7, identiques ou non, sont choisis parmi un groupe halogène,

- N02,-SO3R1o,-NCO,-CN,-OR10,-SR10,-N (R1O) 2,-COOR10, - 02CR''o,-CON (R10) ,-NCO (R''0) et-CnF (2n+i) avec n compris entre 1 et
20, de préférence égal à 1 ; - avec Rio représentant : * un atome d'hydrogène, * ou un radical alkyle, alcényle, alcynyle, cycloacényle, cycloalcynyle, alkaryle, aralkyle, hétéroaryle ou aryle éventuellement condensé à un hétérocycle aromatique ou non ; ces radicaux pouvant éventuellement être substitués par : . un ou plusieurs groupes identiques ou différents, choisis parmi les atomes d'halogènes, =0, =S, -OH, alcoxy, SH, thioalcoxy, NH2, mono ou di-alkylamino, CN, COOH, ester, amide, CnF (2n+1) et/ou éventuellement interrompu par un ou plusieurs atomes choisis parmi 0, S, N, P ; . ou un groupe hétérocyclique éventuellement substitué par un ou plusieurs groupes tels que définis précédemment ; . ou R6 et R7 forment ensemble avec l'atome de carbone auquel ils sont attachés, un groupe =0, =S, un cycle hydrocarboné ou un hétérocycle ; - et R8 et R9, identiques ou différents, représentent un groupe tel que défini ci-dessus pour R10 ; ou forment ensemble une chaîne hydrocarbonée en
C2-C4, éventuellement interrompue par un hétéroatome choisi parmi 0, S et N ; - V et V, identiques ou différents, représentent : H, un groupe alkyle ou un halogène, - X et X', identiques ou différents, représentent H, un halogène ou un groupe
R4, OR4, 02COR4, NHCOH, OH, NH2, NHR4, N (R4) 2, (R4) 2N+O-,
NHCOR4, C02H, C02R4, CN, CONH2, CONHR4 ou CONR, dans lesquels R4 est choisi parmi les groupes alkyle, aryle, aralkyle, alkaryle, quaternaries), R5, identical or different, representing an alkyl or aryl group, and / or a polymer chain,

- a group (iv) of formute-CnF (zni) with n between 1 and 20, - a group (v) of the following formula:

in which: - R6, R7, identical or not, are chosen from a halogen group,

- N02, -SO3R1o, -NCO, -CN, -OR10, -SR10, -N (R1O) 2, -COOR10, - 02CR''o, -CON (R10), -NCO (R''0) and- CnF (2n + i) with n between 1 and
20, preferably equal to 1; - With Rio representing: * a hydrogen atom, * or an alkyl, alkenyl, alkynyl, cycloacenyl, cycloalkynyl, alkaryl, aralkyl, heteroaryl or aryl radical optionally condensed to an aromatic or non-aromatic heterocycle; these radicals possibly being substituted by:. one or more identical or different groups, chosen from halogen atoms, = 0, = S, -OH, alkoxy, SH, thioalkoxy, NH2, mono or di-alkylamino, CN, COOH, ester, amide, CnF (2n +1) and / or optionally interrupted by one or more atoms chosen from 0, S, N, P; . or a heterocyclic group optionally substituted with one or more groups as defined above; . or R6 and R7 together with the carbon atom to which they are attached form a group = O, = S, a hydrocarbon ring or a heterocycle; - and R8 and R9, identical or different, represent a group as defined above for R10; or together form a hydrocarbon chain in
C2-C4, optionally interrupted by a heteroatom chosen from 0, S and N; - V and V, identical or different, represent: H, an alkyl group or a halogen, - X and X ', identical or different, represent H, a halogen or a group
R4, OR4, 02COR4, NHCOH, OH, NH2, NHR4, N (R4) 2, (R4) 2N + O-,
NHCOR4, C02H, C02R4, CN, CONH2, CONHR4 or CONR, in which R4 is chosen from alkyl, aryl, aralkyl, alkaryl,

<Desc / Clms Page number 32>

un atome d'hydrogène, des groupes : alkoxycarbonyle, aryloxycarbonyle 555 (-COOR), carboxy (-COOH), acyloxy (-O2CR), carbamoyle (-CONR 2), cyano (-CN), alkylcarbonyle, alkylarylcarbonyle, arylcarbonyle, arylalkylcarbonyle, phtalimido, maleïmido, succinimido, amidino, guanidimo, 5 5 hydroxy (-OH), amino (-NR52), halogène, allyle, époxy, alkoxy (-OR5), S-alkyle, S-aryle, des groupes présentant un caractère hydrophile ou ionique tels que les sels alcalins d'acides carboxyliques, les sels alcalins d'acide

sulfonique, les chaînes polyoxyde d'alkylène (POE, POP), les substituants 5 cationiques (sels d'ammonium quaternaires), R5, identiques ou différents, représentant un groupe alkyle ou aryle, et/ou une chaîne polymère, - les radicaux (i), (ii) et (iii) pouvant être substitués avantageusement par : des groupes phényles substitués, des groupes aromatiques substitués, ou des groupes : alkoxycarbonyle, aryloxycarbonyle (-COOR), carboxy (-COOH),

5 5 acyloxy (-02CR), carbamoyle (-CONR 2), cyano (-CN), alkylcarbonyl, alkylarylcarbonyle, arylcarbonyle, arylalkylcarbonyle, phtalimido, maleïmido, succinimido, amidino, guanidimo, hydroxy (-OH), amino (-NR52), halogène, allyle, époxy, alkoxy (-OR5), S-alkyle, S-aryle, des groupes présentant un caractère hydrophile ou ionique tels que les sels alcalins d'acides carboxyliques, les sels alcalins d'acide sulfonique, les chaînes polyoxyde

d'alkylène (POE, POP), les substituants cationiques (sels d'ammonium 5 quaternaires), R5, identiques ou différents, représentant un groupe alkyle ou aryle, et/ou une chaîne polymère, - W, identiques ou différents,alkene or organosilyl, optionally perfluorinated and optionally substituted with one or more carboxyl, epoxy, hydroxyl, alkoxy, amino, halogen or sulfonic groups,? 3 - R2 and R, identical or different, represent: a group (i) alkyl, acyl, aryl, alkene or alkyne optionally substituted, a carbon ring (ii), saturated or not, optionally substituted and / or aromatic, a heterocycle ( iii), saturated or not, optionally substituted,

a hydrogen atom, groups: alkoxycarbonyl, aryloxycarbonyl 555 (-COOR), carboxy (-COOH), acyloxy (-O2CR), carbamoyl (-CONR 2), cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl , phthalimido, maleimido, succinimido, amidino, guanidimo, 5 5 hydroxy (-OH), amino (-NR52), halogen, allyl, epoxy, alkoxy (-OR5), S-alkyl, S-aryl, groups having a character hydrophilic or ionic such as alkali salts of carboxylic acids, alkali salts of acid

sulfonic acid, polyalkylene oxide chains (POE, POP), cationic substituents (quaternary ammonium salts), R5, identical or different, representing an alkyl or aryl group, and / or a polymer chain, - radicals ( i), (ii) and (iii) possibly being substituted advantageously by: substituted phenyl groups, substituted aromatic groups, or groups: alkoxycarbonyl, aryloxycarbonyl (-COOR), carboxy (-COOH),

5 5 acyloxy (-02CR), carbamoyl (-CONR 2), cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidimo, hydroxy (-OH), amino (-NR52) , halogen, allyl, epoxy, alkoxy (-OR5), S-alkyl, S-aryl, groups having a hydrophilic or ionic character such as alkali metal salts of carboxylic acids, alkali metal salts of sulphonic acid, polyoxide chains

of alkylene (POE, POP), the cationic substituents (quaternary ammonium salts), R5, identical or different, representing an alkyl or aryl group, and / or a polymer chain, - W, identical or different,

* represent a divalent radical chosen from-0-, - NR -, - NH -, - S-, - Sp, identical or different, represent a ball consisting of a divalent organic radical of formula - (CH2) x "'- in which X "'is between 1 and
20, this radical possibly being substituted and / or containing at least one heteroatom, - a = 0 or 1, - m> 1, and when m> 1, the repeating unit units of index m are identical or different,

<Desc / Clms Page number 33>

- un composé silicone précurseur comprenant des motifs, identiques ou différents de formule (IV) :

RxU'ySiO [4- (x+y)]/2 dans lequel : - R, x et y correspondent aux valeurs données précédemment, et le radical monovalent U'est selon la formule suivante (V) :

- et un initiateur de polymérisation radicalaire. process in which the following are brought into contact: - at least one ethylenically unsaturated monomer of formula (III):

- a precursor silicone compound comprising units, identical or different, of formula (IV):

RxU'ySiO [4- (x + y)] / 2 in which: - R, x and y correspond to the values given previously, and the monovalent radical U is according to the following formula (V):

- and a radical polymerization initiator.

- les peroxydes d'hydrogène, tels que l'hydroperoxyde de butyle tertiaire, l'hydroperoxyde de cumène, le t-butyl-peroxyacétate, le t-butylperoxybenzoate, le tbutylperoxyoctoate, le t-butylperoxynéodécanoate, le t-butylperoxyisobutarate, le peroxyde de lauroyle, le t-amylperoxypivalte, le t-butylperoxypivalate, le peroxyde de dicumyl, le peroxyde de benzoyle, le persulfate de potassium, le persulfate d'ammonium, - les composés azoïques tels que : le 2-2'-azobis (isobutyronitrile), le 2,2'-azobis (2butanenitrile), le 4,4'-azobis (4-acide pentanoïque), le 1, 1'-azobis (cyclohexanecarbonitrile), le 2- (t-butylazo)-2-cyanopropane, le 2, 2'-azobis [2-méthyl-N- (1, 1)- bis (hydroxyméthyl) -2-hydroxyéthyl] propionamide, le 2,2'-azobis (2-méthyl-N- hydroxyéthyl]-propionamide, le dichlorure de 2,2'-azobis (N, N'-diméthylène isobutyramidine), le dichlorure de 2,2'-azobis (2-amidinopropane), le 2,2'-azobis (N, N'- diméthylèneisobutyramide), le 2,2'-azobis (2-méthyl-N-[1, 1-bis (hydroxyméthyl) -2- hydroxyéthyl] propionamide), le 2,2'-azobis (2-méthyl-N-[1, 1-bis (hydroxyméthyl) éthyl] propionamide), le 2, 2'-azobis[2-méthyl-N- (2-hydroxyéthyl) propionamide], le 2,2'azobis (isobutyramide) dihydrate, - les systèmes redox comportant des combinaisons telles que : les mélanges de peroxyde d'hydrogène, d'alkyle, peresters, percarbonates et similaires et de n'importe lequel des sels de fer, de sels titaneux, formaldéhyde sulfoxylate de zinc ou formaldéhyde sulfoxylate de sodium, et des sucres réducteurs ; les persulfates, The radical polymerization initiator can be chosen from the initiators conventionally used in radical polymerization. It may be, for example, one of the following initiators:

- hydrogen peroxides, such as tertiary butyl hydroperoxide, cumene hydroperoxide, t-butyl-peroxyacetate, t-butylperoxybenzoate, tbutylperoxyoctoate, t-butylperoxyneodecanoate, t-butylperoxyisobutarate, lauroyl, t-amylperoxypivalte, t-butylperoxypivalate, dicumyl peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate, - azo compounds such as: 2-2'-azobis (isobutyronitrile) , 2,2'-azobis (2butanenitrile), 4,4'-azobis (4-pentanoic acid), 1, 1'-azobis (cyclohexanecarbonitrile), 2- (t-butylazo) -2-cyanopropane, 2,2'-azobis [2-methyl-N- (1, 1) - bis (hydroxymethyl) -2-hydroxyethyl] propionamide, 2,2'-azobis (2-methyl-N-hydroxyethyl] -propionamide, 2,2'-azobis (N, N'-dimethylene isobutyramidine) dichloride, 2,2'-azobis (2-amidinopropane) dichloride, 2,2'-azobis (N, N'-dimethyleneisobutyramide), 2,2'-azobis (2-methyl-N- [1, 1-bis (hydroxymethyl) -2- hydroxyethyl] propionamide), 2,2'-azobis (2-methyl-N- [1, 1-bis (hydroxymethyl) ethyl] propionamide), 2, 2'-azobis [2-methyl-N- (2- hydroxyethyl) propionamide], 2,2'azobis (isobutyramide) dihydrate, - redox systems comprising combinations such as: mixtures of hydrogen peroxide, alkyl, peresters, percarbonates and the like and any of the iron salts, titanium salts, zinc formaldehyde sulfoxylate or sodium formaldehyde sulfoxylate, and reducing sugars; persulphates,

<Desc / Clms Page number 34>

alkali metal or ammonium perborate or perchlorate in combination with an alkali metal bisulphite, such as sodium metabisulphite, and reducing sugars; alkali metal persulfates in combination with an arylphosphinic acid, such as benzene phosphonic acid and the like, and reducing sugars.

The amount of initiator to be used is determined so that the amount of radicals generated is at most 20% by mole relative to the amount of silicone precursor compound (IV), preferably at most 5% by mole. mole.

As ethylenically unsaturated monomer, those which have been mentioned above are used to define the fraction of the polymer soluble in the internal organic phase.

It should also be noted that butadiene and chloroprene correspond to the case where a = 1 in formulas (1) and (III).

For the preparation of the hybrid polymers of formula (1) for which X = H and X '= NH2, vinylamine amides, for example vinylformamid or vinylacetamide, are preferably used as ethylenically unsaturated monomers. The polymer obtained is then hydrolyzed at acidic or basic pH.

For the preparation of the hybrid polymers of formula (1) for which X = H and X ′ = OH, vinyl esters of carboxylic acid, such as for example vinyl acetate, are preferably used as ethylenically unsaturated monomers. The polymer obtained is then hydrolyzed at acidic or basic pH.

The types and amounts of copolymerizable monomers used according to the present invention vary depending on the particular end application for which the hybrid polymer is intended.

According to a first preferred variant, the hybrid silicone and organic polymer consists of a linear silicone backbone comprising from 1 to 500 units of formula (1), preferably 1 to 200, and bearing from 1 to 50 U radicals.

2 3 dans laquelle R2 et R, identiques ou différents, représentent un atome d'hydrogène, un groupe cyano, alikoxycarbonyle, alkyle, acyle, aryle, alcène ou alcyne éventuellement substitué ; et W est de définition identique à celle donnée précédemment, et de préférence est égal à un atome d'oxygène. A titre d'exemples, on citera les précurseurs silicones dans lesquelles U'correspond à : According to a second variant, at least one of the monovalent radicals U ′ is preferably of formula (VI):

2 3 in which R2 and R, identical or different, represent a hydrogen atom, an optionally substituted cyano, alikoxycarbonyl, alkyl, acyl, aryl, alkene or alkyne group; and W is of definition identical to that given previously, and preferably is equal to an oxygen atom. By way of examples, mention will be made of the silicone precursors in which U 'corresponds to:

<Desc / Clms Page number 35>

According to a third variant, at least part of the monovalent radicals U 'of the silicone precursor (s) (IV) and therefore at least part of the groups U of the hybrid polymer obtained are such that Z is an atom d oxygen and / or a sulfur atom.

According to a fourth variant, in addition to the units of formula (1), the hybrid silicone and organic polymer according to the invention may comprise RxUyFzSiO [4- (x + y + z)] / 2 (XIV) units in which: - x is equal to 0, 1, 2 or 3, y is equal to 0, 1, 2 or 3 and z is equal to 1, 2 or 3 with with 2 <(x + y + z)::; ; 3, - and F is a group bearing at least one function such as hydroxy, alkoxy, thiol, amine, epoxy and / or polyether.

These groups F can optionally provide complementary and / or additional properties to the hybrid polymers prepared according to the process of the invention. They may in particular be initially contained within the silicone precursor of formula (IV).

In addition to hybrid polymers with homopolymeric organic segments, the process which has just been described makes it possible to prepare hybrid polymers bearing organic block (that is to say multiblock) groups. For this, the process consists in repeating the implementation of the preparation process described above using:

<Desc / Clms Page number 36>

- different monomers from the previous implementation, and - instead of the precursor silicone compound (II), the hybrid polymer comprising units (1) with blocks resulting from the previous implementation.

According to this process for preparing block polymers, when it is desired to obtain polymers with homogeneous blocks and not with a composition gradient, and if all the successive polymerizations are carried out in the same reactor, it is essential that all the monomers used during of a step have been consumed before the polymerization of the next step begins, therefore before the new monomers are introduced.

As for the monoblock polymer polymerization process, this process for polymerizing block polymers has the advantage of leading to block polymers having a low polydispersity index. It also makes it possible to control the molecular mass of block polymers.

où le radical monovalent un est selon la formule suivante (vil) :

dans laquelle : - W et Sp sont de définitions identiques à celles données précédemment, - L est un groupement électrofuge, par exemples : B CI-, l-, OTs-, OMs-, (C6H6)-(C=O)-O-, (CH3)-(C=O)-O-, (CF3)-(C=O)-O-.

The precursor silicone compound of general formula (IV) used in the process for preparing hybrid polymers can be obtained by reaction: (i) of a silicone comprising units of formula (VII):

where the monovalent radical un is according to the following formula (vil):

in which: - W and Sp are of identical definitions to those given previously, - L is an electrofuge group, for example: B CI-, l-, OTs-, OMs-, (C6H6) - (C = O) -O -, (CH3) - (C = O) -O-, (CF3) - (C = O) -O-.

1 S. C-S-, M" C-S-. M' ./ (X) , 2 su 9 s C-S-- (M) m (R1) x'-- Z (XI) et n dans lesquelles : (ii) with a compound chosen from those of the following general formulas (IX), (X) or (XI):

1 S. CS-, M "CS-. M './ (X), 2 su 9 s CS-- (M) m (R1) x' - Z (XI) and n in which:

<Desc / Clms Page number 37>

- M '+ represents K +, Na +, NR /, or PR4 +' R being of a definition similar to that given for R of formula (1), - M "2+ represents an alkaline earth metal such as Ca, Ba and S , - Mm represents Zn, Cd, m is equal to 1 or 2, n is equal to 1.2, 3 or 4 and preferably m is equal to 1 and n is equal to 2.

This silicone of formula (VII) can be obtained in particular from (i) a silicone comprising units of formula (XII): RxU "'ySiO [4- (x + y)] / 2 where the monovalent radical U'"is of formula (XIII): -Sp-WH and (ii) of a compound of formula:

The polymerization can be carried out in bulk, in solution or in emulsion. Preferably, it is used as an emulsion.

Preferably, the process is carried out semi-continuously.

The temperature can vary between room temperature and 150 ° C. depending on the nature of the monomers used.

In general, during the polymerization, the instantaneous polymer content relative to the instantaneous quantity of monomer and polymer is between 50 and 99% by weight, preferably between 75 and 99%, even more preferably between 90 and 99% . This content is maintained, in a known manner, by controlling the temperature, the rate of addition of the reactants and of the polymerization initiator.

Finally, the method is generally carried out in the absence of a UV source.

It should be noted that it may be advantageous to chemically modify the xanthate ends of the polymer obtained, by implementing any method known to those skilled in the art, such as for example a hydrolysis step.

The process and the polymers obtained by this process are described in French application No. 00 09722 filed on 07/25/00.

Other methods of synthesizing this type of polymer can be implemented, in particular that described in international applications WO 00/71606 and WO 00/71607.

In the case where the dispersed phase is the oil phase and where the silicone phase is the continuous phase, the latter comprises at least one comb or block polymer. All that has been said previously on the nature and preparation of the polymer included in the continuous oil phase remains valid in this case, except for the fact that the fraction soluble in the silicone is greater than the fraction soluble in the phase. oil, so as to satisfy Bancroft's rule.

<Desc / Clms Page number 38>

According to a particular embodiment of the invention, phase B comprises at least one polymer as has just been described, in an amount of between 0.5 to 10% by weight of phase A, preferably between 1 and 4% by weight relative to the same reference.

The external aqueous phase C further comprises at least one surfactant and / or an amphiphilic polymer
More particularly, whether phase B is an oil or silicone phase, phase C comprises: at least one nonionic surfactant and / or at least one nonionic amphiphilic polymer optionally combined with at least one anionic surfactant and / or at least one polymer anionic amphiphilic; the total content of nonionic and anionic amphiphilic surfactant (s) and / or polymer (s) is between 0.5 and
10% by weight, preferably between 1 and 5% by weight, relative to phase B; the amount of anionic amphiphilic surfactant (s) and / or polymer (s) represents
0.5 to 10% by weight, preferably 0.5 to 5% by weight, relative to the weight of nonionic amphiphilic surfactant (s) and / or polymer (s); or at least one anionic amphiphilic polymer optionally combined with at least one anionic surfactant; the total content of amphiphilic polymer (s) and / or anionic surfactant (s) is between 0.5 and 10% by weight, preferably between 1 and 5% by weight, relative to the phase B.

Here again, reference may be made to the various lists of surfactants / polymers which can be envisaged in the context of a continuous aqueous phase for the emulsions of the first category.

Finally, said aqueous external phase optionally comprises at least one thickening agent.

The thickening agent is preferably chosen from polysaccharides such as xanthan gum and guar, alone or as mixtures.

Furthermore, the thickening agent content is advantageously between 0.1 and 2% by weight of the multiple emulsion.

In the context of this second category of multiple emulsions, the phase A / phase B weight ratio is advantageously between 10/90 and 90/10, preferably between 30/70 and 50/50.

Furthermore, the weight ratio of the whole phase A and phase B / phase C is included, more particularly between 30/70 and 90/10, preferably between 50/50 and 90/10.

The emulsion of phase A in phase B can be made in a manner known per se.

For example, in the case of first category emulsions (that is to say where one of the phases A or B is an aqueous phase), and more particularly when the

<Desc / Clms Page number 39>

phase A is an aqueous phase and B an oil phase, it is possible to proceed by preparing, on the one hand, a first mixture comprising water, optionally the hydrophilic active material (s), optionally at least one additive (sugar, salt, polysaccharide), at least one cationic surfactant if present; and a second mixture comprising the compound constituting said phase, optionally the hydrophobic active material (s), optionally at least one nonionic surfactant and / or at least one amphiphilic block polymer. As regards the gelling polymer (s) present in the oil phase, several possibilities can be envisaged. Thus, the gelling polymer can be introduced into the oil phase either before obtaining the reverse emulsion, or once the reverse emulsion has been prepared.

Still in the case of first category emulsions, but in those where phase A is an oil phase and B an aqueous phase, the preparation of the emulsion can be carried out by preparing two mixtures. The first mixture comprises water, optionally or hydrophilic active materials, and depending on the variant adopted, either at least one surfactant and / or at least one nonionic amphiphilic polymer optionally combined with at least one anionic surfactant, or at least one polymer anionic amphiphilic optionally combined with at least one anionic surfactant. The second mixture comprises the compound constituting the oil phase, optionally the hydrophobic active material (s) and the gelling polymer (s).

In each of the preceding cases, the mixture which constitutes the dispersed phase of the emulsion is then added to the mixture constituting the continuous phase of the emulsion, with stirring.

In the case where the oil phase is not very viscous (for example having a viscosity of less than 1 Pa. S; dynamic viscosity measured in a Brookfield at 25 ° C., according to the NFT 76 102 standard of February 1972) the stirring is preferably strong and can be advantageously provided by the use of an Ultra-Turraxo type device,
Microfluidizer, or any high pressure homogenizer.

In the case where the oil phase is viscous (for example having a viscosity greater than or equal to 1 Pa · s, measured as above), the stirring can advantageously be carried out by means of a frame blade.

In the context of the emulsions of the second category (in which one of the phases A or B is a silicone phase), a first mixture is prepared comprising the compound constituting the oil phase, optionally the hydrophobic active material (s), the hydrophobic active material (s), gelling polymers, and where appropriate at least one surfactant and / or polymer. A second mixture is prepared comprising the silicone, optionally the hydrophobic active material (s), optionally at least one surfactant and / or polymer.

<Desc / Clms Page number 40>

In this case, the addition of the gelling polymer can also take place according to several possibilities; the first consisting in adding it to the oil phase before obtaining the reverse emulsion, the second once the reverse emulsion has been prepared.

The mixture which constitutes phase A of the emulsion (dispersed phase) is then added to the mixture constituting phase B of the emulsion (continuous phase), with stirring.

The stirring means used will be adapted according to the ratio of viscosities between phases A and B. If it is large (for example greater than or equal to 1000), the procedure will be carried out in the same way as in the previous case, where the oil is viscous; and if it is low, we will proceed as in the case where the oil is not very viscous.

médian en volume (dso) qui représente le diamètre de la particule égal à 50 % de la distribution cumulative. The duration of the stirring, whatever the category of multiple emulsion, can be determined without difficulty by a person skilled in the art and depends on the type of equipment used. It is preferably sufficient to obtain an average droplet size of between 0.1 and 10 µm, preferably between 0.1 and 5 µm (measured by means of a Horiba particle size analyzer). It is recalled that the average size corresponds to the diameter

volume median (dso) which represents the diameter of the particle equal to 50% of the cumulative distribution.

The preparation of the A / B emulsion is generally carried out at a temperature greater than or equal to the melting point of the gelling polymer. Furthermore, such a temperature is maintained until the multiple emulsion is obtained.

As regards the preparation of the multiple emulsion A / B / C, and in the case where phase C is an aqueous phase, a mixture is prepared comprising water, optionally one or more hydrophilic active materials, optionally at least an additive (sugar, salt, polysaccharide), and depending on the possible variants, either at least one surfactant and / or at least one nonionic amphiphilic polymer optionally combined with at least one anionic surfactant, or at least one anionic amphiphilic polymer optionally combined with at least one anionic surfactant.

Advantageously, if a thickener is present, the latter is introduced once the multiple emulsion has been obtained, but before it has cooled.

In the case where phase C is an oil phase, a mixture is prepared comprising the compound constituting the oil phase, optionally a hydrophobic active material and at least one nonionic surfactant and / or at least one amphiphilic block polymer.

Whatever the envisaged case, the A / B emulsion prepared above is then added to the appropriate mixture which has just been described.

The multiple emulsion is obtained at a temperature greater than or equal to the melting point of the gelling polymer.

<Desc / Clms Page number 41>

The stirring can be done by means of a frame blade. Typically, the stirring speed is relatively slow, of the order of 400 rpm.

Once the multiple emulsion is obtained, the temperature of the latter is allowed to fall below the melting point of the gelling polymer. This operation can take place without active external intervention, or else by cooling the multiple emulsion.

This operation is preferably carried out in the absence of agitation.

The emulsion according to the invention can be used as a constituent element in formulations which can be used in many fields, such as cosmetics, food, the field of phytosanitary active materials, that of the exploitation or construction of oil field wells. or gas, that of silicones, or in the field of papermaking, among others.

A concrete but nonlimiting example of the invention will now be presented.

EXAMPLE 1 / Synthesis of a gelling polymer.

The reaction takes place in a 400 ml cylindrical glass reactor fitted with a tetracol cover, a column head extended by a descending condenser connected to a 50 ml receiving flask cooled in a dry ice / acetone bath and to an outlet. vacuum, a stainless steel mechanical stirring anchor and a nitrogen inlet. This system is heated by means of a thermoregulated Wood alloy bath.

All the following reagents are loaded:

Selon ces conditions, le rapport molaire jeffamine/acide béhénique est de 1/3. <tb>
<tb> Jeffamine <SEP> T <SEP> 403 &commat;<SEP> (*) <SEP> 35 <SEP> g
<tb> Behenic <SEP><SEP> 74, <SEP> 97 <SEP> g
<tb> Hypophosphorous <SEP><SEP> to <SEP> 50 <SEP>% <SEP> in <SEP> weight <SEP> in <SEP> water <SEP> 11 <SEP> (Jt
<tb>
(*) Polyoxypropylene Triamine marketed by the Huntsman company - with the formula:

Under these conditions, the jeffamine / behenic acid molar ratio is 1/3.

<Desc / Clms Page number 42>

The reaction mass is deoxygenated by four vacuum / nitrogen purges and it is maintained under a nitrogen purge.

The reaction mass is then gradually brought to 2300C with stirring at 50 revolutions per minute. The temperature is raised at 10 C / min up to 200 C, then at 1 C / min from 200 to 230 C.

The reaction mass becomes clear and homogeneous from 150 C.

Water begins to distill from 200 C.

The reaction mass is maintained at a temperature of 230 ° C. under a nitrogen purge for 30 minutes, then gradually placed under vacuum (20 mbar reached in 45 minutes, then maintained under 20 mbar of vacuum for 10 minutes).

Atmospheric pressure is then reestablished under nitrogen flushing.

The reaction mixture is then cooled by quenching.

A solid mass of pale yellow color with a waxy appearance is recovered.

Analysis of the distillate shows that it consists of water (titration by the Karl Fischer method) and caprolactam (titration by gas chromatography).

The quantity of water collected corresponds to an advancement of the polycondensation reaction (-CO 2 H / -NH 2) of the order of 95%.

The number molecular mass of the polymer obtained is 1050 g / mol, for a molecular mass by weight of 1610 g / mol (values expressed as polystyrene equivalents in dichloromethane).

In differential thermal analysis with a scanning speed of 10 C / min, the polymer exhibits a melting peak, the top of which is at 71 C.

2 / Preparation of a multiple emulsion 2. 1 / Inverse emulsion Composition of the inverse emulsion: * 30% aqueous phase: - 14% lactic acid (% by weight of 0.1 M solution expressed relative to the weight of aqueous phase) - 86% NaCl (% by weight of 0.1 M solution expressed relative to the weight of aqueous phase)

<Desc / Clms Page number 43>

* 70% of oil phase (soybean oil and surfactant + gelling polymer) comprising 5% of surfactant (Arlacel P135; ICI-Uniquema (*);% expressed by weight relative to the weight of aqueous phase) and comprising 3% of gelling polymer (obtained in Example 1;% expressed by weight relative to the oil phase).

(*) Arlacel P 135: Polyhydroxystéa rate-PEG-Polyhydroxystearate; HLB = 5-6; Mw 5000 g / mol) Preparation of the inverse emulsion
49.965 g of reverse emulsion are prepared, comprising 15 g of internal aqueous phase and 34.965 g of internal oil phase.

On the one hand, 2.1 g of 0.1M lactic acid solution is mixed with 12.9 g of 0.1M NaCl solution.

The temperature of the internal aqueous phase is brought to 75 C.

On the other hand, 0.75 g of Arlacel P135 is mixed with 33.9 g of soybean oil.

Prior to mixing, soybean oil and Arlacel were placed in an oven at 75 C.

The internal aqueous phase is then added to the internal oil phase, with stirring with Ultraturrax at 9500 rev / min. The mixing is carried out at 75 C. Refining is then carried out at 9500 rev / min for 2 minutes.

Then added 0.315 g of gelling polymer, finely ground (mixing with a spatula).

The temperature is maintained at 75 C.

2. 2 / Multiple emulsion Composition of the multiple emulsion: * 50% inverse emulsion (15 g) * 50% external aqueous phase (15 g) containing: - 2% Arlatone F127G (**) (HERE -Uniquema;% by weight expressed relative to the weight of the reverse emulsion); - 3, 6% of glucose (% by weight expressed relative to the weight of the external aqueous phase); - 0.5% of Phenonip (NIPA Laboratories;% by weight expressed relative to the weight of the external aqueous phase); - 1% of Rhodopol 23 (Rhodia Chimie;% by weight expressed relative to the weight of the external aqueous phase).

<Desc / Clms Page number 44>

(*) Arlatone F127G: HO (CH2CH20) x (OCH (CH3) CH20) y (CH2CH20) zH.

(**) Phenonip: biocide (***) Rhodopol 23: xanthan gum; dry extract: 87.7% Preparation of the multiple emulsion Preparation of the external aqueous phase:
A 2% solution of Rhodopol 23 in water (with a few drops of formaldehyde) is mixed at 75 ° C. with a 4% solution of Arlatone F127G, 7.2% glucose and 1% Phenonip.

Preparation of the multiple emulsion:
15 g of the reverse emulsion obtained in point 1 / are introduced, with stirring with a frame paddle at 400 rev / minute, dropwise and then slowly, into the 15 g of external aqueous phase described above, at 75 ° C. Stirring is maintained for 5 minutes for refining.

The multiple emulsion obtained is allowed to cool for 1 hour at room temperature.

A multiple emulsion is obtained in which the internal oil phase is gelled.

Claims (25)

CLAIMS 1. Multiple emulsions A / B / C comprising a dispersed phase A in a continuous phase B, the whole of phase B comprising phase A, constituting a phase dispersed in a continuous phase C; phases A and B on the one hand, and phases B and C on the other hand, being immiscible with one another; the multiple emulsions A / B / C being of the water / oil / water, oil / water / oil, silicone / oil / water or oil / silicone / water type, characterized in that the internal oil phase A or B comprises at least one gelling polymer substantially insoluble in aqueous medium, having at least three identical or different branches, each branch consisting of: an internal block comprising repeating units oxypropylene and / or oxybutylene, and optionally oxyethylene, - an external block comprising an hydrocarbon chain, linear or branched, saturated or not, comprising at least 18 carbon atoms in the longest chain, and optionally interrupted by one or more aromatic rings; - the two sequences being linked together via a spacer segment of formula: - XCOX'r- [Ri-XCOX'ri-p-R2-XCOX'r] q; formula in which: - X, X ', identical or not, represent-0 -, - NH-; -NHCO- - R1, R2, identical or not, represent a divalent alkyl radical, linear or branched, comprising 1 to 12 atoms of carbon, preferably 4 to 10 carbon atoms, in the longest chain, a divalent aryl radical comprising one or more aromatic rings, optionally substituted, - p is an integer between 0 and 9, preferably between 0 and 3; - q is equal to 0 or 1; - r is equal to 0 or 1. 2. Emulsions according to the preceding claim, characterized in that the total number of oxypropylene and / or oxybutylene repeat units is between 1 and 10, advantageously between 1 and 5. 3. Emulsions according to one of the preceding claims, characterized in that the total number of oxyethylene repeat units in the polymer, if they are present in one or more of the blocks, represents less than 10% of the total number of. 'oxypropylene and / or oxybutylene units. <Desc / Clms Page number 46> 4. Emulsions according to one of the preceding claims, characterized in that the hydrocarbon chain comprises 18 to 40 carbon atoms, is saturated, linear or having one or more branches not comprising more than four carbon atoms. 5. Emulsions according to one of the preceding claims, characterized in that the radicals R1, R2, identical or different, correspond to the following formula: - (CH2) n- (CH (CH3)) n'-; formula in which n, n ', identical or not, are integers varying from 0 to 12, on the condition that at least one of the two coefficients is not zero and that the sum n + n is at least plus 12, preferably at most 10. 6. Emulsions according to one of the preceding claims, characterized in that the gelling polymer is obtained by implementing polycondensation reactions during which water molecules are released. 7. Emulsions according to one of the preceding claims, characterized in that the gelling polymer content represents 0.5 to 10% by weight of the internal oil phase A or B, preferably 1 to 5% by weight of the oil phase. internal A or B. 8. Emulsions according to one of the preceding claims, characterized in that at least one of the phases of the multiple emulsion comprises at least one active material, different from the phase concerned, the active material content is between 0 , 1 and 50% by weight of said phase, and preferably between 0.1 and 20% by weight of said phase. 9. Emulsions according to one of the preceding claims, characterized in that the internal oil phase A or B comprising the gelling polymer is chosen from the following compounds: - organic oils of animal or plant origin; - products resulting from the alcoholysis of the aforementioned oils; - essential oils ; - mono-, di- and tri-glycerides - esters of fatty acids, saturated or not, comprising 10 to 40 carbon atoms and alcohols comprising 1 to 6 carbon atoms; - alcohols, saturated or not, comprising 4 to 40 carbon atoms, and optionally comprising several hydroxyl groups; these compounds being used alone or as a mixture. <Desc / Clms Page number 47> 10. Emulsions according to the preceding claim, characterized in that the oil intended not to include the gelling polymer, is chosen from: - organic oils of animal or plant origin; - mineral oils; - products resulting from the alcoholysis of the aforementioned oils; - essential oils ; - mono-, di- and tri-glycerides; - esters of fatty acids, saturated or not, comprising 10 to 40 carbon atoms and alcohols comprising 1 to 6 carbon atoms; - alcohols, saturated or not, comprising 4 to 40 carbon atoms, and optionally comprising several hydroxyl groups; these compounds being used alone or as a mixture. 11. Emulsions according to one of the preceding claims, characterized in that the inverse emulsion comprises at least one surfactant and / or at least one polymer, chosen from those which satisfy both the two conditions below: - when ' they are mixed with phase B, at a concentration between 0.1 and 10% by weight of phase B and at a temperature between 20 C and the preparation temperature of emulsion A / B, are in the form of a solution in phase B, in all or part of the range of indicated concentration; - when mixed with phase A, at a concentration between 0.1 and 10% by weight of phase A and at a temperature between 200C and the preparation temperature of emulsion A / B, are in the form of a dispersion in phase A, in all or part of the range of indicated concentration. 12. Emulsions according to one of the preceding claims, characterized in that the multiple emulsion comprises at least one surfactant and / or at least one polymer, chosen from those which satisfy both the two conditions below: - when ' they are mixed with phase C, at a concentration between 0.1 and 10% by weight of phase C and at a temperature between 20 C and the preparation temperature of the A / B / C emulsion, are in the form of a solution in phase C, in all or part of the indicated concentration range; - when they are mixed with phase B, at a concentration between 0.1 and 10% by weight of phase B and at a temperature between 200C and <Desc / Clms Page number 48> preparation temperature of the A / B / C emulsion, are in the form of a dispersion in phase B, in all or part of the concentration range indicated. 13. Emulsions according to one of the preceding claims, characterized in that when phase A is an aqueous phase and B an oil phase, or when phase B is an aqueous phase and phase C is an oil phase, respectively phase B or phase C comprises at least one nonionic surfactant and / or at least one block amphiphilic polymer comprising at least one hydrophobic block and at least one neutral, anionic or cationic hydrophilic block; the total content of nonionic surfactant (s) and / or amphiphilic block polymer (s) being between 0.1 and 10% by weight, preferably between 2 and 10% by weight relative respectively in phase A or in phase B. 14. Emulsions according to one of the preceding claims, characterized in that when phase A is an aqueous phase and B an oil phase, said phase A comprises at least one cationic surfactant; the total content of cationic surfactant (s) and of nonionic surfactant (s) and / or of block amphiphilic polymer (s) is between 0.1 and 10% by weight, preferably between 2 and 10% by weight relative to phase A. 15. Emulsions according to one of claims 1 to 10 and 12, characterized in that when phase A is an aqueous phase and B an oil phase, said phase A comprises at least one cationic surfactant; the total content of cationic surfactant (s) is between 0.1 and 10% by weight, preferably between 2 and 10% by weight relative to phase A. 16. Emulsions according to one of claims 1 to 13, characterized in that when phase A or B is an oil phase and phase B or C is an aqueous phase, respectively, said phase B or C comprises: at least one nonionic surfactant and / or at least one nonionic amphiphilic polymer optionally combined with at least one anionic surfactant and / or at least one anionic amphiphilic polymer; the total content of nonionic and anionic amphiphilic surfactant (s) and / or polymer (s) is between 0.5 and 10% by weight, preferably between 1 and 5% by weight, relative to phase A or to phase B; the amount of anionic amphiphilic surfactant (s) and / or polymer (s) represents 0.5 to 10% by weight, preferably 0.5 to 5% by weight, relative to the weight of surfactant ( s) and / or nonionic amphiphilic polymer (s); or <Desc / Clms Page number 49> - at least one anionic amphiphilic polymer optionally combined with at least one anionic surfactant; the total content of amphiphilic polymer (s) and / or anionic surfactant (s) is between 0.5 and 10% by weight, preferably between 1 and 5% by weight, relative to the phase A or phase B. 17. Emulsions according to one of claims 1 to 15, characterized in that, when phase B is an oil or silicone phase and phase C is an aqueous phase, said phase C comprises: - at least one nonionic surfactant and / or at least one nonionic amphiphilic polymer optionally combined with at least one anionic surfactant and / or at least one anionic amphiphilic polymer; the total content of nonionic and anionic amphiphilic surfactant (s) and / or polymer (s) is between 0.5 and 10% by weight, preferably between 1 and 5% by weight, relative to phase B; the amount of anionic amphiphilic surfactant (s) and / or polymer (s) represents 0.5 to 10% by weight, preferably 0.5 to 5% by weight, relative to the weight of nonionic amphiphilic surfactant (s) and / or polymer (s); or - at least one anionic amphiphilic polymer optionally combined with at least one anionic surfactant; the total content of amphiphilic polymer (s) and / or anionic surfactant (s) is between 0.5 and 10% by weight, preferably between 1 and 5% by weight, relative to the phase B. 18. Emulsions according to one of the preceding claims, characterized in that the phase A / phase B weight ratio is between 10/90 and 90/10, preferably between 30/70 and 80/20. 19. Emulsions according to one of the preceding claims, characterized in that the weight ratio of the whole phase A and phase B / phase C is between 30/70 and 90/10, preferably between 50/50 and 90. / 10. 20. Emulsions according to one of claims 1 to 9 and 11 to 12, characterized in that the multiple emulsions are of the silicone / oil / water type or of the oil / silicone / water type, and in that the silicone phase is present. in liquid form at room temperature, is chosen from silicones consisting in all or part of units of formula: R'3-aRaSi01 / 2 (M unit) and / or R2SiO (D unit) formulas where: - a is an integer from 0 to 3; - the R radicals are identical or different and represent: <Desc / Clms Page number 50> - a saturated or unsaturated aliphatic hydrocarbon group containing from 1 to 10 carbon atoms; - an aromatic hydrocarbon group containing from 6 to 13 carbon atoms; a polar organic group bonded to silicon via an Si-C or Si-O-C bond; - the radicals R 'are identical or different and represent: - a saturated or unsaturated aliphatic hydrocarbon group containing from 1 to 10 carbon atoms; - an aromatic hydrocarbon group containing from 6 to 13 carbon atoms; - an -OH function; - an amino- or amido-functional group containing from 1 to 6 carbon atoms, bonded to silicon via an Si-N bond; alone or in combination. 21. Emulsions according to the preceding claim, characterized in that, phase B comprises at least one polymer in an amount of between 0.5 to 10% by weight of phase A, preferably between 1 and 4% by weight relative to to the same reference. 22. Emulsions according to one of claims 20 or 21, characterized in that phase C comprises: - at least one nonionic surfactant and / or at least one nonionic amphiphilic polymer optionally combined with at least one anionic surfactant and / or at least one anionic amphiphilic polymer; the total content of nonionic and anionic amphiphilic surfactant (s) and / or polymer (s) is between 0.5 and 10% by weight, preferably between 1 and 5% by weight, relative to phase A; the amount of anionic amphiphilic surfactant (s) and / or polymer (s) represents 0.5 to 10% by weight, preferably 0.5 to 5% by weight, relative to the weight of nonionic amphiphilic surfactant (s) and / or polymer (s); or at least one anionic amphiphilic polymer optionally combined with at least one anionic surfactant; the total content of amphiphilic polymer (s) and / or anionic surfactant (s) is between 0.5 and 10% by weight, preferably between 1 and 5% by weight, relative to the phase AT. 23. Emulsions according to one of claims 20 to 22, characterized in that the phase A / phase B weight ratio is between 10/90 and 90/10, preferably between 30/70 and 50/50. <Desc / Clms Page number 51> 24. Emulsions according to one of claims 20 to 23, characterized in that the weight ratio of the whole phase A and phase B / phase C is between 30/70 and 90/10, preferably between 50/50 and 90/10. 25. Use of multiple emulsions according to one of the preceding claims in the fields of cosmetics, food, the field of phytosanitary active materials, that of the operation or construction of oil or gas field wells, that of silicones, or in the field of papermaking.