FR2835432A1 - Water/oil/water emulsions comprising an external aqueous phase, an oily phase with an internal aqueous phase and a primary water/oil emulsion, for external application in cosmetics and dermatology - Google Patents

Abstract

A water/oil/water emulsion for external application comprises an external aqueous phase, an oily constituent with an aqueous phase and a primary water/oil emulsion ; the aqueous phase contains a hydrophilic amphiphilic non-cross-linked polymer with at least two hydrophobic side-chains. Independent claims are also included for the use of the emulsion and cosmetic procedure.

Description

<Desc / Clms Page number 1>

The present invention relates to a triple water / oil / water emulsion for topical application, containing a particular polymer, and to its uses in the cosmetic and dermatological fields, in particular with a view to treating and / or protecting and / or cleaning the skin and / or mucous membranes and / or keratinous fibers.

It is known to use, especially in the cosmetic and dermatological fields, topical compositions in the form of emulsions. These emulsions are generally oil-in-water (O / W) or water-in-oil (W / O) emulsions. It can also be multiple emulsions of water / oil / water (W / O / W) or oil / water / oil (W / W / H) type. Among the multiple emulsions, it is preferable to use emulsions with an external aqueous phase, namely W / O / W emulsions, which combine the advantages of freshness with the application provided by the water present in the aqueous external phase. and comfort provided by a relatively large amount of oil.

Furthermore, W / O / W emulsions are generally used in the cosmetic, dermatological and / or pharmaceutical fields, for stabilizing active ingredients as described for example in document EP-A-0908170, or for modifying the release of active ingredients. on the skin or on the hair as described for example in EP-A-0717978. These emulsions make it possible in particular to protect sensitive assets against external agents harmful to the stability of these active agents, such as water or oxygen. Indeed, these emulsions are particularly interesting because the inner and outer aqueous phases are separated by an oily layer. An encapsulated asset in the internal phase can therefore be maintained outside the outer phase (see article by DAHMER TAGAWA 19th IFSCC Congress Sydney 1996). Thus, EP-A-779071 discloses an W / O / W emulsion containing a water-sensitive active ingredient.

However, multiple emulsions are little exploited because they are difficult to achieve: the primary emulsion can be reversed during its introduction into the secondary aqueous phase. Moreover, they frequently have problems of stability over time. The destabilization mechanism most frequently encountered is the migration of water from the internal droplets to the external aqueous medium through the intermediate oily layer, either by simple diffusion of water through the oily membrane, or by prior rupture of the oily film causing the coalescence of the internal water droplets and leading to release of internal water in the external aqueous medium. Generally speaking, this phenomenon of loss of multiple character eventually results in a macroscopically visible phase shift and in obtaining a simple O / W emulsion instead of a triple emulsion.

 On the other hand, the oil droplets of the secondary O / W emulsion must be coarse (generally from 10 to 50 μ) in order to be able to contain the E / H primary emulsion drops. Large droplets coalesce more easily than small droplets, and conventional surfactants are not always sufficient to stabilize them.

<Desc / Clms Page number 2>

Attempts have been made to stabilize triple emulsions with emulsifiers such as polyglycerol alkyl esters (see DE-A-19719297), polyoxyethylene alkyl ethers (see EP-A-735853), or mixtures thereof (see DE-A- 19649101), amino acid derivatives (see JP-A-60/16604), lecithins (see FR-A-2766737), or surfactants forming lamellar phases (see EP-A-715842 and EP-A-717978). ). However, the emulsions obtained have insufficient stability, and for reasons of safety, it is difficult to increase the amounts of emulsifiers.

To improve the stability of these triple emulsions, one solution is to strongly gel the external aqueous phase, using polymers such as hydroxypropyl cellulose as described in JP-A-03016635, such as poloxamers as described in US-A-5,478,561, or such as polysaccharides as described in US-A-5,258,184. However, these polymers provide a tacky composition upon application to the skin.

Another solution consists in using emulsifying polymers such as copolymers of acrylic acid of the Pemulen type as described in document FR-2,693,733, these copolymers possibly being used optionally in combination with a non-emulsifying polymer, and in particular a carbomer or an AMPS polymer as described in EPA-0908170. However, if the use of these emulsifying polymers improves the stability of the multiple emulsions, they lead to the production of gelled products which are heavy on application and therefore unpleasant, and all the more so since the compositions mentioned contain a significant amount of glycerin in the internal phase. In addition, when the amount of polyol and especially glycerin is too low, these emulsions tend to destabilize into a simple emulsion O / W.

There remains therefore the need to obtain a water-in-oil-in-water emulsion (W / O / W), easy to prepare and stable, even in the absence of gelling agents in the external aqueous phase, while having good cosmetic qualities, especially lighter than those of the state of the art.

Applicant has now unexpectedly found that multiple W / O / W emulsions can be made in a simple manner using as emulsifier of the secondary emulsion, a non-crosslinked hydrophilic polymeric polymer emulsifier having hydrophobic side links.

Also, the subject of the present invention is a water / oil / water emulsion for topical application, comprising an external aqueous phase, an oily phase constituting, with an internal aqueous phase, a primary water / oil emulsion, characterized in that the aqueous phase external container contains at least one non-crosslinked hydrophilic amphiphilic polymer having at least two hydrophobic side members.

Amphiphilic polymer is understood to mean any polymer comprising both a hydrophilic part and a hydrophobic part.

<Desc / Clms Page number 3>

The term "hydrophilic polymer" means any polymer that is soluble or dispersible in water, either as such or in neutralized form.

The term "non-crosslinked polymer" means a polymer that has not reacted with crosslinking agents and therefore does not contain crosslinking groups. It can be a linear or connected polymer.

The emulsion according to the invention is intended for topical application, it contains a topically acceptable medium, that is to say compatible with the skin, mucous membranes and keratin fibers such as the hair. It may constitute in particular a cosmetic or dermatological composition.

The triple emulsion according to the invention has the advantage of being stable, even in the absence of gelling agents in the external aqueous phase.

The non-crosslinked polymers used according to the invention are generally polymers capable of being obtained from at least one hydrophilic monomer A containing ethylenic unsaturation and at least one hydrophobic monomer B. They are soluble or dispersible in water , in neutralized form.

The monomer A comprises at least one oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a chlorine atom, a fluorine atom or their mixtures. Preferably, the monomer A has a strong acid function, in particular a sulphonic acid or phosphonic acid function.

The hydrophobic monomer B comprises at least one hydrophobic radical chosen from: linear or saturated C 8 -C 20 alkyl radicals (for example n-hexyl, n-octyl, n-decyl, n-dodecyl, n-hexadecyl, n octadecyl, n-behenyl, oleyl), branched (for example isostearic) or cyclic (for example cyclododecane or adamantane); fluorinated or alkylfluorinated radicals in Cl-go (for example the group of formula- (CHCFs-CFs); the cholesteryl radical or the radicals derived from cholesterol (for example cholesteryl hexanoate); polycyclic aromatic groups such as naphthalene or pyrene; silicone or alkylsilicone or alkylfluorosilicone radicals.

Among these radicals, linear and branched alkyl radicals are more particularly preferred. Preferably, the hydrophobic monomer is an alkyl chain comprising from 6 to 30 carbon atoms, more preferably from 6 to 22 carbon atoms and even more preferably from 6 to 18 atoms and more particularly from 12 to 18 carbon atoms.

Preferably, the polymers in accordance with the invention are partially or completely neutralized with a mineral base (sodium hydroxide, potassium hydroxide, ammonia) or an organic base such as mono-, di- or tri-ethanolamine,

<Desc / Clms Page number 4>

 aminomethylpropanediol, N-methylglucamine, basic amino acids such as arginine and lysine, and mixtures of these compounds.

The amphiphilic polymers according to the invention generally have a number-average molecular weight ranging from 1000 to 20,000,000 g / mol, preferably ranging from 20,000 to 5,000,000 and even more preferably from 100,000 to 1,500,000 gimole.

In particular, the polymers used according to the invention are preferably amphiphilic polymers capable of being obtained from at least one ethylenically unsaturated monomer containing a sulphonic group, in free form or partially or completely neutralized, and from minus one hydrophobic monomer.

choisis notamment parmi l'acide vinylsulfonique, l'acide styrènesulfonique, les acides (méth) acrylamido (C1-C22) alkylsulfoniques, les acides N- (C1-C22) alkyl- (méth) acrylamido (Cl-C, alkylsulfoniques comme l'acide undécyl-acrylamidométhane-sulfonique, ainsi que leurs formes partiellement ou totalement neutralisées, et leurs mélanges. The ethylenically unsaturated monomers containing a sulfonic group can be

chosen especially from vinylsulfonic acid, styrenesulphonic acid, (meth) acrylamido (C1-C22) alkylsulphonic acids, N- (C1-C22) alkyl- (meth) acrylamido (C1-C) alkylsulphonic acids such as undecyl-acrylamidomethanesulfonic acid, as well as their partially or completely neutralized forms, and mixtures thereof.

propane-sulfonique, l'acide 2-acrylamido-2-méthylpropane-sulfonique, l'acide 2méthacry) amido-2-méthytpropane-sutfonique, t'acide 2-acry) amido-n-butane- sulfonique, l'acide 2-acrylamido-2, 4, 4-triméthylpentane-sulfonique, l'acide 2- méthacrylamido-dodécyl-sulfoniq ue, l'acide 2-acrylamido-2, 6-diméthyl-3-heptane- sulfonique, ainsi que leurs formes partiellement ou totalement neutralisées, et leurs mélanges. According to a preferred embodiment of the invention, the (meth) acrylamido (C 1 -C 22) alkylsulfonic acids, such as, for example, acrylamidomethanesulfonic acid, acrylamido acid, are used as ethylenically unsaturated monomers containing a sulfonic group. ethanesulfonic acid, acrylamido acid

propanesulphonic acid, 2-acrylamido-2-methylpropanesulphonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-acylamido-n-butanesulfonic acid, 2- acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamido-dodecylsulfonic acid, 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid and their partially or totally neutralized, and their mixtures.

More particularly, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its partially or completely neutralized forms are used.

The amphiphilic polymers in accordance with the invention may especially be chosen from AMPS random amphiphilic polymers modified by reaction with a n-monoalkylamine or a C6-C22 di-n-alkylamine, such as those described in document WO-A -00/31154 (forming part of the content of the description). They may also be chosen from the polymers described in documents EP-A-1,069,142 and EP-A-1,138,703 (forming an integral part of the content of the description). Although these documents describe polymers that may be used in the present application, they do not describe or suggest that these polymers, and in particular those that are non-crosslinked, make it possible to obtain stable W / O / W emulsions without the addition of emulsifier or gelling agents in the external aqueous phase.

<Desc / Clms Page number 5>

 In addition to the monomers indicated above, these polymers may also contain other hydrophilic ethylenically unsaturated monomers (not comprising a hydrophobic fatty chain) chosen, for example, from (meth) acrylic acids, their p-substituted alkyl derivatives or their esters. obtained with monoalcohols or mono- or polyalkylene glycols, (meth) acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid, maleic acid, cationic monomers such as diallyl dimethylammonium chloride, or mixtures of these compounds.

The preferred polymers used of the invention are chosen from AMPS amphiphilic copolymers and at least one hydrophobic monomer containing ethylenic unsaturation, comprising at least one hydrophobic part having from 6 to 30 carbon atoms, more preferably from 6 to 22. carbon atoms, more preferably 6 to 18 carbon atoms and more particularly 12 to 18 carbon atoms.

As indicated above, these AMPS copolymers may also contain one or more ethylenically unsaturated monomers having no fatty chain, such as (meth) acrylic acids, their ss-substituted alkyl derivatives or their esters obtained with monoalcohols. or mono or polyalkylene glycols, (meth) acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid, maleic acid, cationic monomers or mixtures thereof.

Such AMPS copolymers are described in particular in patent application EP-A-750899, US-A-5,089,578 and in the following Yotaro Morishima publications: Self-assembling amphiphilic polyelectrolytes and their nanostructuresChinese Journal of Polymer Science Vol. 18, N040, (2000), 323-336; - Miscellanous formation of random copolymers of 2- (acrylamido) -2-methylpropanesulfonate and a non-ionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering-Macromolecules 2000, Vol.

33,? 10-3694-3704)>; Solution properties of non-ionic moieties covalently bound to a polyelectrolyte: salt effects on rheological behavior-
Langmuir, 2000, Vol. 16, N 12, 5324-5332; Stimuli responsive amphiphilic copolymers of sodium 2- (acrylamido) -2-methylpropanesulfonate and associative macromonomers-Polym. Preprint, Div.

 Polym. Chem. 1999, 40 (2), 220-221.

 The hydrophobic monomers with ethylenic unsaturation of these particular copolymers are preferably chosen from acrylates, alkyl acrylates, acrylamides or alkyl acrylamides of formula (1) below:

<Desc / Clms Page number 6>

dans laquelle R1 et Ru, identiques ou différents, désignent un atome d'hydrogène ou un radical alkyle linéaire ou ramifié en Cl-C. (de préférence méthyle) ; Y désigne 0 ou NH ; R2 désigne un radical hydrocarboné hydrophobe comportant au moins de 6 à 50 atomes de carbone, plus préférentiellement de 6 à 22 atomes de carbone, encore plus préférentiellement de 6 à 18 atomes de carbone et plus particulièrement de 12 à 18 atomes de carbone ; x désigne un nombre de moles d'oxyde d'alkylène et varie de 0 à 100.

in which R1 and Ru, identical or different, denote a hydrogen atom or a linear or branched C1-C alkyl radical. (preferably methyl); Y is 0 or NH; R2 denotes a hydrophobic hydrocarbon radical containing at least 6 to 50 carbon atoms, more preferably 6 to 22 carbon atoms, even more preferably 6 to 18 carbon atoms and more particularly 12 to 18 carbon atoms; x denotes a number of moles of alkylene oxide and ranges from 0 to 100.

les radicaux a ! kytperf) uorés en Cg-Cg (par exempte te groupement de formule- (CHsCFg-CFg) ; le radical cholestéryle (C27) ou un reste d'ester de cholestérol comme le groupe oxyhexanoate de cholestéryle ; les groupes polycycliques aromatiques comme le naphtalène ou le pyrène. Parmi ces radicaux, on préfère plus particulièrement les radicaux alkyles linéaires et plus particulièrement le radical n-dodécyle, n-hexadecyle, n-octadécyle ou leur mélanges. The radical R 2 is preferably chosen from linear C 8 -C 18 alkyl (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl, n-dodecyl), branched or cyclic (for example cyclododecane (C 12) radicals). or adamantane (C1O));

the radicals a! C 7 -C 8 alkyl groups (for example, the group of the formula - (CH 3 CF 2 -C 8)), the cholesteryl radical (C 27) or a cholesteryl ester residue such as the cholesteryl oxyhexanoate group, polycyclic aromatic groups such as naphthalene or Among these radicals, linear alkyl radicals, and more particularly the n-dodecyl, n-hexadecyl or n-octadecyl radical, or mixtures thereof, are more particularly preferred.

According to a particularly preferred form of the invention, the monomer of formula (1) comprises at least one alkylene oxide unit (x = 1) and preferably several alkylene oxide units (x> 1) constituting a polyoxyalkylene chain. The polyoxyalkylene chain is preferably composed of ethylene oxide units and / or propylene oxide units and even more particularly ethylene oxide units. The number of oxyalkylenated units (or number of moles of alkylene oxide) generally varies from 3 to 100, more preferably from 3 to 50 and even more preferably from 7 to 25.

Among these polymers, mention may be made of: the non-crosslinked, neutralized or non-neutralized copolymers comprising from 15 to 60% by weight of AMPS units and from 40 to 85% by weight of (Ca-C16) alkyl (meth) acrylamide units or (Ca-C16) alkyl (meth) acrylate units relative to the polymer, such as those described in EP-A-750 899; terpolymers comprising from 10 to 90% by mole of acrylamide units, from 0.1 to 10% by mole of AMPS units and from 5 to 80% by mole of n- (C 6 -C 1a) alkylacrylamide units, such as those described in US-A-5,089,578.

<Desc / Clms Page number 7>

 Mention may also be made of the copolymers of partially or completely neutralized AMPS and of dodecyl methacrylate, of n-hexadecyl and / or of noctadecyl, as well as the copolymers of partially or completely neutralized AMPS and n-dodecylmethacrylamide, not crosslinked, such as those described in the Morishima articles quoted above.

dans laquelle X+ est un proton, un cation de métal alcalin, un cation alcalinoterreux ou !'ion ammonium, et de motifs de formule (III) suivante :

dans laquelle x désigne un nombre entier variant de 3 à 100, de préférence de 5 à 80 et plus préférentiellement de 7 à 25 ; R1 a la même signification que celle indiquée ci-dessus dans la formule (1) et R4 désigne un alkyle linéaire ou ramifié

en Cg-Cz et p ! us préférentie ! ! ement en C-Css. There may be mentioned more particularly the copolymers consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) units of formula (II) below:

wherein X + is a proton, an alkali metal cation, an alkaline earth cation or ammonium ion, and units of the following formula (III):

in which x denotes an integer ranging from 3 to 100, preferably from 5 to 80 and more preferably from 7 to 25; R1 has the same meaning as that indicated above in formula (1) and R4 denotes a linear or branched alkyl

in Cg-Cz and p! we prefer! ! in C-Css.

radical méthyle (CH3), et R4 représente n-hexadécyle (Cie) ou n-octadécyle (C1s) ou leurs mélanges ; et notamment ceux pour lesquels x = 8, R1 désigne le radical méthyle (CH3) et R4 = C16-18. Particularly preferred polymers are those wherein x = 25, R 1 denotes methyl and R 4 represents n-dodecyl, which are described in the Morishima articles mentioned above; those for which x = 25, R1 denotes the

methyl radical (CH3), and R4 represents n-hexadecyl (C18) or n-octadecyl (C1s) or mixtures thereof; and in particular those for which x = 8, R1 denotes the methyl radical (CH3) and R4 = C16-18.

The polymers for which X + denotes sodium or ammonium are more particularly preferred.

<Desc / Clms Page number 8>

The preferred amphiphilic polymers used according to the invention can be obtained according to the conventional methods of radical polymerization in the presence of one or more initiators, such as, for example, azobisisobutyronitrile (AIBN), azobisdimethylvaleronitrile, 2,2-dihydrochloride. azobis- [2-amidinopropane] (ABAH = 2,2-AzoBis- [2-Amidinopropane] Hydrochloride), organic peroxides such as dilauryl peroxide, benzoyl peroxide, tert-butyl hydroperoxide, etc. inorganic peroxidized compounds such as potassium or ammonium persulfate, or H 2 O 2 optionally in the presence of reducing agents.

The polymers may in particular be obtained by radical polymerization in tert-butanol medium in which they precipitate. By using precipitation polymerization in tert-butanol, it is possible to obtain a particle size distribution of the polymer which is particularly favorable for its uses.

The polymerization reaction may be conducted at a temperature between 0 and 150 C, preferably between 10 and 100OC, either at atmospheric pressure or under reduced pressure. It can also be carried out under an inert atmosphere, and preferably under nitrogen.

- d'un a) coo ! en C-C oxyéthy) éné par 7 moles d'oxyde d'éthylène (GENAPOLO LA-070 de la société HOECHST/CLARIANT), - d'un a) coo ! en C-C oxyéthyténé par 9 moles d'oxyde d'éthylène (GENAPOLO LA-090 de la société HOECHST/CLARIANT), - d'un alcool en C12-C14 oxyéthyléné par 11 moles d'oxyde d'éthylène

(GENAPOL LA-110 de la société HOECHST/CLARIANT), - d'un atcoot en Cie-Cig oxyéthyténé par 8 moles d'oxyde d'éthylène (GENAPOLO T-080 de la société HOECHST/CLARIANT), - d'un alcool en Cig-Cig oxyéthyléné par 15 moles d'oxyde d'éthylène (GENAPOL# T-150 de la société HOECHST/CLARIANT), - d'un alcool en C16-C18 oxyéthyléné par 11 moles d'oxyde d'éthylène (GENAPOL# T-110 de la société HOECHST/CLARIANT), - d'un alcool en C16-C18 oxyéthyléné par 20 moles d'oxyde d'éthylène (GENAPOL&commat; T-200 de la société HOECHST/CLARIANT), - d'un alcool en C16-C18 oxyéthyléné par 25 moles d'oxyde d'éthylène (GENAPOLO T-250 de la société HOECHST/CLARIANT),

- d'un atcoo ! en Cig-C oxyéthyténé par 25 moles d'oxyde d'éthylène et/ou d'un a) coot iso-Cie-Cig oxyéthy) éné par 25 moles d'oxyde d'éthylène. According to this process, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) or one of its sodium or ammonium salts, with a (meth) acrylic acid ester, has been polymerized in particular. an alcohol of Clo-Cls oxyethylenated with 8 moles of ethylene oxide (GENAPOL # C-080 from the company HOECHST / CLARIANT), - a C10 oxo alcohol oxyethylenated with 8 moles of ethylene oxide (GENAPOLO UD-080 from the company HOECHST / CLARIANT), - a C10 oxo alcohol oxyethylenated with 7 moles of ethylene oxide (GENAPOL # UD-070 from the company HOECHST / CLARIANT),

- of a) coo! in carbon monoxide with 7 moles of ethylene oxide (GENAPOLO LA-070 from the company HOECHST / CLARIANT), - from a) coo! in CC oxyethylenated with 9 moles of ethylene oxide (GENAPOLO LA-090 from the company HOECHST / CLARIANT), - a C12-C14 alcohol oxyethylenated with 11 moles of ethylene oxide

(GENAPOL LA-110 from the company HOECHST / CLARIANT), - an atcoot in Cie-Cig oxyethylenated with 8 moles of ethylene oxide (GENAPOLO T-080 from Hoechst / Clariant), - an alcohol C 9 -C 18 oxyethylenated with 15 moles of ethylene oxide (GENAPOL # T-150 from HOECHST / CLARIANT), - of a C16-C18 alcohol oxyethylenated with 11 moles of ethylene oxide (GENAPOL # T-110 from HOECHST / CLARIANT), - a C16-C18 alcohol oxyethylenated with 20 moles of ethylene oxide (GENAPOL &commat; T-200 from Hoechst / Clariant), - an alcohol C16-C18 oxyethylenated with 25 moles of ethylene oxide (GENAPOLO T-250 from the company HOECHST / CLARIANT),

- an atcoo! C 10 -C 20 ethylene oxide and / or an iso-C 1 -C 18 -alkyl oxyethylenediamine by 25 moles of ethylene oxide.

<Desc / Clms Page number 9>

The molar concentration in% of the units of formula (II) and units of formulas (1) or (III) in the polymers according to the invention varies according to the desired cosmetic application and the rheological properties of the formulation sought. It can vary between 0.1 and 99.9 mol%.

Preferably for the most hydrophobic polymers, the molar proportion of units of formula (1) or (III) ranges from 40 to 99.9%, more particularly from 50 to 90% and even more particularly from 60 to 80%.

Preferably for the low hydrophobic polymers, the molar proportion of units of formula (1) or (III) ranges from 0.1 to 50%, more particularly from 1 to 25% and even more particularly from 2 to 20%.

The distribution of the monomers in the polymers of the invention may be, for example, alternating, block (including multiblock) or any.

Preferred copolymers that may be mentioned more particularly are those described in EP-A-1,069,142.

The amphiphilic polymers used in accordance with the invention may be present in the compositions of the invention in amounts ranging from 0.01% to 20% by weight of active ingredient, more preferably from 0.02% to 10% of active ingredient. more preferably from 0.05 to 5% by weight of active material relative to the total weight of the triple emulsion.

The amphiphilic polymer is introduced into the external aqueous phase of the triple emulsion according to the invention.

polyglycérol-4), les sels d'acides gras tels que le Stéarate d'Aluminium, les tensioactifs dérivés de sucre tels que l'isostéarate de méthylglucose, les émulsionnants siliconés et leurs mélanges. Les émulsionnants siliconés peuvent être choisis par exemple dans le groupe comprenant les diméthicone copolyols, les alkyldiméthicone copolyols pouvant comporter des hétéroatomes tels que le fluor, et les mélanges les contenant, par exemple le mélange de Polyglyceryl-4 isostearate/Cetyl dimethicone copolyol/Hexyl laurate vendu sous la dénomination Abil WE 09 par la société Goldschmidt, le Cetyl dimethicone copolyol vendu sous la dénomination Abil EM 90 par la société Goldschmidt et le mélange de cyclomethicone/dimethicone copolyol vendu sous la dénomination Q2-3225C par la société Dow Corning. Le taux d'émulsionnant dans l'émulsion primaire va en général de 0,1 à 10 % en poids de matière active et de préférence de 0,5 à 5 % en poids par rapport au poids total de l'émulsion primaire. In the triple emulsion according to the invention, the primary W / O emulsion advantageously comprises at least one HLB emulsifier of less than 10 (HLB = hydrophilic lipophilic balance). The emulsifiers may be chosen, for example, from the group comprising alkoxylated and in particular ethoxylated fatty alcohols, alkoxylated and in particular ethoxylated fatty esters, glycerolated esters or ethers (for example the isostearate of

polyglycerol-4), fatty acid salts such as aluminum stearate, sugar-derived surfactants such as methylglucose isostearate, silicone emulsifiers and mixtures thereof. The silicone emulsifiers may be chosen for example from the group comprising dimethicone copolyols, alkyldimethicone copolyols may contain heteroatoms such as fluorine, and mixtures containing them, for example the mixture of Polyglyceryl-4 isostearate / Cetyl dimethicone copolyol / Hexyl laurate sold under the name Abil WE 09 by the company Goldschmidt, cetyl dimethicone copolyol sold under the name Abil EM 90 by the company Goldschmidt and the mixture of cyclomethicone / dimethicone copolyol sold under the name Q2-3225C by the company Dow Corning. The level of emulsifier in the primary emulsion generally ranges from 0.1 to 10% by weight of active material and preferably from 0.5 to 5% by weight relative to the total weight of the primary emulsion.

<Desc / Clms Page number 10>

The primary W / O emulsion may represent, for example, from 5 to 70% by weight, preferably from 10 to 60% by weight and better still from 15 to 50% by weight relative to the total weight of the triple emulsion.

The internal aqueous phase of the primary W / O emulsion preferably represents from 5 to 90%, better still from 30 to 90% and even more preferably from 40 to 80% of the total weight of the primary emulsion.

tels que le glucose ; les sels tels que le sulfate de magnésium, le chlorure de magnésium, le chlorure de sodium, le chlorure de potassium, le chlorure de strontium, le chlorure d'aluminium, l'hydroxychlorure d'aluminium, l'acétate d'aluminum, le chlorure de zinc ; les polymères tels que les polymères naturels comme par exemple les guars et leurs dérivés, les xanthanes, les dérivés de cellulose, les carraghénanes, les pectines, les chitosanes, les polymères synthétiques comme par exemple, les polymères acryliques comme le carbopol 980, les dérivés d'acrylamide comme le Sepigel 305, la polyvinylpyrrolidone ou PVP et ses dérivés, les polymères cationiques tels que le Salcare SC96, les polymères amphotères ; et leurs mélanges. La quantité d'agent osmotique dans la composition de l'invention peut aller par exemple de 0,01 à 50 %, de préférence de 0,05 à 30 %, mieux de 0,1 à 20 % et encore mieux de 0,5 à 10 % du poids total de l'émulsion triple. According to a preferred embodiment of the invention, the internal aqueous phase of the primary W / O emulsion and / or the external aqueous phase contain at least one osmotic agent chosen from polyols such as glycerine; glycols such as propylene glycol and polyethylene glycols such as PEG-8; sugars

such as glucose; salts such as magnesium sulfate, magnesium chloride, sodium chloride, potassium chloride, strontium chloride, aluminum chloride, aluminum hydroxychloride, aluminum acetate, zinc chloride; polymers such as natural polymers such as, for example, guars and their derivatives, xanthans, cellulose derivatives, carrageenans, pectins, chitosans, synthetic polymers, for example acrylic polymers such as carbopol 980, derivatives thereof, acrylamide such as Sepigel 305, polyvinylpyrrolidone or PVP and its derivatives, cationic polymers such as Salcare SC96, amphoteric polymers; and their mixtures. The amount of osmotic agent in the composition of the invention may range, for example, from 0.01 to 50%, preferably from 0.05 to 30%, better still from 0.1 to 20% and better still from 0.5 to at 10% of the total weight of the triple emulsion.

The oily phase of the primary emulsion contains at least one oil, this oil being physiologically acceptable. The oily phase may represent from 10 to 95% by weight, better still from 10 to 70% by weight and even more preferably from 20 to 60% by weight relative to the total weight of the primary W / O emulsion, ie 0.5% by weight. to 66.5% by weight relative to the total weight of the triple emulsion, better still from 0.5 to 49% by weight and more preferably 1 to 42% by weight relative to the total weight of the triple emulsion.

huiles de formules RICOOR et ROR dans taquette R représente te reste d'un As oils that can be used in the composition of the invention, mention may be made, for example, of: hydrocarbon-based oils of animal origin, such as perhydrosqualene; hydrocarbon-based oils of vegetable origin, such as liquid triglycerides of fatty acids containing from 4 to 10 carbon atoms, for instance triglycerides of heptanoic or octanoic acids or, for example, sunflower, corn or soybean oils, squash, grape seed, sesame, hazelnut, apricot, macadamia, arara, sunflower, castor oil, avocado, triglycerides of caprylic / capric acids such as those sold by Stearineries Dubois or those sold under the names Miglyol 810,812 and 818 by the company Dynamit Nobel, jojoba oil, shea butter oil; esters and synthetic ethers, in particular of fatty acids, such as

oils of formulas RICOOR and ROR in plate R represents the rest of a

<Desc / Clms Page number 11>

vaseline, les polydécènes, le polyisobutène hydrogéné tel que l'huile de Parléam&commat; ; - des huiles essentielles naturelles ou synthétiques telles que, par exemple, les huiles d'eucalyptus, de lavandin, de lavande, de vétiver, de litsea cubeba, de citron, de santal, de romarin, de camomille, de sarriette, de noix de muscade, de cannelle, d'hysope, de carvi, d'orange, de géraniol, de cade et de bergamote ; - les alcools et acides gras ayant de 8 à 26 atomes de carbone, comme l'alcool ou l'acide cétylique, l'alcool stéarylique, l'acide stéarique, le mélange d'alcool cétylique et d'alcool stéarylique (alcool cétylstéarylique), l'octyl dodécanol, le 2- butyloctanol, le 2-hexyldécanol, le 2-undécylpentadécanol, l'alcool oléique ou l'alcool linoléique ; - les huiles fluorées partiellement hydrocarbonées et/ou siliconées comme celles décrites dans le document JP-A-2-295912 ; - les huiles de silicone comme les polyméthylsiloxanes (PDMS) volatiles ou non à chaîne siliconée linéaire ou cyclique, liquides ou pâteux à température ambiante, notamment les cyclopolydiméthylsiloxanes (cyclométhicones) telles que la cyclohexasiloxane ; les polydiméthylsiloxanes comportant des groupements alkyle, alcoxy ou phényle, pendant ou en bout de chaîne siliconée, groupements ayant de 2 à 24 atomes de carbone ; les silicones phénylées comme les phényltriméthicones, les p hényldiméth icones, les phényltriméthylsiloxydiphényl- siloxane, les d ip hényl-d iméth icones, les diphénylméthyldiphényl trisiloxanes, les 2-phényléthyltriméthyl-siloxysilicates, et les polyméthylphénylsiloxanes ; - leurs mélanges. fatty acid having from 8 to 29 carbon atoms, and R2 represents a hydrocarbon chain, branched or unbranched, containing from 3 to 30 carbon atoms, for example purcellin oil, isononyl isononanoate, myristate d isopropyl, 2-ethylhexyl palmitate, octyl-2-dodecyl stearate, octyl-2-dodecyl erucate, isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, heptanoates, octanoates, decanoates of fatty alcohols; polyol esters, such as propylene glycol dioctanoate, neopentyl glycol diheptanoate and diethylene glycol diisononanoate; and pentaerythritol esters such as pentaerythrityl tetraisostearate; linear or branched hydrocarbons of mineral or synthetic origin, such as volatile or nonvolatile liquid paraffins, and derivatives thereof, branched chain hydrocarbon oils containing from 10 to 20 carbon atoms, such as isohexadecane, isododecane, isoparaffins and their mixtures, the

petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam oil; ; natural or synthetic essential oils such as, for example, eucalyptus, lavandin, lavender, vetiver, litsea cubeba, lemon, sandalwood, rosemary, chamomile, savory, walnut nutmeg, cinnamon, hyssop, caraway, orange, geraniol, cade and bergamot; alcohols and fatty acids having from 8 to 26 carbon atoms, such as alcohol or cetyl acid, stearyl alcohol, stearic acid, cetyl alcohol and stearyl alcohol mixture (cetylstearyl alcohol) octyl dodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol or linoleic alcohol; partially fluorinated hydrocarbon oils and / or silicone oils such as those described in document JP-A-2-295912; silicone oils such as volatile or non-volatile polymethylsiloxanes (PDMS) with a linear or cyclic silicone chain, which are liquid or pasty at room temperature, in particular cyclopolydimethylsiloxanes (cyclomethicones) such as cyclohexasiloxane; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, during or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenyl silicones such as phenyltrimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxane, diphenyl-imethicones, diphenylmethyldiphenyltrisiloxanes, 2-phenylethyltrimethylsiloxysilicates, and polymethylphenylsiloxanes; - their mixtures.

By hydrocarbon oil is meant in the list of oils mentioned above, any oil predominantly comprising carbon and hydrogen atoms, and optionally ester, ether, fluoro, carboxylic acid and / or alcohol groups.

According to one particular embodiment of the invention, the oily phase of the W / O emulsion comprises at least one oil chosen from silicone oils, especially volatile silicone oils (cyclomethicone) such as

<Desc / Clms Page number 12>

 cyclopentadimethylsiloxane and cyclotetradimethylsiloxane, branched chain hydrocarbon oils, such as isohexadecane, isododecane, isoparaffins, and mixtures thereof. The amount of these oils may range, for example, from 0.5 to 66.5% and preferably from 1 to 40% of the total weight of the triple emulsion.

The primary emulsion of the invention may further comprise one or more other fatty substances chosen from waxes, silicone gums and silicone resins.

As waxes, it is possible to use in particular silicone waxes such as alkoxydimethylsiloxanes, and more particularly stearoxypolydimethylsiloxane, alkylpolysiloxanes and mercapto-functional polydimethylsiloxanes.

As gums, it is possible to use in particular silicone gums such as high molecular weight polydimethylsiloxanes, hydroxyl-terminated polydimethylsiloxanes (dimethiconols).

As resins, it is possible to use in particular silicone resins such as trimethylsiloxysilicates.

The triple emulsion is prepared conventionally by preparing the primary emulsion and incorporating a determined amount of the primary emulsion into the external aqueous phase.

The emulsions of the invention may constitute cosmetic or dermatological compositions and may contain any adjuvants usually used in the cosmetic or dermatological field. They can be used in all the applications of these fields, in particular as skincare, protection, make-up, cleansing and / or make-up removal products for the skin and / or the hair, in particular for the face, the neck, for the hands, for the hair, for the scalp or for the body, as well as for the eyelashes, as sun products, as hair products and as shaving products.

et/ou les fibres kératiniques, c'est-à-dire les cheveux et/ou les cils. Also, the subject of the invention is also the cosmetic use of the emulsion according to the invention for cleaning and / or treating and / or protecting the skin and / or the mucous membranes

and / or the keratinous fibers, that is to say the hair and / or the eyelashes.

The subject of the invention is also the use of the emulsion according to the invention for the preparation of a dermatological ointment intended to treat and / or protect the skin and / or the mucous membranes and / or the keratinous fibers, it is to say the hair and / or eyelashes.

en ce qu'il consiste à appliquer sur la peau et/ou les muqueuses et/ou les fibres kératiniques, une composition telle que définie ci-dessus. The subject of the invention is also a cosmetic process for cleaning and / or treating and / or protecting the skin, the mucous membranes and / or the keratinous fibers, characterized

in that it consists in applying to the skin and / or the mucous membranes and / or the keratin fibers, a composition as defined above.

<Desc / Clms Page number 13>

The composition according to the invention may constitute, in particular, creams for the protection, treatment or care of the face, for the hands, for the feet, body care or care milks, lotions, gels or mousses for the care of the skin. skin, mucous membranes, hair and scalp.

As adjuvants, mention may be made, for example, of hydrophilic or lipophilic active agents, preservatives, antioxidants, perfumes, solvents, fillers, sunscreens, dyestuffs, basic agents (triethanolamine, sodium hydroxide) or acidic agents and also the lipid vesicles or any other type of vector (nanocapsules, microcapsules, etc ...). These adjuvants are used in the usual proportions in the cosmetics field, and for example from 0.01 to 30% of the total weight of the emulsion, and they are, according to their nature, introduced into the aqueous phase or the oily phase of the emulsion, or in vesicles or any other type of vector. These adjuvants, depending on their nature, can be introduced into the oily phase or into the aqueous phases. These adjuvants and their concentrations must be such that they do not modify the property desired for the emulsion of the invention.

la vitamine B5 (panthénol), la vitamine B3 (niacinamide), les dérivés de ces vitamines (notamment esters) et leurs mélanges ; l'urée ; la caféine ; les dépigmentants tels que l'acide kojique, l'hydroquinone et l'acide caféique ; l'acide salicylique et ses dérivés ; les alpha-hydroxyacides tels que l'acide lactique et l'acide glycolique et leurs dérivés ; les rétinoïdes tels que les caroténoïdes et les dérivés de vitamine A ; les filtres solaires ; l'hydrocortisone ; la mélatonine ; les extraits d'algues, de champignons, de végétaux, de levures, de bactéries ; les stéroïdes ; les actifs anti-bactériens comme le 2,4, 4'-trichloro-2'-hydroxy diphenyl éther (ou triclosan), le 3,4, 4'-trichlorocarbanilide (ou triclocarban) et les acides indiqués ci-dessus et notamment l'acide salicylique et ses dérivés ; les agents matifiants comme les fibres ; les agents tenseurs ; les céramides ; les huiles essentielles ; et leurs mélanges ; et tout actif approprié pour le but final de la composition. As active agents that can be used in the composition of the invention, mention may be made, for example, of enzymes (for example lactoperoxidase, lipase, protease, phospholipase, cellulases) and flavonoids; moisturizing agents such as hydrolysas of proteins; sodium hyaluronate; polyols such as glycerin, glycols such as polyethylene glycols, and sugar derivatives; anti-inflammatories; procyannidol oligomers; vitamins such as vitamin A (retinol), vitamin E (tocopherol), vitamin C (ascorbic acid),

vitamin B5 (panthenol), vitamin B3 (niacinamide), derivatives of these vitamins (especially esters) and mixtures thereof; urea; caffeine; depigmenting agents such as kojic acid, hydroquinone and caffeic acid; salicylic acid and its derivatives; alpha-hydroxy acids such as lactic acid and glycolic acid and their derivatives; retinoids such as carotenoids and vitamin A derivatives; solar filters; hydrocortisone; melatonin; extracts of algae, mushrooms, vegetables, yeasts, bacteria; steroids; anti-bacterial active agents such as 2,4,4'-trichloro-2'-hydroxy diphenyl ether (or triclosan), 3,4,4'-trichlorocarbanilide (or triclocarban) and the acids indicated above, and in particular salicylic acid and its derivatives; mattifying agents such as fibers; tensors; ceramides; essential oils ; and their mixtures; and any suitable asset for the ultimate purpose of the composition.

As examples of steroids, mention may be made of dehydroepiandrosterone (or DHEA), as well as (1) its precursors and biological derivatives, in particular salts and esters of DHEA, such as DHEA sulfate and salicylate, 7-hydroxy-DHEA. 7-keto DHEA, 7-hydroxy and 7-keto DHEA esters, especially 3beta-acetoxy-7-oxo DHEA, and (2) its precursors and chemical derivatives, in particular sapogenins such as diosgenin or hecogenin, and / or their derivatives such as hecogenin acetate, and / or natural extracts containing it and in particular extracts of Dioscoreas, such as wild yam (Wild Yam).

<Desc / Clms Page number 14>

As filters, one can use for example in the composition of the invention, organic U.V. filters or physical filters. The filter or filters may be present in an amount ranging from 0.1 to 25% by weight of active material, preferably from 1 to 20% by weight, and better still from 5 to 15% by weight relative to the total weight of the composition. .

Dérivés de / ?'-d/phény/ac/y/ae : Examples of organic screening agents that are active in the UV-A and / or UV-B range that may be used in the composition of the invention include, for example, designated above under their CTFA name: Derivatives of para-aminobenzoic acid (PABA): PABA, Ethyl PABA, Ethyl Dihydroxypropyl PABA, Ethylhexyl Dimethyl PABA sold in particular under the trade name
ESCALOL 507 by ISP, Glyceryl PABA, PEG-25 PABA sold under the trade name Uvinul P25 by BASF, Salicylic derivatives: Homosalate sold under the trade name EUSOLEX HMS by RONA / EM
INDUSTRIES, - Ethylhexyl salicylate (or ethyl hexyl salicylate) sold under the trade name NEO HELIOPAN OS by HAARMANN and REIMER, - Dipropylene glycol salicylate sold under the trade name DIPSAL by
SCHER, - TEA Salicylate, sold under the trade name NEO HELIOPAN TS by
HAARMANN and REIMER, Derivatives of dibenzoylmethane: butyl methoxydibenzoylmethane sold in particular under the trade name
PARSOL 1789 by HOFFMANN LA ROCHE, - Isopropyl Dibenzoylmethane, cinnamic derivatives: - Ethylhexyl Methoxycinnamate (or Octyl Methoxycinnamate) sold in particular under the trade name PARSOL MCX by HOFFMANN LA
ROCHE, - Isopropyl Methoxycinnamate, - Isoamyl Methoxycinnamate sold under the trade name NEO HELIOPAN E
1000 by HAARMANN and REIMER, - Cinoxate, - DEA Methoxycinnamate, - Diisopropyl Methylcinnamate, - Glyceryl Ethylhexanoate Dimethoxycinnamate

Derivatives of /? '- d / pheny / ac / y / ae:

<Desc / Clms Page number 15>

- Octocrylene (α-cyano-p-s-diphenylacrylate of 2-ethylhexyl) sold in particular under the trade name UVINUL N539 by BASF, - Etocrylene, sold in particular under the trade name UVINUL N35 by
BASF, Derivatives of benzophenone: Benzophenone-1 sold under the trade name UVINUL 400 by BASF; Benzophenone-2 sold under the trade name UVINUL D50 by BASF-Benzophenone-3 or Oxybenzone, sold under the trade name Uvinul
M40 by BASF, - Benzophenone-4 sold under the trade name UVINUL MS40 by BASF, - Benzophenone-5, - Benzophenone-6 sold under the trade name HELISORB 11 by
NORQUAY, - Benzophenone-8 sold under the trade name SPECTRA-SORB UV-24 by
AMERICAN CYANAMID, Benzophenone-9 sold under the trade name UVINUL OS-49 by BASF, Benzophenone-12, Derivatives of benzylidene camphor: 3-Benzylidene camphor manufactured under the name MEXORYL SD by CHIMEX, 4-Methylbenzylidene camphor sold under the trade name EUSOLEX 6300 by MERCK 1 - Benzylidene Camphor Sulfonic Acid manufactured under the name MEXORYL SL by CHIMEX, - Camphor Benzalkonium Methosulfate manufactured under the name MEXORYL SO by
CHIMEX, Terephthalylidene Dicamphor Sulfonic Acid manufactured under the name MEXORYL SX by CHIMEX, - Polyacrylamidomethyl Benzylidene Camphor manufactured under the name MESORYL
SW by CHIMEX, Derivatives of phenyl benzimidazole: - Phenylbenzimidazole Sulfonic Acid sold in particular under the trade name
EUSOLEX 232 by MERCK, - Benzimidazilate sold under the trade name NEO HELIOPAN
PA by HAARMANN and REIMER, Triazine derivatives: Anisotriazine sold under the trade name Tinosorb S by Ciba Geigy, Ethylhexyl triazone sold in particular under the trade name UVINUL T150 by BASF, BASF, Diethylhexyl butamido triazone sold under the trade name UVASORB
HEB by SIGMA 3V, Derivatives of phenyl benzotriazole: Drometrizole Trisiloxane sold under the trade name SILATRIZOLE by
RHODIA CHEMISTRY,

<Desc / Clms Page number 16>

Anthranilic Derivatives: Menthyl anthranilate sold under the trade name NEO HELIOPAN MA by
HAARMANN and REIMER, Imidazoline derivatives: Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate, Derivatives of benzalmalonate: Polyorganosiloxane with benzalmalonate functions sold under the trade name PARSOL SLX by HOFFMANN LA ROCHE and their mixtures.

The more particularly preferred organic UV filters are chosen from the following compounds: Ethylhexyl salicylate, Butyl Methoxydibenzoylmethane, Ethylhexyl Methoxycinnamate, Octocrylene, Phenylbenzimidazole Sulfonic Acid (phenylbenzimidazole sulfonic acid), Terephthalylidene Dicamphor Sulfonic (terephthalylidene dicamphosulphonic acid).

- Methylene bis-Benzotriazolyl Tetramethylbutylphenol (méthylène bisbenzotriazolyl tétraméthylbutylphenol), - Drometrizole Trisiloxane, - et leurs mélanges. Benzophenone-3, Benzophenone-4, Benzophenone-5, 4-Methylbenzylidene camphor (4-methylbenzylidene camphor), Benzimidazilate, Anisotriazine, Ethylhexyl triazone, Diethylhexylbutamido triazone,

Methylene bis-benzotriazolyl tetramethylbutylphenol (methylenebisbenzotriazolyl tetramethylbutylphenol), drometrizole trisiloxane, and mixtures thereof.

Tioveil Fin, Tioveil OP, Tioveil MOTG et Tioveil IPM par la société TIOXIDE, As physical filters which may be added in the composition of the invention, mention may be made, for example, of pigments and nano-pigments of metal oxides, coated or uncoated, in particular the oxides of titanium, iron, zirconium, zinc or cerium, and mixtures thereof, these oxides may be in the form of micro-or nanoparticles (nanopigments), optionally coated. The treated nanopigments may more particularly be titanium oxides treated with: silica and alumina, such as the products sold under the names Microtitanium Dioxide MT 500 SA and Microtitanium Dioxide MT 100 SA by the company Tayca, and the products marketed under the denominations

Tioveil Fin, Tioveil OP, Tioveil MOTG and Tioveil IPM by the company TIOXIDE,

<Desc / Clms Page number 17>

- l'alumine et le stéarate d'aluminium, tels que le produit commercialisé sous la dénomination Microtitanium Dioxide MT 100 T par la société TAYCA, - l'alumine et le laurate d'aluminium, tels que le produit commercialisé sous la dénomination Microtitanium Dioxide MT 100 S par la société TAYCA, - des oxydes de fer et le stéarate de fer, tels que le produit commercialisé sous la dénomination Microtitanium Dioxide MT 100 F par la société TAYCA, - la silice, l'alumine et la silicone, tels que les produits commercialisés sous les dénominations Microtitanium Dioxide MT 100 SAS, Microtitanium Dioxide MT 600 SAS et Microtitanium Dioxide MT 500 SAS par la société TAYCA, - l'hexamétaphosphate de sodium, tels que le produit commercialisé sous la dénomination Microtitanium Dioxide MT 150 W par la société TAYCA, - l'octyltriméthoxysilane, tels que le produit commercialisé sous la dénomination T-805 par la société DEGUSSA, - l'alumine et l'acide stéarique, tels que le produit commercialisé sous la dénomination UVT-M160 par la société KEMIRA, - l'alumine et la glycérine, tels que le produit commercialisé sous la dénomination UVT-M212 par la société KEMIRA, - l'alumine et la silicone, tels que le produit commercialisé sous la dénomination UVT-M262 par la société KEMIRA.

aluminum alumina and stearate, such as the product marketed under the name Microtitanium Dioxide MT 100 T by Tayca; aluminum alumina and laurate, such as the product marketed under the name Microtitanium Dioxide; MT 100 S by the company TAYCA, - iron oxides and iron stearate, such as the product marketed under the name Microtitanium Dioxide MT 100 F by the company Tayca, - silica, alumina and silicone, such as the products marketed under the names Microtitanium Dioxide MT 100 SAS, Microtitanium Dioxide MT 600 SAS and Microtitanium Dioxide MT 500 SAS by the company Tayca; sodium hexametaphosphate, such as the product marketed under the name Microtitanium Dioxide MT 150 W by the company TAYCA company, octyltrimethoxysilane, such as the product sold under the name T-805 by Degussa, alumina and stearic acid, such as oduct marketed under the name UVT-M160 by the company KEMIRA, - alumina and glycerine, such as the product sold under the name UVT-M212 by KEMIRA, - alumina and silicone, such as the product marketed under the name UVT-M262 by KEMIRA.

The untreated titanium oxides may, for example, be those sold by Tayca under the trade names Microtitanium Dioxide MT 500 B or Microtitanium Dioxide MT 600 B.

The untreated zinc oxides can for example be those sold by the company SUMITOMO under the name Ultra Fine Zinc Oxide Powder, by the company PRESPERSE under the name Finex 25, by the company IKEDA under the name MZO-25 or by the company SUNSMART under the name ZCOTE. The treated zinc oxides may for example be those sold by Sunsmart under the name Z-Cote HP 1.

The following examples of compositions according to the invention are given by way of illustration and without limitation. Quantities are given in% by weight unless otherwise stated.

EXAMPLE 1 Primary emulsion: Phase A: Polyglyceryl-4 isostearate / hexyl laurate Cetyl dimethicone copolyol (Abil WE 09) 4% - Cyclomethicone 11.7% - Dimethicone 2.7% - Parléam oil 16.7% - Isohexadecane 16 , 7%

<Desc / Clms Page number 18>

 Phase B: - Glycerine 2% - NaCl 0.6% - Demineralized water 45.6% The second phase is poured into the first phase with vigorous stirring at room temperature. The emulsion obtained is an W / O emulsion.

2. Triple Emulsion: Phase A: - Primary Emulsion 40% Phase B: - AMPS Copolymer (*) 0, 6% - 10% Triethanolamine 0.03% - Preservatives 1% - Glucose 4.9% - Glycerin 2 , 8% - Demineralized water qs 100% (*) Copolymer consisting of 80% by weight of NH3 neutralized AMPS units and 20% by weight of methacrylate units of GENAPOL T080 [units of formula (III) in which R1 = CH3, R4 = C16-C18 and x = 8].

Phase A is poured into phase B with moderate stirring. The emulsion obtained according to the invention is a multiple W / O / W emulsion comprising a large number of multiple internal blood cells.

A triple emulsion capable of moisturizing the skin is obtained.

Comparative Examples The table below shows Example 1 according to the invention compared to three comparative examples not forming part of the invention.

<Desc / Clms Page number 19>

<Tb>
<Tb>

Example <SEP> 1 <SEP> Counter-Counterbalance Example <SEP> 1 <SEP> Example <SEP> 2 <SEP> Example <SEP> 3
<tb> A. <SEP> Emulsion <SEP> Primary <SEP> 40% <SEP> 40% <SEP> 40% <SEP> 40%
<tb> B. <SEP> Copolymer <SEP> 0. <SEP> 6%
<tb> of AMPS
<tb> Pemulen <SEP> TRI <SEP> 0. <SEP> 3% <SEP> 0.8% <SEP> 0.3%
<tb> Hostacerin <SEP> AMPS <SEP> - <SEP> - <SEP> - <SEP> 0. <SEP> 4%
<tb> Triethanolamine <SEP> to <SEP> 0.03% <SEP> 0.3% <SEP> 0. <SEP> 8%
<tb> 10%
<tb> Preservatives <SEP> 1% <SEP> 1% <SEP> 1% <SEP> 1%
<tb> Glucose <SEP> 4.9% <SEP> 4.9% <SEP> 4.9% <SEP> 4.9%
<tb> Glycerin <SEP> 2.8% <SEP> 2.8% <SEP> 2.8% <SEP> 2.8%
<tb> Demineralized water <SEP><SEP> Qsp <SEP> 100% <SEP> Qsp <SEP> 100% <SEP> Qsp <SEP> 100% <SEP> 27,7%
<tb> C. <SEP> Triethanolamine <SEP> to <SEP> - <SEP> - <SEP> - <SEP> 0. <SEP> 3%
<tb> 10%
<tb> Demineralized <SEP> Water <SEP> - <SEP> - <SEP> - <SEP> 2%
<tb> D. <SEP> Demineralized <SEP><SEP> Water <SEP> - <SEP> - <SEP> - <SEP> 20
<tb> HostacerinAMPS --- 0. <SEP> 6%
<tb> Results <SEP> Emulsion <SEP> Emulsion <SEP> Emulsion <SEP> Emulsion
<tb> multiple <SEP> multiple <SEP> multiple <SEP> direct <SEP> (H / E)
<tb> Milk <SEP> white <SEP> and <SEP> Milk <SEP> white <SEP> Cream <SEP> Milk <SEP> white
<tb> homogeneous <SEP> of appearance <SEP> granular <SEP> of appearance
<tb> heterogeneous <SEP> heterogeneous
<tb> Stability <SEP> Stable <SEP> after <SEP> Release <SEP> Release <SEP> Stable <SEP> After
<tb> 48 <SEP> hours <SEP> of oil <SEP> of oil <SEP> 48h
<tb> after <SEP> 48 <SEP> after <SEP> 48
<tb> hours <SEP> hours
<Tb>
Procedure: Phase A is poured into phase B with moderate stirring. When present, phases C and D are introduced under the same conditions consecutively.

In the case of Example 1, the emulsion obtained is a multiple W / O / W emulsion comprising a large number of multiple globules. In counterexamples 1 and 2, the emulsions obtained are multiple but have a reduced number of multiple globules. Moreover, they have a heterogeneous aspect and are very unstable over time. In counterexample 3, the emulsion obtained is a direct emulsion (O / W) and not a multiple emulsion.

Claims (44)

 1. Water / oil / water emulsion for topical application, comprising an external aqueous phase, an oily phase constituting, with an internal aqueous phase, a primary emulsion water / oil, characterized in that the external aqueous phase contains at least one polymer uncrosslinked hydrophilic amphiphile having at least two hydrophobic side members. 2. Emulsion according to claim 1, characterized in that the polymer is capable of being obtained from at least one hydrophilic monomer A with ethylenic unsaturation and at least one hydrophobic monomer B. 3. Emulsion according to the preceding claim, characterized in that the monomer A comprises at least one oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a chlorine atom, a fluorine atom or their mixtures. 4. Emulsion according to the preceding claim, characterized in that the monomer A has a sulfonic acid or phosphonic acid function. 5. Emulsion according to any one of claims 2 to 4, characterized in that the hydrophobic monomer B comprises at least one hydrophobic radical selected from: - Cg-Cg alkyl radicals, saturated or unsaturated, linear, branched or cyclic ;

 - fluorinated radicals or a) ky! f) uorés in Cg-Cgo; the cholesteryl radical or the radicals derived from cholesterol; - polycyclic aromatic groups; silicone or alkylsilicone or alkylfluorosilicone radicals. 6. Emulsion according to the preceding claim, characterized in that the hydrophobic monomer B comprises at least one hydrophobic radical selected from linear or branched alkyl radicals. 7. Emulsion according to the preceding claim, characterized in that the hydrophobic monomer is an alkyl chain having from 6 to 30 carbon atoms. 8. Emulsion according to any one of the preceding claims, characterized in that the polymer is neutralized partially or completely by a mineral or organic base. 9. Emulsion according to any one of the preceding claims, characterized in that the polymer has a number average molecular weight ranging from 1000 to 20 000 000 g / mol. 10. Emulsion according to the preceding claim, characterized in that the number average molecular weight ranges from 20,000 to 5,000,000 g / mol. <Desc / Clms Page number 21> 11. Emulsion according to any one of the preceding claims, characterized in that the polymer is capable of being obtained from at least one ethylenically unsaturated monomer containing sulphonic group, in free form or partially or completely neutralized, and at least one hydrophobic monomer. 12. Emulsion according to the preceding claim, characterized in that the ethylenically unsaturated monomer containing sulfonic group is chosen from vinylsulfonic acid, styrene sulfonic acid, (meth) acrylamido (C1-C22) alkylsulphonic acids, N- (C1-C22) (C1-C22) alkyl (meth) acrylamido alkylsulfonic acids and their partially or completely neutralized forms, and mixtures thereof. 13. Emulsion according to the preceding claim, characterized in that the ethylenically unsaturated monomer containing sulfonic group is selected from acrylamido-methanesulfonic acid, acrylamido-ethanesulfonic acid,

 acrylamido-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, acid 2 2,4,4-trimethylpentanesulfonic acid acrylate, 2-methacrylamido-dodecylsulfonic acid, 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and their partially or totally neutralized forms , and their mixtures. 14. Emulsion according to claim 12 or 13, characterized in that the ethylenically unsaturated monomer containing sulfonic group is 2-acrylamido-2-methylpropanesulfonic acid (AMPS), and its partially or completely neutralized forms. 15. Emulsion according to the preceding claim, characterized in that the amphiphilic polymer is chosen from the random polymers of AMPS modified by reaction with a n-mono (C6-C22) alkylamine or a di-n- (C6-C22) alkylamine. 16. Emulsion according to the preceding claim, characterized in that the AMPS amphiphilic polymer additionally contains at least one ethylenically unsaturated monomer chosen from (meth) acrylic acids and their alkyl derivatives substituted in ss, and their esters obtained with monoalcohols or mono or polyalkylene glycols, or from (meth) acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid, maleic acid, cationic monomers, or mixtures thereof. 17. Emulsion according to any one of the preceding claims, characterized in that the amphiphilic polymer is chosen from amphiphilic copolymers of AMPS and at least one hydrophobic monomer with ethylenic unsaturation comprising at least one hydrophobic part having from 6 to 30 carbon atoms. <Desc / Clms Page number 22> 18. Emulsion according to the preceding claim, characterized in that the hydrophobic portion comprises from 6 to 22 carbon atoms. 19. Emulsion according to claim 17 or 18, characterized in that the hydrophobic monomer containing ethylenic unsaturation is chosen from acrylates, alkyl acrylates, acrylamides or alkyl acrylamides of formula (1) below:

 in ! aque! ! e R 1 and R 8, which may be identical or different, denote a hydrogen atom or a linear or branched C 1 -C 6 alkyl radical; Y is 0 or NH; Ruz denotes a hydrophobic hydrocarbon radical containing at least 6 to 50 carbon atoms; x denotes a number of moles of alkylene oxide and ranges from 0 to 100. 20. Emulsion according to the preceding claim, characterized in that the hydrophobic radical R2 is chosen from linear, branched or cyclic C6-C18 alkyl radicals; C 6 -C 18 perfluorinated alkyl radicals; the cholesteryl radical or a cholesterol ester residue; polycyclic aromatic groups. 21. Emulsion according to claim 19 or 20, characterized in that the monomer of formula (1) comprises at least one alkylene oxide unit (x 1). 22. Emulsion according to any one of claims 19 to 21, characterized in that the monomer of formula (1) comprises at least one polyoxyalkylene chain. 23. Emulsion according to the preceding claim, characterized in that the polyoxyalkylene chain consists solely of ethylene oxide units. 24. Emulsion according to any one of claims 19 to 23, characterized in that the number of moles of alkylene oxide ranges from 3 to 100. 25. Emulsion according to the preceding claim, characterized in that the number of moles of alkylene oxide ranges from 3 to 50. 26. Emulsion according to any one of claims 17 to 19, characterized in that the amphiphilic polymer of AMPS is chosen from: - uncrosslinked copolymers, neutralized or not, comprising 15 to 60% by weight of AMPS units and from 40 to 85% by weight of grounds <Desc / Clms Page number 23>  (C 8 -C 18) alkyl (meth) acrylamide or (C 8 -C 18) alkyl (meth) acrylate units, with respect to the polymer; terpolymers comprising from 10 to 90 mol% of acrylamide units, from 0.1 to 10 mol% of AMPS units and 5 to 80 mol% of n- (Ce-Cg) alkylacrylamide units, based on the polymer; uncrosslinked copolymers of partially or totally neutralized AMPS and n-dodecyl methacrylate; , n-hexadecyl and / or n-octadecyl. uncrosslinked copolymers of partially or totally neutralized AMPS and n-dodecylmethacrylamide. 27. Emulsion according to claims 17 to 19, characterized in that the AMPS amphiphilic polymer is chosen from copolymers consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) units of formula (II) below:

 in which X + is a proton, an alkali metal cation, an alkaline earth cation or the ammonium ion, and units of the following formula (III):

 wherein x is an integer ranging from 3 to 100; R1 has the same meaning as that indicated above in formula (1) and R4 denotes linear or branched Cg-C alkyl. 28. Emulsion according to the preceding claim, characterized in that x = 25, R1 denotes the methyl radical and R4 is n-dodecyl, n-hexadecyl, noctadecyl. 29. Emulsion according to claim 27, characterized in that x = 8, R1 denotes the methyl radical and R4 is C16-18. <Desc / Clms Page number 24> 30. Emulsion according to claim 19 or 27, characterized in that the molar proportion in% of units of formula (1) or units of formula (III) in the polymers ranges from 0.1 to 99%. 31. Emulsion according to any one of the preceding claims, characterized in that the amphiphilic polymer is prepared by radical polymerization by precipitation in tert-butanol. 32. Emulsion according to any one of the preceding claims, characterized in that the amount of amphiphilic polymer (s) ranges from 0.01% to 20% by weight of active material and preferably from 0.02% to 10% by weight. % by weight of active material, relative to the total weight of the emulsion. 33. Emulsion according to any one of the preceding claims, characterized in that the primary W / O emulsion comprises at least one HLB emulsifier of less than 10. 34. Emulsion according to the preceding claim, characterized in that the emulsifier is selected from the group comprising alkoxylated fatty alcohols, alkoxylated fatty esters, fatty acid salts, sugar-derived surfactants, silicone emulsifiers and mixtures thereof. . 35. Emulsion according to the preceding claim, characterized in that the emulsifier is chosen from dimethicone copolyols, alkyldimethicone copolyols and mixtures containing them. 36. Emulsion according to any one of claims 35 to 37, characterized in that the emulsifier is present in an amount ranging from 0.1 to 10% and preferably from 0.5 to 5% of the total weight of the primary emulsion. 37. Emulsion according to any one of the preceding claims, characterized in that the aqueous phase of the primary emulsion and / or the external aqueous phase contain at least one osmotic agent chosen from polyols, sugars, salts and polymers. , and their mixtures. 38. Emulsion according to the preceding claim, characterized in that the amount of osmotic agent ranges from 0.01 to 50% by weight relative to the total weight of the triple emulsion. 39. Emulsion according to any one of the preceding claims, characterized in that the primary W / O emulsion represents from 5 to 70% by weight relative to the total weight of the triple emulsion. 40. Emulsion according to any one of the preceding claims, characterized in that the oily phase of the primary emulsion comprises at least one oil selected from silicone oils, branched chain hydrocarbon oils, and mixtures thereof. <Desc / Clms Page number 25> 41. Emulsion according to any one of the preceding claims, characterized in that it constitutes a cosmetic or dermatological composition. 42. Cosmetic use of the emulsion according to any one of claims 1 to 40, for cleaning and / or treating and / or protecting the skin and / or mucous membranes and / or keratinous fibers. 43. Use of the emulsion according to any one of claims 1 to 40 for the preparation of a dermatological ointment for treating and / or protecting the skin and / or mucous membranes and / or keratinous fibers. 44. Cosmetic process for cleaning and / or treating and / or protecting the skin and / or keratinous fibers, characterized in that it consists in applying to the skin, the mucous membranes and / or the keratinous fibers, an emulsion according to any of claims 1 to 40.