Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/04—Dispersions; Emulsions
  • A61K8/06—Emulsions
  • A61K8/066—Multiple emulsions, e.g. water-in-oil-in-water
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/60—Sugars; Derivatives thereof
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/73—Polysaccharides
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/90—Block copolymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin

Definitions

• the present invention relates to cosmetic and / or dermatological formulations comprising at least two active materials in a multiple emulsion of water in oil in water type, optionally mixed with a simple emulsion of oil in water type.
• the present invention which therefore consists of a cosmetic and / or dermatological formulation comprising at least two active materials in a multiple emulsion consisting of an internal aqueous phase dispersed in an internal oily phase, all being dispersed in an external aqueous phase; the multiple emulsion being optionally mixed with a simple emulsion consisting of an external oily phase dispersed in an external aqueous phase: ⁇ the internal oily phase comprising at least one nonionic surfactant and / or at least one amphiphilic polymer and optionally at least one hydrophobic active ingredient; ⁇ the external aqueous phase comprising at least one nonionic surfactant and / or at least one nonionic amphiphilic polymer optionally associated with at least one anionic amphiphilic polymer or comprising at least one anionic amphiphilic polymer optionally associated with at least one anionic surfactant; ⁇ at least one hydrophilic active material found in the internal aqueous phase; and Q
• the term mixed emulsion will denote either the multiple emulsion or the multiple emulsion mixed with the single emulsion.
• the mixed emulsion used in the composition of cosmetic and / or dermatological formulations has the advantage of being easy to prepare and to implement, without requiring significant investment.
• the mixed emulsion is very particularly suitable when using two active materials, advantageously incompatible, one hydrophilic, the other hydrophobic; the first being introduced into the internal aqueous phase and the second into the external oily phase. In this way, the two active materials are isolated from one another in the mixed emulsion.
• a delay effect can be observed, during the application of the formulation, of the least available active material, for example that present in the internal aqueous phase of the mixed emulsion.
• polymer designates both homopolymers and copolymers.
• inverse emulsion of the multiple emulsion and its method of preparation will first be detailed.
• the reverse emulsion therefore consists of a water-in-oil emulsion, consisting of an internal aqueous phase and an internal oily phase.
• the internal oily phase comprises at least one organic oil, of animal or vegetable, or mineral origin, as well as waxes from the same origins, or their mixtures.
• an oily phase is used which is fluid under the conditions for preparing the reverse emulsion.
• the compound used as the oily phase is preferably chosen from the compounds whose solubility in water does not exceed 10% by weight at 25 ° C.
• organic oils of animal origin mention may be made, among others, of sperm whale oil, whale oil, seal oil, sardine oil, herring oil, shark oil, Cod liver oil ; pork and mutton fats (tallow).
• organic oils of vegetable origin there may be mentioned, among others, rapeseed oil, sunflower oil, peanut oil, olive oil, oil nuts, corn oil, soybean oil, linseed oil, hemp oil, grape seed oil, coconut oil, palm oil, oil cottonseed, babassu oil, jojoba oil, sesame oil, castor oil.
• waxes of vegetable origin mention may be made of carnauba wax.
• paraffinic waxes can likewise be suitable for the preparation of the emulsion.
• said acids, esters or alcohols comprise at least one hydrocarbon radical having from 10 to 40 carbon atoms, more particularly 18 to 40 carbon atoms, and can comprise one or more carbon-carbon double bonds, conjugated or not.
• the acids, esters or alcohols can comprise one or more hydroxyl groups.
• saturated fatty acids mention may be made of palmitic, stearic and behenic acids.
• unsaturated fatty acids there may be mentioned myristoleic, palmitoleic, oleic, erucic, linoleic, linolenic, arachidonic, ricinoleic acids, as well as their mixtures.
• fatty acid esters there may be mentioned the esters of the acids previously listed, for which the part deriving from the alcohol comprises 1 to 6 carbon atoms, such as the methyl, ethyl, propyl and isopropyl esters. , etc.
• esters of the abovementioned acids and of polyols such as for example glycerol, polyglycerol (such as for example polyricinoleate of polyglycerol), glycol, propylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol, neopentylglycol (such as neopentylglycol hydroxypivalate), pentaerythritol, dipentaerythritol, trimethylolpropane, sorbitol, mannitol, xylitol, mesoerythritol.
• polyols such as for example glycerol, polyglycerol (such as for example polyricinoleate of polyglycerol), glycol, propylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol, neopentylglycol (such as neopentylglycol hydroxypivalate
• the internal oily phase can likewise be chosen from essential oils, mono-, di- and tri-glycerides, as well as silicone oils. It can comprise at least one hydrophobic active material, as soon as it is compatible with the hydrophilic active material present in the internal aqueous phase and, if it is present, in the external aqueous phase; phases which will be described later.
• Said hydrophobic active materials are in liquid form, dissolved in an organic solvent, or also in the form of a divided solid dispersed in said phase.
• the active ingredients are such that their solubility in water does not exceed 10% by weight, at 25 ° C.
• Active materials whose melting point is less than or equal to 100 ° C., more particularly less than or equal to 80 ° C., can likewise be used.
• silicone oils belonging for example to the family of dimethicones
• lipophilic vitamins such as vitamin A and its derivatives, in particular its esters such as acetate, palmitate, propionate, vitamin B2, pantothenic acid, vitamin D and vitamin E
• mono-, di- and triglycerides bactericides
• UV absorbing agents such as aminobenzoate derivatives of the PABA and PARA type, salicylates, cinnamates, anthranilates, dibenzoylmethanes, camphor derivatives and their mixtures.
• Anti-aging agents can also be used.
• retinoids fat-soluble vitamins, derivatives of vitamin C such as esters, in particular acetate, propionate, palmitate; ceramides, pseudoceramides, phospholipids, fatty acids, fatty alcohols, cholesterol, sterols and their mixtures.
• ceramides pseudoceramides
• phospholipids fatty acids, fatty alcohols, cholesterol, sterols and their mixtures.
• fatty acids and alcohols mention may more particularly be made of those having linear or branched alkyl chains containing from 12 to 20 carbon atoms. It can in particular be linoleic acid.
• anti-cellulite agents such as in particular isobutylmethylxanthine and theophyline
• anti-acne agents such as, for example, resorcinol, resorcinol acetate, benzoyl peroxide and many natural compounds.
• Aromas, perfumes, essential oils, essences can also be used as a hydrophobic active material.
• compounds such as benzal
• the antimicrobial agents can be chosen from thymol, menthol, triclosan, 4-hexylresorcinol, phenol, eucalyptol, benzoic acid, benzoic peroxide, butyl paraben, and their mixtures.
• oily phase itself is considered as a hydrophobic active material.
• the internal oily phase comprises one or more hydrophobic active materials different from the oily phase
• their content represents more particularly 10 to 50% by weight of said internal oily phase.
• the reverse emulsion further comprises at least one nonionic surfactant and / or at least one amphiphilic polymer, preferably with blocks.
• the Bancroft rule can be applied to the nonionic surfactant and to the amphiphilic polymer, preferably to blocks, used (2 nd World Congress of Emulsion, 1997, Bordeaux, France).
• the fraction soluble in the continuous phase is greater than the fraction soluble in the dispersed phase.
• the surfactant and the polymer are preferably chosen from those which satisfy both of the two conditions below:
• the nonionic surfactant is chosen from compounds having an HLB (hydrophilic / lipophilic balance) value less than or equal to 8.
• surfactants capable of entering into the composition of the reverse emulsion, mention may be made of surfactants, alone or as a mixture, chosen from:
• alkoxylated alkyl phenols the number of alkoxylated units (ethoxylated, propoxylated, butoxylated) is such that the value of HLB is less than or equal to 8.
• the alkoxylated fatty alcohols generally comprise from 6 to 22 carbon atoms, the alkoxylated units being excluded of these numbers.
• the alkoxylated triglycerides can be triglycerides of plant or animal origin.
• the optionally alkoxylated sorbitan esters are cyclized fatty acid sorbitol esters comprising from 10 to 20 carbon atoms such as lauric acid, stearic acid or oleic acid.
• Alkoxylated fatty amines generally have from 10 to 22 carbon atoms, the 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.
• amphiphilic polymer this advantageously comprises at least two blocks.
• amphiphilic polymers verifying the Bancroft rule and the two conditions stated above, more particularly comprise at least one hydrophobic block and at least one neutral or anionic hydrophilic block.
• amphiphilic polymer comprises at least three blocks, and more particularly three blocks
• the polymer is preferably linear.
• the hydrophobic blocks are more particularly at the ends. If the polymers comprise more than three blocks, the latter are preferably in the form of grafted or combed polymers.
• amphiphilic block polymer will be used interchangeably for linear block polymers and grafted or combed polymers.
• Said amphiphilic polymers can advantageously be obtained by so-called living or controlled radical polymerization.
• living or controlled polymerization processes reference may in particular be made to applications WO 98/58974 (xanthate), WO 98/01478 (dithioesters), WO 99/03894 (nitroxides); WO 99/31144 (dithiocarbamates).
• Amphiphilic polymers can also be obtained by 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 grafted or combed polymers can also be obtained by methods known as direct grafting and copolymerization.
• Direct grafting consists in polymerizing the monomer (s) chosen by radical, in the presence of the selected polymer to form the backbone of the final product. If the monomer / skeleton couple as well as the operating conditions are judiciously chosen, then there may be a transfer reaction between the growing macroradical and the skeleton. This reaction generates a radical on the skeleton and it is from this radical that the graft grows. The primary radical originating from the initiator can also contribute to the transfer reactions.
• the copolymerization it first implements the grafting at the end of the future pendant segment, of a function which can be polymerized by the radical route. 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 skeleton and a so-called "comb" polymer is obtained.
• hydrophobic monomers from which the hydrophobic block (s) of the amphiphilic polymer can be prepared there may be mentioned in particular: - the esters of mono- or polycarboxylic acids, linear, branched, cyclic or aromatic, comprising at least one ethylenic unsaturation , esters of saturated carboxylic acids preferably comprising 8 to 30 carbon atoms, optionally carrying a hydroxyl group; - ⁇ -ethylenically unsaturated nitriles, vinyl ethers, vinyl esters, vinyl aromatic monomers, vinyl or vinylidene halides, hydrocarbon monomers, linear or branched, aromatic or not, comprising at least one ethylenic unsaturation, monomers of cyclic or non-cyclic siloxane type, chlorosilanes; propylene oxide, butylene oxide; alone or in mixtures, as well as the macromonomers derived from such monomers.
• hydrophobic monomers capable of entering into the preparation of the hydrophobic block (s) of the amphiphilic block polymer
• vinyl nitriles more particularly include those having 3 to 12 carbon atoms, such as in particular acrylonitrile and methacrylonitrile; - styrene, ⁇ -methylstyrene, vinyltoluene, butadiene, isoprene, chloroprene; alone or in mixtures, as well as the macromonomers derived from such monomers.
• the preferred monomers are the esters of acrylic acid with linear or branched C1-C4 alcohols such as methyl, ethyl, propyl and butyl acrylate, vinyl esters such as vinyl acetate, styrene, ⁇ -methylstyrene.
• 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-methyloI (meth) acrylamide; hydrophilic esters derived from (meth) acrylic acid such as for example 2-hydroxyethyl (meth) acrylate; vinyl esters making it possible to obtain polyvinyl alcohol blocks after hydrolysis, such as vinyl acetate, vinyl Versatate®, vinyl propionate, alone, in combination, as well as the macromonomers derived from such monomers. It is recalled that the term macromonomer designates a macromolecule carrying one or more polymerizable functions.
• the preferred hydrophilic monomers are acrylamide and methacrylamide, alone or as a mixture, or in the form of macromonomers.
• the anionic hydrophilic monomers from which the amphiphilic block polymers can be obtained mention may be made, for example, of the monomers comprising at least one carboxylic, sulfonic, sulfuric, phosphonic, phosphoric, sulfosuccinic function, or the corresponding salts.
• the functions of the anionic block or blocks of the polymer are in an at least partially ionized (dissociated) form. More particularly, at least 10 mol% of the functions of the block or blocks are in ionized form.
• the determination of this value poses no 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 monomer carrying ionizable functions used during the preparation of the polymer).
• the monomers are chosen from: - linear, branched, cyclic or aromatic mono- or polycarboxylic acids, N-substituted derivatives of such acids; monoesters of polycarboxylic acids, comprising at least one ethylenic unsaturation;
• anionic monomers there may be mentioned without intending to be limited thereto:
• vinyl sulfonic acid vinylbenzene sulfonic acid, vinyl phosphonic acid, vinylidene phosphoric acid, vinyl benzoic acid, as well as alkali metal salts, such as sodium, potassium, or ammonium ;
• monomers which are precursors of those which have just been mentioned.
• these monomers have units which, once incorporated in the polymer chain, can be transformed, in particular by a chemical treatment such as hydrolysis, to restore the aforementioned anionic species.
• the fully or partially esterified monomers of the aforementioned monomers can be used to be, subsequently, completely or partially hydrolyzed.
• the amphiphilic block polymers have a molar mass by weight 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.
• an amphiphilic polymer with nonionic type blocks is used.
• an amphiphilic block polymer suitable for implementing the invention mention may be made of polyhydroxystearate - polyethylene glycol - polyhydroxystearate triblock polymers (the products of the Arlacel range from ICI are an example), polymers with polydimethylsiloxane blocks grafted polyalkyl polyether (like the products of the brand Tegopren marketed by Goldschmidt).
• At least one surfactant at least one nonionic amphiphilic polymer, or mixtures thereof, is used.
• the reverse emulsion comprises an amphiphilic polymer, preferably block and nonionic, or a mixture of several of them.
• the total amount of surfactant and / or amphiphilic polymer preferably represents from 2 to 10% by weight of the internal oily phase.
• the internal aqueous phase comprises at least one hydrophilic active material, which is in a form soluble in the internal aqueous phase; in a form dissolved in a water-miscible solvent such as methanol, ethanol, propylene glycol, glycerol; in the form of a divided solid dispersed in said phase.
• a water-miscible solvent such as methanol, ethanol, propylene glycol, glycerol
• the content of hydrophilic active material is more particularly between 0.1 and 50% by weight of the internal aqueous phase, and preferably between 0.1 and 20% by weight of the internal aqueous phase.
• 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 skin and hair.
• skin and hair conditioning agents such as in particular polymers comprising quaternary ammoniums which can optionally be used in heterocycles (compounds of the quaternium, polyquaternium type, etc.).
• humectants which are more particularly chosen from polymers (homo-, co- or ter-polymers, for example acrylamide, acrylamide / sodium acrylate, polystyrene sulfonate, etc.), cationic polymers, polyvinylpyrrolidone, polyvinyl acetate, etc.
• coloring agents which can be used in deodorants and which are more particularly aluminum, zirconium salts; antibacterial agents; anti-inflammatory agents, anesthetic agents, sunscreens, etc.
• - and ⁇ -hydroxy acids such as citric, lactic, glycolic and salicylic acids
• dicarboxylic acids preferably unsaturated and 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 biocides, as suitable active materials in cosmetic and / or dermatological formulations.
• the internal aqueous phase may comprise at least one additive chosen from salts such as the halides of alkali or alkaline earth metals (such as sodium chloride, calcium chloride) , or alkali or alkaline earth metal sulfates (such as magnesium sulfate), or mixtures thereof.
• the internal aqueous phase can also comprise, as an additive, at least one sugar, such as glucose for example, or also at least one polysaccharide, such as in particular dextran, or mixtures thereof. We can obviously have a combination of these various types of additives.
• the salt concentration in the internal aqueous phase when the latter is present, is more particularly between 0.05 and 1 mol / l, preferably 0.1 to 0.4 mol / l.
• the sugar and / or polysaccharide concentration is such that the osmotic pressure of the internal aqueous phase comprising the sugar and / or polysaccharide corresponds to the osmotic pressure of a internal aqueous phase comprising 0.05 to 1 mol / l of salt.
• the inverse emulsion of the multiple emulsion more particularly has a weight proportion aqueous phase / oily phase of between 10/90 and 90/10.
• the weight proportion of aqueous phase / oily phase is between 30/70 and 80/20.
• the reverse emulsion is prepared by implementing the conventional methods.
• a first mixture is prepared, comprising water, the hydrophilic active material and optionally the additive (salt, sugar, polysaccharide), and on the other hand, a second mixture comprising the oil, optionally the hydrophobic active material and the surfactant and / or the amphiphilic polymer.
• the first mixture is then added to the second, with stirring.
• the stirring is preferably strong and can be, advantageously, provided by the use of an apparatus of the Ultra-Turrax® type, Microfluidizer, or any high pressure homogenizer.
• the stirring can advantageously be carried out by means of a frame blade.
• the preparation of the reverse emulsion is generally carried out at a temperature above the melting temperature of the oily phase. Usually, the temperature for preparing the reverse emulsion is between 20 and 80 ° C.
• the duration of the agitation can be determined without difficulty by a person skilled in the art and depends on the type of apparatus used. It is preferably sufficient to obtain an average droplet size of between 0.1 and 10 ⁇ m, preferably between 0.1 and 5 ⁇ m (measured using a Horiba granulometer)
• the external aqueous phase can comprise at least one active material which is dissolved in the external aqueous phase, either in a form dissolved in a solvent miscible with the external aqueous phase, such as methanol, ethanol , propylene glycol, glycerol, either in the form of a divided solid dispersed in said external aqueous phase.
• active material such as methanol, ethanol , propylene glycol, glycerol
• the content of active material is more particularly between 0.1 and 50% by weight of the external aqueous phase, and preferably between 0.1 and 20% by weight of the external aqueous phase.
• the external aqueous phase additionally comprises at least nonionic surfactant and / or at least one nonionic amphiphilic polymer optionally associated with at least one anionic amphiphilic polymer.
• the external aqueous phase comprises at least one anionic amphiphilic polymer optionally combined with at least one anionic surfactant.
• the Bancroft rule can be applied to the surfactants and polymers used (fraction soluble in the continuous phase is greater than the fraction soluble in the dispersed phase).
• the surfactant and the polymer are preferably chosen from those which satisfy both of the two conditions below:
• the external aqueous phase 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) / polymer (s) is between 0.5 and 10% by weight, preferably between 1 and 5% by weight, relative to the oily phase or to the reverse emulsion if it is present; the amount of anionic amphiphilic surfactant and / or polymer represents 0.5 to 5% by weight, preferably 0.5 to 2% by weight, relative to the weight of nonionic amphiphilic surfactant / polymer; or
• At least one anionic amphiphilic polymer optionally combined with at least one anionic surfactant; the total content of amphiphilic polymer / anionic surfactant is between 0.5 and 10% by weight, preferably between 1 and 5% by weight, relative to the oily phase or to the reverse emulsion if it is present.
• the surfactants and polymers chosen do not give a liquid crystal phase in the aqueous phase.
• nonionic surfactants polyalkoxylated nonionic surfactants are preferably used.
• said nonionic surfactant is chosen from the following surfactants, alone or as a mixture:
• the alkoxylated alkylphenols 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.
• nonionic amphiphilic polymer a polymer comprising at least two blocks is used, one of them being hydrophilic, the other hydrophobic.
• the polymer is obtained from hydrophilic monomers chosen from acrylamide and methacrylamide, alone or as a mixture, or in the form of macromonomers; hydrophobic monomers preferred are acrylic acid esters with linear or branched C1-C4 alcohols such as methyl, ethyl, propyl and butyl acrylate, vinyl esters such as vinyl acetate, styrene, the ⁇ -methylstyrene.
• the polymer comprises at least three blocks, and more particularly three blocks
• the polymer is advantageously linear.
• the hydrophilic blocks are more particularly at the ends.
• the polymers comprise more than three blocks, the latter are preferably in the form of grafted or combed polymers.
• the amphiphilic polymer comprises polyalkoxy blocks, and preferably only comprises polyalkoxy blocks, at least one of which is hydrophobic, the other hydrophilic.
• these polymers are obtained by bringing into play ring-opening polymerizations, in particular anionic.
• said nonionic polyalkoxy amphiphilic polymers are chosen from polymers whose molar mass by weight is less than or equal to 100,000 g / mol (measured by GPC, polyethylene glycol standard), preferably between 1,000 and 50,000 g / mol, preferably between 1000 and 20000 g / mol.
• polymers of this type that may be mentioned, inter alia, are polyethylene glycol / polypropylene glycol / polyethylene glycol triblock polymers. Such polymers are well known and are in particular marketed under the brands Pluronic (marketed by BASF), Arlatone (marketed by ICI).
• anionic surfactants there may be mentioned, among others, alone or in mixtures:
• alkyl esters sulfonates for example of formula R-CH (SO 3 M) -COOR ', where R represents an alkyl radical in C 8 -C 2 o, preferably in C 10 -C 16 , R' an alkyl radical in Ci-Ce, preferably in C Ca and M an alkali cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ). Mention may very particularly be made of methyl ester sulfonates whose radical R is in
• R represents a C 10 -C 24 , preferably C 12 -C 2 o, alkyl or hydroxyalkyl radical
• RCONHR'OSO 3 M where R represents a C 2 -C 22 , preferably C 6 -C 20 , alkyl radical, R ′ a C 2 -C 3 alkyl radical, M representing a hydrogen atom or a cation of the same definition as above, as well as their polyalkoxy derivatives (ethoxylates (OE), propoxyls (OP), or their combinations);
• salts of saturated or unsaturated fatty acids for example such as those in C 8 - C 24 , preferably in C 14 -C 20 , N-acyl N-alkyltaurates, alkylisethionates, alkylsuccinamates and alkylsulfosuccinates, monoesters or sulfosuccinate diesters, N-acyl sarcosinates, polyethoxycarboxylates; and
• anionic polymers capable of being used, mention may be made most particularly of block polymers, preferably diblocks or triblocks, obtained by polymerization of at least one anionic hydrophilic monomer, optionally of at least one nonionic hydrophilic monomer, and at least one hydrophobic monomer.
• Non-ionic, anionic hydrophilic monomers, hydrophobic monomers as well as the methods of synthesis 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 for obtaining polymers according to this variant. We can therefore refer to it.
• the external aqueous phase comprises one or more amphiphilic polymers.
• a cationic amphiphilic polymer in combination with the nonionic surfactant and / or the aforementioned nonionic amphiphilic polymer.
• the cationic polymers capable of being used in the context of the present invention mention may very particularly be made of cationic derivatives of polysaccharides, such as guar or cellulose derivatives.
• hydrophobic groups such as C1-C14, preferably C2-C8 alkyl chains, optionally having a hydroxyl group. These hydrophobic groups are attached to the main polymer chain via ether bonds.
• the cationic group is a quaternary ammonium group carrying three radicals, identical or not, chosen from hydrogen, an alkyl radical comprising 1 to
• the counter ion is a halogen, preferably chlorine.
• the cationic group is a quaternary ammonium group carrying three radicals, identical or not, chosen from hydrogen, an alkyl radical comprising 1 to
• the counter ion is a halogen, preferably chlorine.
• the weight ratio of inverse emulsion relative to the external aqueous phase in the multiple emulsion is usually between 30/70 and 90/10, preferably between 50/50 and 90/10.
• the external aqueous phase In order to balance the osmotic pressures of the external aqueous phase and of the internal aqueous phase, it is possible to add to the external aqueous phase at least one additive chosen from salts such as the halides of alkali or alkaline earth metals (such as chloride sodium, calcium chloride), among alkali or alkaline earth metal sulfates (such as magnesium sulfate), among sugars (glucose for example), or among polysaccharides (especially dextran) or their mixtures.
• salts such as the halides of alkali or alkaline earth metals (such as chloride sodium, calcium chloride), among alkali or alkaline earth metal sulfates (such as magnesium sulfate), among sugars (glucose for example), or among polysaccharides (especially dextran) or their mixtures.
• the additive (salt, sugar and / or polysaccharide) concentrations are such that the osmotic pressures of the external and internal aqueous phases are balanced.
• base salt, sugar and / or polysaccharide
• base sodium, potassium, sodium tartrate, sodium tartrate, sodium tartrate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate
• the internal oily phase has a relatively high viscosity, for example greater than or equal to 1 Pa.s, more particularly greater or equal to 5 Pa.s, it may be advantageous to add to the external aqueous phase, at least one heat-thickening polymer.
• this type of polymer has the particularity of giving aqueous solutions whose viscosity increases when the temperature exceeds a certain threshold temperature. More particularly, these polymers are soluble in water at ambient temperature, and beyond the threshold temperature, part of the polymer becomes hydrophobic (thermosensitive part): the polymer thus forms a physical network on a microscopic scale, this which results at the macroscopic scale by an increase in viscosity.
• the heat-thickening polymer used is chosen from polymers having a viscosity jump between 25 and 80 ° C such that the value of the logio ratio (viscosity at 80 ° C) / logio ( viscosity at 25 ° C) is at least equal to at least 1.
• the ratio is measured under the following conditions: * The polymer is first dissolved in water (dry extract of 4%).
• the rheological profile is then measured in flow mode with imposed stress, by performing a temperature sweep between 20 ° C and 80 ° C.
• the configuration used is the 4cm / 1 degree cone-plane geometry.
• the constraint introduced in the program is chosen (in manual mode) so that the gradient at 25 ° C is 10 s 1 .
• thermo-thickening power of the polymer namely the ratio logio (viscosity at 80 ° C) / logio (viscosity at 25 ° C)
• logio viscosity at 80 ° C
• logio viscosity at 25 ° C
• the heat-thickening polymer is chosen so that the variation in viscosity is reversible.
• hydrophobic modified polysaccharides such as carboxymethyl celluloses, methyl celluloses, hydroxyethyl celluloses, hydroxypropyl celluloses.
• Synthetic polymers such as polymers based on N-isopropyl acrylamide, polymers based on N, N-dimethyl aminoethyl methacrylate are also suitable.
• Comb structure polymers consisting of a polymer backbone segment on which are grafted at least two polymer side segments, identical or not, for which either the polymer backbone segment or the side segments polymers have a lower critical solubility temperature, LCST, between 25 and 80 ° C.
• the polymeric lateral segments are heat-sensitive and are derived from polyoxyalkylenated polymers.
• polymers of this type mention may be made in particular of polymers prepared from tri-block polymer POE-POP-POE and acrylic acid (respective molar percentages: 2.3%, 97.7% , direct grafting), polymers prepared from macromonomer of POE-POP-POE tri-blocks and acrylic acid (respective molar%: 1.6%, 98.4%, copolymerization), polymers prepared from POE-POP-POE tri-block macromonomer and acrylic acid (respective mol%: 3%, 97%, copolymerization), polymers prepared from POE-POP-POE tri-block macromonomer and acrylic acid (respective molar%: 2%, 98%, copolymerization).
• the content of heat-thickening polymer more particularly represents, when it is present, 0.2 to 10% by weight of the external aqueous phase.
• the content of this polymer represents 1 to 5% by weight of the external aqueous phase.
• the external aqueous phase of the multiple emulsion can comprise at least one thickening polymer.
• This polymer has the particular effect of avoiding creaming and / or sedimentation of the final emulsion.
• thickening polymers extracted from plants and optionally modified such as carrageenans, alginates, carboxymethyl celluloses, methylcelluloses, hydroxypropyl celluloses, hydroxyethyl celluloses.
• thickening polymers of the type of polysaccharides of animal, vegetable or bacterial origin there may be mentioned by way of nonlimiting example, xanthan gum, guar and derivatives (such as hydroxypropyl guar for example) , polydextroses, or combinations thereof.
• the thickening polymer content is more particularly between 0.1 and 2% by weight relative to the external aqueous phase, preferably between 0.1 and 0.5% by weight relative to the phase external aqueous.
• the thickening polymer is soluble in the aqueous phase.
• the external aqueous phase comprises a dispersed external oily phase.
• said external aqueous phase may also comprise at least one dispersed divided solid.
• the external oily phase can also comprise at least one hydrophobic active material.
• the external oily phase comprises one or more hydrophobic active materials different from the oily phase
• their content represents more particularly less than or equal to 50% by weight of said external oily phase, preferably from 0.5 to 50% by weight , advantageously between 0.5 and 20% by weight.
• the external aqueous phase does not comprise a soluble active material, solubilized or dispersed in the form of a divided solid
• the external oily phase then comprises at least one hydrophobic active material. Note that it is not excluded that both the external aqueous and oily phases each comprise at least one active ingredient.
• the external oily phase represents from 1 to 50% by weight of the external aqueous phase, preferably 5 to 25% by weight of the external aqueous phase.
• the size of the droplets of the external oily phase is at most of the same order of magnitude as that of the reverse emulsion dispersed in the external aqueous phase.
• the solids used in the various types of cosmetic and / or dermatological formulations may be suitable.
• the size of this or these dispersed solids is close to or smaller than that of the droplets of the reverse emulsion.
• the dispersed solid is present, its content is more 'particularly 1 to 50% by weight of the external aqueous phase, preferably 5 to 25% by weight.
• the preparation of the multiple emulsion can be carried out according to any known method.
• the external aqueous phase is prepared by mixing the surfactant and / or the amphiphilic polymer, optionally the active material if the latter is present in a form soluble in the aqueous phase or dissolved in a solvent miscible with this phase, optionally the heat-thickening polymer, and water.
• the water and the surfactant and / or the amphiphilic polymer are firstly mixed, with stirring, then optionally the active material and the heat-thickening polymer, and optionally the additive (salt / sugar / polysaccharide).
• the external aqueous phase can optionally be left to stand for 1 to
• the actual multiple emulsion is prepared by adding the reverse emulsion to the external aqueous phase. It should be noted that advantageously, part of the external aqueous phase is discarded, in order to be used for the preparation of the simple emulsion comprising the external oily phase dispersed in the external aqueous phase, in the event that such an emulsion is present.
• the preparation of the multiple emulsion preferably takes place with stirring, adding the reverse emulsion slowly at the start.
• Agitation can be done by means of a paddle frame.
• the stirring speed is relatively slow, of the order of 400 rpm.
• said emulsion composed of the external oily phase is advantageously dispersed in the same external aqueous phase as that used for the multiple emulsion. It should however be noted that it is not excluded to use different external aqueous phases, insofar as there is no destabilization of the mixed emulsion. Obviously, the quantities of external aqueous phase introduced with the inverse and simple emulsions are such that the weight proportions of each of the phases satisfy the conditions explained above for the mixed emulsion.
• the direct emulsion is carried out according to any known method, by mixing with stirring of the two phases: the external oily phase, where appropriate the hydrophobic active material and the external aqueous phase comprising the surfactant and / or the amphiphilic polymer, optionally the soluble or solubilized active material and optionally the heat-thickening polymer.
• the external aqueous phase comprises a dispersed solid
• the obtaining of the multiple emulsion can be carried out as indicated in the first case, then said solid dispersed in the external aqueous phase is added.
• the average size of the droplets of the multiple emulsion advantageously varies between 5 and 15 ⁇ m (Horiba).
• the multiple emulsion comprises a thickening agent, the latter is very advantageously incorporated once the mixed emulsion has been obtained, that is to say once all the other ingredients have been added.
• the mixed emulsion which has just been detailed can be used as a constituent element of cosmetic and / or dermatological formulations.
• the content of mixed emulsion is preferably such that the total content of active material (s) present in the aqueous and oily phases, in the cosmetic and / or dermatological formulation is between 0.01 and 10% by weight of said formulation.
• the cosmetic and / or dermatological formulations which are the subject of the invention can be formulated in a large number of types of products for the skin, the hair, the eyelashes and / or the nails, the conditioners, the formulations for styling or to facilitate combing of the hair, hand and body lotions, products regulating the hydration of the skin, toilet milks, makeup-removing compositions, depilatory products, sun protection creams or lotions and ultraviolet radiation, skincare creams, anti-acne preparations, make-up formulations such as mascaras, foundations, nail polish, products intended to be applied to the lips, etc.
• Cosmetic and / or dermatological formulations in addition to mixed emulsions, include conventional additives in the field.
• bactericidal or fungicidal agents in order to improve the disinfection of the skin, such as for example triclosan; anti-dandruff agents, such as in particular zinc pyrithione or octopyrox; insecticidal agents such as natural or synthetic pyrethroids.
• Cosmetic and / or dermatological formulations can also contain agents for protecting the skin and / or hair against the aggressions of the sun and UV rays.
• the compositions may include sunscreens which are chemical compounds which strongly absorb UV radiation, such as the compounds authorized in European directive N ° 76/768 / EEC, its annexes and subsequent modifications to this directive, in particular mineral particles.
• sunscreens which are chemical compounds which strongly absorb UV radiation, such as the compounds authorized in European directive N ° 76/768 / EEC, its annexes and subsequent modifications to this directive, in particular mineral particles.
• mineral particles such as zinc oxide, titanium dioxide or cerium oxides in the form of powder or colloidal particles, alone or as a mixture.
• These powders can optionally be surface-treated to increase the effectiveness of their anti-UV action or to facilitate their incorporation into cosmetic formulations or to inhibit surface photoreactivity.
• Said formulations may also contain fixative resins.
• fixative resins when they are present, are generally present at concentrations of between 0.01 and 10%, preferably between 0.5 and 5%.
• the fixing resins used in the cosmetic compositions are more particularly chosen from the following resins: • methyl acrylate / acrylamide copolymers, polyvinylmethylether / maleic anhydride copolymers, vinyl acetate / crotonic acid copolymers, octylacrylamide / methyl acrylate / butylaminoethylmethacrylate, polyvinylpyrrolidones, polyvinylpyrrolidone copolymers, polyvinyl acrylate, , polyvinyl alcohol / crotonic acid copolymers, polyvinyl alcohol / maleic anhydride copolymers, hydroxypropyl celluloses, hydroxypropyl guars, sodium polystyrene sulfonates, polyvinylpyrrolidone / ethyl methacrylate / methacrylic acid, monomethyl ethers of poly (methylvinyl ether / polyvinyl acid) poly
• copolyesters derived from acid, anhydride or a terephthalic and / or isophthalic and / or sulfoisophthalic diester and a diol such as:
• polyester copolymers based on propylene terephthalate and polyoxyethylene terephthalate units and terminated by ethyl, methyl units (US-A-4,711,730) or polyester oligomers terminated by alkylpolyethoxy groups (US-A-4,702,857) or anionic sulfopolyethoxy groups (US-A-4,721,580), sulfoaroyl groups (US-A-4,877,896);
• polyesters - polyurethanes obtained by reaction of a polyester obtained from adipic acid and / or terephthalic acid and / or sulfoisophthalic acid and a diol, on a prepolymer with terminal isocyanate groups obtained from 'a polyoxyethylene glycol and a diisocyanate (FR-A-2 334 698); • ethoxylated monoamines or polyamines, polymers of ethoxylated amines (US-A-4,597,898, EP-A-11,984).
• the fixing resins are chosen from polyvinylpyrrolidone (PVP), copolymers of polyvinylpyrrolidone and of methyl methacrylate, copolymer of polyvinylpyrrolidone and vinyl acetate (VA), polyterephthalene ethylene glycol / polyethylene glycol copolymers, polyethylene glycol terephthalate / polyethylene glycol / polyisophthalate sulfonate copolymers, and mixtures thereof.
• PVP polyvinylpyrrolidone
• VA vinyl acetate
• fixative resins are preferably dispersed or dissolved in the chosen vehicle.
• Cosmetic and / or dermatological formulations can also contain polymeric derivatives exercising a protective function.
• These polymer derivatives can be present in amounts of the order of 0.01-10% by weight of the cosmetic and / or dermatological formulation, preferably about 0.1-5% by weight, and very particularly of the order of 0.2-3% by weight.
• agents can in particular be chosen from:. non-ionic cellulose derivatives such as cellulose hydroxyethers, methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose;
• polyvinyl esters grafted on polyalkylenated trunks such as polyvinylacetates grafted on polyoxyethylene trunks (EP-A-219048); . polyvinyl alcohols.
• Cosmetic and / or dermatological formulations can also include plasticizing agents.
• Said agents can represent between 0.1 to 20% by weight of the formulation, preferably from 1 to 15% by weight.
• plasticizers there may be mentioned adipates, phthalates, isophthalates, azelates, stearates, silicone copolyols, glycols, castor oil, or mixtures thereof.
• humectants which include, among others, glycerol, sorbitol, urea, collagen, gelatin, aloe vera, hyaluronic acid or solvents water-soluble volatiles such as ethanol or propylene glycol, the contents of which can reach up to 60% by weight of the composition.
• water-soluble or water-dispersible polymers such as collagen or certain non-allergenic derivatives of animal or vegetable proteins (wheat protein hydrolysates for example), natural hydrocolloids ( guar, carob, tara gum, etc.) or derived from fermentation processes, and derivatives of these polycarbohydrates such as non-ionic modified celluloses such as hydroxyethylcellulose, or anionics such as carboxymethylcellulose; guar or carob derivatives such as their nonionic derivatives (for example hydroxypropylguar) or anionic derivatives (carboxymethylguar and carboxymethylhydroxypropylguar).
• non-ionic modified celluloses such as hydroxyethylcellulose, or anionics
• carboxymethylcellulose such as hydroxyethylcellulose
• guar or carob derivatives such as their nonionic derivatives (for example hydroxypropylguar) or anionic derivatives (carboxymethylguar and carboxymethylhydroxypropylguar).
• powders or mineral particles such as calcium carbonate, sodium bicarbonate, calcium dihydrogen phosphate, mineral oxides in powder form or in colloidal form (particles of smaller size or on the order of a micrometer, sometimes a few tens of nanometers) such as titanium dioxide, silica, aluminum salts generally used as antiperspirants, kaolin, talc, clays and their derivatives, etc.
• Preservatives such as methyl, ethyl, propyl and butyl esters of p-hydroxybenzoic acid, sodium benzoate, GERMABEN ® or any chemical agent preventing the proliferation of bacteria or molds and traditionally used in cosmetic formulations and / or dermatological, can also be introduced into the present formulations, generally up to 0.01 to 3% by weight of the formulation.
• the amount of these products is usually adjusted to avoid any proliferation of bacteria, molds or yeasts in cosmetic compositions.
• perfumes coloring agents among which mention may be made of the products described in Annex IV ("List of coloring agents allowed for use in cosmetic products") of European Directive No. 76/768 / EEC of July 27, 1976, called the Cosmetic Directive, and / or opacifying agents such as pigments.
• the formulation may also contain viscous or gelling polymers so as to adjust the texture of the formulation, such as crosslinked polyacrylates (Carbopol sold by Goodrich), non-cationic cellulose derivatives such as hydroxypropylcellulose. , carboxymethylcellulose, guars and their nonionic derivatives, xanthan gum and its derivatives, used alone or in combination, or the same compounds, generally in the form of water-soluble polymers modified by hydrophobic groups covalently linked to the polymer backbone such as described in patent WO 92/16187.
• crosslinked polyacrylates Carbopol sold by Goodrich
• non-cationic cellulose derivatives such as hydroxypropylcellulose.
• carboxymethylcellulose, guars and their nonionic derivatives carboxymethylcellulose, guars and their nonionic derivatives
• xanthan gum and its derivatives used alone or in combination, or the same compounds, generally in the form of water-soluble polymers modified by hydrophobic groups covalently linked to the polymer backbone such as described
• Cosmetic and / or dermatological formulations can also contain polymeric dispersing agents in an amount of the order of 0.1-7% by weight, to control the hardness of calcium and magnesium, agents such as:
• the water-soluble salts of polycarboxylic acids with a molecular weight by weight of the order of 2000 to 100,000 g / mol obtained by polymerization or copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, acid or maleic anhydride, fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and very particularly polyacrylates of molecular weight by weight of the order of 2,000 to 10,000 g / mol (US-A-3,308,067), copolymers of acrylic acid and maleic anhydride with a molecular weight of about 5,000 to 75,000 g / mol (EP-A- 66915);
• metal sequestering agents more particularly those sequestering calcium such as citrate ions.
• composition of the reverse emulsion Composition of the reverse emulsion:
• 100 g of reverse emulsion are prepared, comprising 70 g of internal oily phase and 30 g of internal aqueous phase.
• soybean oil and Arlacel were placed in an oven at 75 ° C.
• the internal aqueous phase is then added to the internal oily phase, with stirring with Ultraturrax at 9500 rpm.
• the mixing is carried out at 75 ° C. 2 / Multiple emulsion
• composition of the multiple emulsion * 50% reverse emulsion
• Rhodopol 23 (**) (Rhodia Chimie;% by weight expressed relative to the weight of external aqueous phase).
• Arlatone F127G HO (CH2CH 2 O) ⁇ (OCH (CH3) CH2 ⁇ ) y (CH2CH 2 O) z H with verification of the following inequality: 82 ⁇ x + z ⁇ 90 and the polymer comprises 7 OP units for 1 mole of product).
• Rhodopol 23 xanthan gum.
• 40 g of external aqueous phase are prepared by weighing 20 g of 2% Rhodopol 23 solution and 20 g of 4% Arlatone F F127G solution and 7.2% glucose are added.
• the whole is mixed with the pale frame at 200 rpm for 5 minutes.
• the 50 g of the reverse emulsion obtained in point 1 / are introduced, with stirring with a frame paddle at 400 rpm, drop by drop into the external aqueous phase, at ambient temperature. Stirring is continued for another 10 minutes.
• composition of the direct emulsion is a composition of the direct emulsion
• Rhodopol 23 % by weight expressed relative to the weight of aqueous phase
• retinol 10% solution in miglyol.
• Alkamuls T85 sorbitan ester comprising 20 ethoxylated units.
• the emulsion is obtained in the following manner:
• a stable mixed emulsion comprising 0.5% by weight of retinol relative to the total water.

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• 2002
  • 2002-03-04 WO PCT/FR2002/000769 patent/WO2003074010A1/fr not_active Application Discontinuation
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  • 2002-03-04 JP JP2003572532A patent/JP2005525359A/ja active Pending
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