WO2013013903A1 - Process for treating perspiration using an anhydrous composition comprising two reagents that together produce an antiperspirant effect in situ on the skin - Google Patents
Process for treating perspiration using an anhydrous composition comprising two reagents that together produce an antiperspirant effect in situ on the skin Download PDFInfo
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- WO2013013903A1 WO2013013903A1 PCT/EP2012/061884 EP2012061884W WO2013013903A1 WO 2013013903 A1 WO2013013903 A1 WO 2013013903A1 EP 2012061884 W EP2012061884 W EP 2012061884W WO 2013013903 A1 WO2013013903 A1 WO 2013013903A1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q15/00—Anti-perspirants or body deodorants
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- 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
- A61K8/0216—Solid or semisolid forms
- A61K8/0229—Sticks
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- 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
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
-
- 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
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/20—Halogens; Compounds thereof
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- 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
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/23—Sulfur; Selenium; Tellurium; Compounds thereof
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- 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
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/24—Phosphorous; Compounds thereof
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- 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
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
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- 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
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
- A61K8/365—Hydroxycarboxylic acids; Ketocarboxylic acids
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- 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
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
- A61K8/4913—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/30—Characterized by the absence of a particular group of ingredients
- A61K2800/31—Anhydrous
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
- A61K2800/88—Two- or multipart kits
- A61K2800/884—Sequential application
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
- A61K2800/94—Involves covalent bonding to the substrate
Definitions
- the present invention relates to a cosmetic process for treating human perspiration and possibly the body odour resulting from perspiration, which comprises the application to the skin of an anhydrous composition comprising, in a cosmetically acceptable medium, at least one compound (1 ) and at least one compound (2) that together produce an antiperspirant effect in situ on the skin; the said compounds (1 ) and (2) being capable of:
- the present invention also relates to an anhydrous composition
- an anhydrous composition comprising, in a cosmetically acceptable medium, a salt of an inorganic multivalent cation (1 ) and a salt of an inorganic anion (2) forming in situ on the skin a salt that produces an antiperspirant effect.
- the armpits and also certain other parts of the body are generally the site of much discomfort that may arise directly or indirectly from perspiration.
- This discomfort often leads to unpleasant and disagreeable sensations that are mainly due to the presence of sweat resulting from perspiration, which may, in certain cases, make the skin and clothing wet, especially in the region of the armpits or on the back, thus leaving visible marks.
- the presence of sweat may give rise to the production of body odour, which is generally unpleasant.
- sweat may also leave salts and/or proteins at the surface of the skin, which may result in whitish marks on clothing. Such discomfort should be dealt with, including in the case of moderate perspiration.
- antiperspirant products containing substances that have the effect of limiting or even preventing the flow of sweat in order to overcome the problems mentioned above.
- These products are generally available in the form of roll-ons, sticks, aerosols or sprays.
- Antiperspirant substances generally consist of a halogenated aluminium and/or zirconium salt, especially aluminium and/or zirconium chlorohyd rates. These substances reduce the flow of sweat by forming a plug in the sweat duct. However, these substances may cause discomfort in the case of certain users, in relation with the acidic pH of the formulations.
- patent FR 2 940 062 has already disclosed a multi-component agent for treating human perspiration, comprising two components that are intended to be mixed together before application to the skin or to be applied to the skin simultaneously, separately or sequentially over time; the said components being capable of reacting together to form one or more physical interactions in order to impart an antiperspirant effect.
- patent WO 2010/070 143 has already disclosed a multi-component agent for treating human perspiration, comprising two components that are intended to be mixed together before application to the skin or to be applied to the skin simultaneously, separately or sequentially over time; one of the components being capable of treating the skin and the other component being capable of acting on the skin once treated, the said combination imparting an antiperspirant effect.
- patent WO 2010/070 139 has already disclosed a multi-component agent for treating human perspiration, comprising two components that are intended to be mixed together before application to the skin or to be applied to the skin simultaneously, separately or sequentially over time; the said components being capable of reacting together to form covalent bonds.
- the antiperspirant efficacy of these three processes is not entirely satisfactory.
- the systems proposed in these patent applications require the use of a twofold action or of extemporaneous preparation, which are a constraint on consumers.
- Several patents describe anhydrous compositions containing calcium salts.
- Patent JP61 183208 from Kobayashi Kose KK describes anhydrous aerosols containing calcium carbonate particles.
- Patents JP1 1278816 and JP2000219505 from Sekisui Plastics describe aerosols containing amorphous calcium phosphate particles optionally in combination with aluminium salts.
- the cited compositions are only deodorant when they do not contain aluminium salts. They are made antiperspirant by the addition of aluminium salts.
- anhydrous composition comprising, in a cosmetically acceptable medium, at least one compound (1 ) and at least one compound (2) that together produce an antiperspirant effect in situ on the skin; the said compounds (1 ) and (2) being capable of:
- composition not containing any antiperspirant halogenated aluminium and/or zirconium salt.
- the present invention relates to a cosmetic process for treating human perspiration and possibly the body odour resulting from perspiration, which comprises the application to the skin of an anhydrous composition comprising, in a cosmetically acceptable medium, at least one compound (1 ) and at least one compound (2) that together produce an antiperspirant effect in situ on the skin; the said compounds (1 ) and (2) being capable of:
- the present invention also relates to an anhydrous composition
- an anhydrous composition comprising, in a cosmetically acceptable medium, a salt of an inorganic or multivalent cation (1 ) and a salt of an inorganic anion (2); the said compounds (1 ) and (2) producing an antiperspirant effect; in particular, the said composition does not contain any antiperspirant halogenated aluminium and/or zirconium salt.
- anhydrous composition means a composition containing less than 1 % by weight of added water, or even less than 0.5% of added water, and especially free of water, the water not being added during the preparation of the composition but corresponding to the residual water provided by the mixed ingredients.
- cosmetically acceptable means compatible with the skin and/or its integuments or mucous membranes, having a pleasant colour, odour and feel and not causing any unacceptable discomfort (stinging, tautness or redness) liable to discourage the consumer from using this composition.
- antiperspirant means any substance which has the effect of reducing the flow of sweat and/or of reducing the sensation of moisture associated with human sweat, and/or of masking human sweat.
- multivalent cations means any monoatomic or polyatomic ion bearing at least two positive electrical charges and having a valency of at least 2 and preferably 2 or 3.
- anion means any monoatomic or polyatomic ion bearing one or more negative electrical charges.
- composition not containing any antiperspirant aluminium and/or zirconium salt means any composition containing less than 1 % or even less than 0.5% by weight, relative to the total weight of the composition, of antiperspirant aluminium and/or zirconium salt comprising in its structure at least one halogen atom (for example aluminium and/or zirconium chlorohydrate), and especially free of the said salt.
- Compounds (1 ) and (2) of the invention are preferably dispersed in the anhydrous composition in powder form.
- the mean particle size is preferably less than 100 ⁇ .
- the concentration of each of the compounds (1 ) and (2) of the invention in the composition preferably ranges from 0.1 % to 20% by weight and more preferentially from 0.5% to 15% by weight relative to the total weight of the composition.
- At least one of the compounds (1 ) and (2) may be encapsulated according to the known encapsulation techniques.
- compounds (1 ) and (2) are capable of reacting together by means of one or more physical interactions, i.e. by forming together one or more non-covalent bonds chosen from ionic bonds, hydrogen bonds, Van der Waals bonds and hydrophobic bonds.
- compounds (1 ) and (2) are capable of reacting together by means of one or more hydrogen bonds to impart an antiperspirant effect.
- the combination of the two compounds (1 ) and (2) interacting by means of one or more hydrogen bonds may lead to the formation on the skin of complexes with antiperspirant activity.
- compound (1 ) may be chosen from oxyalkylenated polymers, polyvinylpyrrolidone, polyvinyl acetates and copolymers thereof, and compound (2) may be chosen from mineral fillers bearing a free hydrogen bond.
- compound (1 ) is preferably chosen from oxyalkylenated polymers.
- the oxyalkylenated polymers may comprise ethylene oxide groups (oxyethylenated compounds), propylene oxide groups (oxypropylenated compounds) or both (oxyethylenated/oxypropylenated compounds).
- mineral filler bearing a free hydrogen bond means that the mineral fillers contain one or more free chemical groups capable of inducing one or more hydrogen bonds.
- the oxyalkylenated polymers and the mineral fillers containing one or more free chemical groups capable of inducing one or more hydrogen bonds will be chosen from those described in patent FR 2 940 062.
- the oxyalkylenated polymer(s) are polyethylene glycols and ethoxylated alkyl or acyl derivatives of polyols, in particular the oxyethylenated (120 OE) methyl glucose dioleate sold under the name Glucamate DOE-120 Vegetal® by the company Amerchol.
- the mineral filler(s) bearing a free hydrogen bond are preferably chosen from metal oxides, hydrophilic silicas and natural silica-based minerals such as perlite or diatomaceous earth.
- hydrophilic silica means a silica that is compatible with water or a polar solvent and that forms a homogeneous phase, for example a colloidal solution or a gel.
- hydrophilic silica covers both pure silicas and silica-coated particles. Fumed silicas and in particular fumed silicas with a specific surface area of between 180 and 350 m 2 g, with a number-average particle size of between 10 and 20 nm and with a density of between 50 and 150 g/l are preferably used as hydrophilic silica. Such fumed silicas are sold under the names Aerosil 200 and Aerosil 300 by the company Degussa-Huls. Among the natural silica-based minerals that may be used, mention may be made especially of perlite and diatomaceous earth.
- the perlites that may be used in the cosmetic composition B are generally aluminosilicates of volcanic origin and have as composition:
- aluminium oxide AI2O3 12.0-15.0% by weight of aluminium oxide AI2O3 ,
- magnesium oxide MgO 0.2-0.7% by weight of magnesium oxide MgO
- the perlite may be ground, dried and then calibrated to obtain perlite particles with a size of about 100 m.
- a compound (1 ) chosen from oxyalkylenated polymers combined with a compound (2) chosen from hydrophilic silicas will preferably be used.
- the cosmetic composition A comprises one or more compounds chosen from oxyalkylenated polymers and ethoxylated alkyl or acyl derivatives of polyols, in particular oxyethylenated (120 OE) methyl glucose dioleate
- the cosmetic composition B comprises one or more compounds chosen from hydrophilic silica.
- hydrophilic silica particles may combine with the oxyalkylenated groups by forming one or more hydrogen bonds in order to form a viscous gel having satisfactory antiperspirant activity.
- compound (1 ) is chosen from polymers comprising one or more vicinal diols and compound (1 ) is a crosslinking agent.
- the polymers comprising vicinal diols may be synthetic or natural.
- Such polymers are chosen from polymers of polyvinyl alcohol type, galactomannans such as guar gum or locust bean gum, and glucomannans such as konjac gum.
- the crosslinking agent is sodium borate.
- the weight ratio between the crosslinking agent and the polymer comprising one or more vicinal diols is between 0.025 and 2.
- compound (1 ) is a guar gum and compound (2) is sodium borate.
- compound (1 ) is chosen from polyethylene glycol derivatives such as those described in patent FR 2 940 062 and compound (2) is chosen from organic acids and derivatives thereof such as acrylic acid polymers or copolymers such as those described in patent FR 2 940 062.
- compounds (1 ) and (2) are capable of reacting together by means of a hydrogen bond so as to impart an antiperspirant effect.
- compound (1 ) is capable of reacting with compound (2) via an acid-base reaction.
- compound (1 ) may be chosen from polymers based on (meth)acrylic acid such as those described in patent FR 2 940 062.
- compound (2) may be chosen from organic bases, in particular organic amines.
- the organic amine(s) comprise one or two primary, secondary or tertiary amine functions, and one or more linear or branched Ci -Cs alkyl groups bearing one or more hydroxyl radicals.
- Organic amines chosen from alkanolamines such as monoalkanolamines, dialkanolamines or trialkanolamines comprising one to three identical or different Ci -C 4 hydroxyalkyl radicals are in particular suitable for use.
- W is a C1 -C6 alkylene residue optionally substituted with a hydroxyl group or a C1 -C6 alkyl radical
- Rx, Ry, Rz and Rt which may be identical or different, represent a hydrogen atom or a C1 -C6 alkyl, C1 -C6 hydroxyalkyl or C1 -C6 aminoalkyl radical, are also suitable for use.
- Examples of such amines that may be mentioned include 1 ,3-diaminopropane, 1 ,3-diamino-2-propanol, spermine and spermidine.
- the organic amine is monoethanolamine.
- compound (1 ) is chosen from crosslinked methacrylic acid or acrylic acid homopolymers and compound (2) is an organic amine, in particular monoethanolamine.
- compound (1 ) and compound (2) are capable of reacting by means of a cation/anion reaction.
- cation means any monoatomic or polyatomic ion bearing one or more positive electrical charges.
- anion means any monoatomic or polyatomic ion bearing one or more negative electrical charges.
- anion/cation reaction means that compound (1 ) and compound (2) are capable of reacting by forming one or more ionic bonds of cation/anion type, i.e. involving a reaction between a compound (1 ) containing at least one cationic charge and a compound (2) containing at least one anionic charge.
- compound (1 ) comprises in its structure one or more cationic charges and compound (2) comprises in its structure one or more anionic charges.
- compound (1 ) may be chosen from cationic surfactants, cationic polymers, cationic particles, inorganic cation salts or mixtures thereof and compound (2) may be chosen from anionic surfactants, anionic polymers, anionic particles and crosslinking agents, or mixtures thereof.
- compound (1 ) of cationic surfactants, cationic polymers, cationic particles, inorganic cation salts or mixtures thereof such as those described in patent FR 2 940 062
- compound (2) may be chosen from anionic surfactants, anionic polymers, anionic particles and crosslinking agents or mixtures thereof such as those described in patent FR 2 940 062.
- compound (1 ) is chosen from cationic surfactants and compound (2) is chosen from anionic surfactants.
- compound (1 ) is chosen from cationic polymers and compound (2) is chosen from anionic polymers.
- the cationic polymer(s) are chosen from cyclopolymers, in particular diallyldimethylammonium salt homopolymers, quaternized or non-quaternized copolymers of vinylpyrrolidone and of dialkylaminoalkyl acrylate or methacrylate, quaternary polymers of vinylpyrrolidone and of vinylimidazole, cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and/or guar gums modified with a hydroxypropyltrimethylammonium salt.
- cyclopolymers in particular diallyldimethylammonium salt homopolymers, quaternized or non-quaternized copolymers of vinylpyrrolidone and of dialkylaminoalkyl acrylate or methacrylate, quaternary polymers of vinylpyrrolidone and of vinylimidazole, cellulose copolymers or cellulose derivatives grafted with a water
- the anionic polymer(s) may be chosen from terpolymers of vinyl acetate, vinyl tert-butylbenzoate and crotonic acid, methyl vinyl ether/monoesterified maleic anhydride copolymers and/or diblock polymers comprising a nonionic hydrophilic polymeric block and a hydrophobic polymeric block.
- compound (1 ) is chosen from cationic polymers and compound (2) is chosen from anionic particles preferably in the form of a colloidal particle dispersion.
- the cationic polymers are chosen from cyclopolymers such as diallyldimethylammonium salt homopolymers and polyalkyleneimines, in particular polyethyleneimine.
- the weight ratio between the cationic polymer(s) and the anionic silica(s) ranges from 0.7 to 0.14.
- compound (1 ) is chosen from cationic particles, especially cationic silicas, and compound (2) is chosen from anionic polymers, preferably chosen from non-crosslinked copolymers of AMPS and of an ethoxylated C12-C14 alkyl methacrylate.
- compound (1 ) is chosen from cationic polymers and compound (2) is chosen from anionic surfactants.
- compound (1 ) is chosen from cationic surfactants and compound (2) is chosen from anionic polymers.
- compound (1 ) is chosen from alkali metal or alkaline-earth metal salts and compound (2) is chosen from anionic polymers comprising a sugar unit, especially alginates and derivatives thereof such as propylene glycol alginate, or salts thereof such as sodium alginate or calcium alginate.
- the alkali metal or alkaline-earth metal salt(s) are chosen from the chlorides of these metals, in particular calcium chloride.
- compound (1 ) and compound (2) are capable of reacting together by precipitation or flocculation.
- compound (1 ) is capable of precipitating or flocculating in the presence of a compound (2) by forming one or more ionic bonds.
- compound (1 ) may be chosen from cationic polymers chosen from guar gums such as hydroxypropyl guar, salts of an inorganic cation, and organic acids.
- compound (2) may be chosen from salts of an inorganic anion, amino acids, in particular cystine, crosslinking agents, anionic polymers chosen from polystyrene and terpolymers based on vinyl acetate, vinyl tert-butylbenzoate and crotonic acid, or a mixture of these compounds.
- compound (1 ) may be an organic acid such as citric acid, and compound (2) is an amino acid, in particular cystine.
- compound (1 ) may be polystyrene and compound (2) is an alkali metal salt, in particular sodium chloride.
- compound (1 ) may be an alkaline-earth metal salt, in particular a mixture of zinc chloride and magnesium chloride, and compound (2) is an anionic polymer chosen from terpolymers based on vinyl acetate, vinyl tert-butylbenzoate and crotonic acid.
- compound (1 ) may be a cationic polymer chosen from guar gums modified with a hydroxypropyltrimethylammonium salt, in particular the chloride, and compound (2) is a crosslinking agent, in particular sodium tetraborate.
- compound (1 ) may be a salt of a multivalent inorganic cation
- compound (2) is a salt of an inorganic anion.
- the cations in accordance with the invention are preferably chosen from multivalent inorganic cations whose valency n is by definition at least 2.
- the multivalent cations are chosen from
- alkaline-earth metal cations such as beryllium, magnesium, calcium, strontium and barium;
- transition metal cations such as titanium (Ti 2+ , Ti 3+ , Ti 4+ ), manganese (Mn 2 +, Mn 3+ , Mn 4+ , Mn 7+ ), zinc (Zn 2+ ), zirconium (Zr 4+ ), hafnium (Hf 4+ ) and aluminum (Al 3+ ).
- the preferential alkaline-earth metal cations will be chosen from strontium, magnesium and calcium.
- the transition metal cations will preferably be chosen from zinc, manganese and aluminium.
- the multivalent cation salts that may be used according to the invention are preferably chosen from those with a solubility in water of greater than 2%, between 15°C and 30°C and at a pH of between 6 and 8.
- halides are a chemical series consisting of the chemical elements of group 17 of the Periodic Table, also known as group VII or group VIIA. Use will be made, as halides, of fluorides (fluorine), chlorides (chlorine), bromides (bromine) and iodides (iodine) and more particularly chlorides.
- carboxylic acid salts such as acetates, propionates, pyrrol idonecarboxylates (or pidolates) or sorbates; polyhydroxylated carboxylic acid salts such as gluconates, heptagluconates, ketogluconates, lactate- gluconates, ascorbates or pentothenates; mono- or polycarboxylic hydroxy acid salts such as citrates or lactates; amino acid salts such as aspartates or glutamates; fulvate salts.
- carboxylic acid salts such as acetates, propionates, pyrrol idonecarboxylates (or pidolates) or sorbates
- polyhydroxylated carboxylic acid salts such as gluconates, heptagluconates, ketogluconates, lactate- gluconates, ascorbates or pentothenates
- mono- or polycarboxylic hydroxy acid salts such as citrates or lactates
- cation salts in accordance with the invention, mention may be made of calcium chloride, calcium pidolate, calcium aspartate, calcium gluconate, calcium glutamate, calcium heptagluconate, calcium propionate, calcium 2- ketogluconate, calcium lactate, calcium ascorbate, calcium citrate, calcium pentothenate, calcium bicarbonate, calcium sorbate, calcium lactate gluconate, calcium fulvate, magnesium chloride, magnesium sulfate, magnesium acetate, magnesium pidolate, magnesium gluconate, magnesium glutamate, magnesium heptagluconate, magnesium 2-ketogluconate, magnesium lactate, magnesium ascorbate, magnesium citrate, magnesium aspartate, manganese gluconate, magnesium pentothenate, magnesium bicarbonate, magnesium sorbate, magnesium lactate gluconate, magnesium fulvate, manganese chloride and manganese gluconate.
- Magnesium chloride, manganese chloride, calcium chloride, calcium aspartate, calcium lactate, calcium propionate, calcium pidolate, calcium pentothenate, calcium bicarbonate, calcium sorbate, calcium lactate gluconate or calcium fulvate will preferably be chosen, and even more particularly calcium chloride.
- the anions in accordance with the invention are preferably chosen from carbonate (CO3 2" ), hydrogen carbonate (HCO3 " ), phosphate (PO 4 3” ), polyphosphates such as diphosphate P2O7 4" (also known as pyrophosphate), triphosphate P3O10 5" , phosphonate (PO3 3" ), hydrogen phosphate (HPO 4 2” ), sulfate (SO 4 2” ), sulfonate (SO3 ), hydrogen sulfate (HSO 4 " ), and hydrogen sulfonate (HSO3 " ). Hydrogen phosphate or hydrogen carbonate will be used more particularly.
- the inorganic anion salt may be chosen, for example, from:
- - ammonium salts salts of an amine, in particular of mono-, di- or trialkanolamines; comprising one to three identical or different Ci-C 4 hydroxyalkyl radicals.
- alkanolamine compounds mention may be made of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N-dimethylaminoethanolamine, 2-amino-2-methyl-1 -propanol, triisopropanolamine, 2-amino-2-methyl-1 ,3-propanediol, 3-amino-1 ,2-propanediol, 3-dimetnylamino-1 ,2-propanediol and tris(hydroxymethylamino)methane.
- Use will preferentially be made of an alkali metal salt, in particular a sodium or potassium salt.
- an alkali metal salt in particular a sodium or potassium salt.
- preferential non-halogenated anion salts mention may be made of Na 2 CO 3 , K2CO3, NaHCOs, KHCO 3 , Na 3 PO 3 , Na 2 HPO 4 , NaH 2 PO 4 , Na 2 H 2 P2O 7 , Na 4 P 2 O 7 , K 2 HPO 4 , KH 2 PO 4 , K 2 H 2 P 2 O 7 , K4P 2 O 7 , Na 2 SO 4 , MgSO 4 and K 2 SO 4 .
- Use will preferably be made of sodium hydrogen carbonate NaHCO3.
- the cation and the anion form when they are placed in contact, a salt having a solubility product in water at 25°C of less than 10 "3 and preferably less than 10 "5 .
- solubility product in water at 25°C means the equilibrium constant at 25°C corresponding to the dissolution of the salt X n Y m in water.
- the solubility product is written Ks and is equal to:
- Ks x
- antiperspirant salts formed after application of composition A and of composition B mention may be made of the following salts and of their solubility product: CaSO 4 (7.1 .10 “5 ), CaCO 3 (4.96x10 “9 ), Ca 3 (PO 4 ) 2 (2.07x10 “33 ), MgCO 3 (6.82x10 “6 ), Mg 3 fPO 4 ) 2 (9.86x10 "25 ), MnCO 3 (2.24x.10 “11 ), SrCO 3 (5.6x10 "10 ), ZnCO 3 (1 .19*10 ).
- the cited values are those referenced in the Handbook of Chemistry and Physics (70th Edition) CRC Press, page b207-b208.
- the cited values are those referenced in the Handbook of Chemistry and Physics (70th Edition) CRC Press, page b207-b208.
- the composition of the invention is a water/oil/water emulsion comprising two or three components, in which compound (1 ): multivalent cation salt and compound (2): anion salt are present separately in each of the inner and outer aqueous phases.
- the mole ratio between the cation and the anion preferably ranges from 10/1 to 1/10 and more preferentially from 4/1 to 1/4.
- the total concentration of cation and anion preferably ranges from 2% to 25%, and more preferentially from 5% to 20% by weight relative to the total weight of the composition.
- compound (1 ) comprises one or more functions capable of reacting with one or more functions borne by compound (2) so as to impart an antiperspirant effect.
- compound (1 ) and compound (2) bear one or more complementary chemical functions.
- the term "complementary chemical function" means that compound (1 ) comprises one or more functions that are capable of reacting with one or more functions borne by compound (2) by means, for example, of a condensation reaction by forming one or more covalent bonds.
- compound (1 ) may comprise one or more functions chosen from the following:
- vinyl and activated vinyl in particular acrylonitrile and acrylic and methacrylic esters
- aminals aminals, hemiaminals,
- ketones alpha-hydroxy ketones, alpha-halo ketones,
- halide of unsaturated carbon-based ring or heterocycle especially chlorotriazine, chloropyrimidine, chloroquinoxaline or chlorobenzotriazole,
- RSO2CI or F sulfonyl halide: RSO2CI or F, R being a C1-C30 alkyl.
- activated vinyl means that the vinyl function has an asymmetrical electronic distribution and is thus more reactive.
- compound (1 ) comprises one or more functions chosen from epoxide, anhydride, chlorotriazine and/or thiosulfate functions.
- compound (1 ) comprises one or more functions chosen from epoxide, anhydride and aldehyde functions.
- compound (2) comprises one or more functions chosen from alcohol, amine, thiol and/or carboxylic acid functions.
- the chemical function(s) of compound (1 ) may react with the chemical function(s) of compound (2) either spontaneously or by activation by temperature, the pH, a co-reagent, a chemical or biochemical catalyst, for instance metal salts such as the metal salts chosen from manganese, copper, iron and/or titanium salts, or enzymes such as oxidases or laccases.
- metal salts such as the metal salts chosen from manganese, copper, iron and/or titanium salts, or enzymes such as oxidases or laccases.
- compound (1 ) and compound (2) are preferably polymers such as those described in patent application WO 2010/070 139.
- compound (1 ) is capable of reacting with compound (2) via a radical chemical reaction.
- compounds (1 ) and (2) respectively present may be ethylenic compounds.
- compounds (1 ) and (2) may be chosen from ethylenic compounds comprising acrylate, acrylic acid, acrylamide, methacrylate, methacrylic acid, methacrylamide and/or styrene functions.
- the radical reaction between the compound(s) (1 ) and the compound(s) (2) may be activated by light, heat, one or more catalysts or a composition comprising one or more photoinitiators and optionally one or more photosensitizers.
- Photopolyme zable and/or photocrosslinkable compositions are described in particular, for example, in patents CA 1 306 954 and US 5 456 905.
- the ethylenic compound(s) may be chosen from polymers comprising ethylenic double bonds such as those described in patent application WO 2010/070 139.
- compound (1 ) is capable of reacting with compound (2) via an oxidation reaction.
- compounds (1 ) and (2) that are capable of reacting together via an oxidation reaction may be chosen from aromatic compounds, such as those bearing at least two hydroxyl functions or one hydroxyl function and one amine function or alternatively only a hydroxyl function.
- the oxidation reaction between compound (1 ) and compound (2) involves the presence of one or more oxidizing agents.
- the oxidizing agent is preferably aqueous hydrogen peroxide solution or may originate from atmospheric oxygen.
- compounds (1 ) and (2) may be chosen from catechol, dihydroxyindole and 4-hydroxyindole.
- compound (1 ) will be a polyphenol precursor of an antiperspirant agent and compound (2) is an enzymatic oxidation catalytic system and/or a chemical oxidation catalytic system.
- polyphenol means any molecule comprising one or more aromatic rings, in particular benzene rings or fused aromatic rings bearing one or more hydroxyl functions.
- precursor of an antiperspirant agent means any substance or any chemical compound that is capable via an oxidation reaction of forming a material constituting an antiperspirant agent.
- a polyphenol compound (1 ) and in particular an ortho-diphenol namely a compound comprising at least one aromatic ring bearing at least two hydroxyl groups borne by two consecutive carbon atoms of the aromatic ring as defined below, proves to be capable of polymerizing in situ when it is placed in contact with a suitable catalytic system, in the presence of oxygen, and of forming an efficient, advantageously biocompatible polymeric antiperspirant agent, which is capable of reducing the flow of sweat and of reducing or even eliminating the body odour associated with human perspiration.
- compound (1 ) is capable of reacting with compound (2) via a crosslinking reaction.
- highly hydrophobic coatings may thus be produced, especially for treating the parts of the body that perspire the most, for instance the chest or the armpits.
- the coatings thus obtained show improved resistance to water and moisture.
- compound (1 ) may be chosen from polyols, for instance a cellulose derivative, and compound (2) may be chosen from compounds of perfluoroalkyltriethoxysilane type.
- the composition according to the invention may also contain one or more crosslinking agents in order to produce coatings that are rendered solid on elongation or tearing.
- Such improvements may be useful for applications to the parts of the body that are the most subject to movements, such as the lips, the hands, the armpits, the neck or any area close to the joints. Coatings that are rendered more resistant to abrasion may also be produced. These improvements may be useful for applications to the covered body. Specifically, these areas may be subject to friction from clothing.
- lubricant active agents and especially solid lubricant active agents for example boron nitride or aluminium nitride
- Solid fillers, and especially fillers that are hydrophilic or that have been rendered hydrophilic may also be incorporated, such as metal oxide, metal hydroxide or metal carbonate particles or organic particles.
- compound (1 ) in accordance with the invention is capable of chemically or physically modifying the skin such that compound (2) can become active or such that its activity is reinforced on the pretreated skin in order to impart an antiperspirant effect.
- compound (1 ) is capable of treating the skin by involving a chemical reaction.
- the expression "compounds that are capable of treating the skin by involving a chemical reaction” means that the cosmetic composition A comprises one or more compounds that are capable of inducing a chemical reaction with the skin, for example a chemical reaction with the skin proteins or with other compounds such as water or body fats in order thereafter to react with the skin.
- Compound (1 ) may be chosen especially from:
- compound (1 ) is capable of grafting to the skin.
- compound (1 ) includes one or more functions capable of grafting to the skin, especially by reacting with the nucleophilic functions of the skin, such as the hydroxyl, mercaptan and amine functions of the skin.
- compound (1 ) may include one or more functions capable of grafting to the skin, which may be chosen from the following functions:
- vinyl and activated vinyl in particular acrylonitrile and acrylic and methacrylic esters, crotonic acid and crotonic esters, cinnamic acid and cinnamic esters, styrene and derivatives thereof, and butadiene,
- aminals aminals, hemiaminals,
- ketones alpha-hydroxy ketones, alpha-halo ketones,
- halide of unsaturated carbon-based ring or heterocycle especially chlorotriazine, chloropyrimidine, chloroquinoxaline or chlorobenzotriazole,
- RSO2CI or F R being a C1-C30 alkyl
- activated vinyl means that the vinyl function has an asymmetrical electronic distribution and is thus more reactive.
- compound (1 ) may include one or more siloxane functions that may react, for example, with one or more hydroxyl or amine functions of the skin.
- compound (1 ) is capable of opening one or more bonds of the skin, in particular the disulfide bonds or the peptide bonds of the keratin constituting the skin.
- the expression "opening the disulfide or peptide bonds of the keratin constituting the skin” means that compound (1 ) comprises one or more compounds that are capable of breaking the disulfide bonds (S-S) or the peptide bonds (carbon/nitrogen bonds between two amino acids) of keratin.
- Compound (1 ) that is capable of opening one or more disulfide or peptide bonds of keratin may generate one or more reactive groups at the surface of the skin.
- such compounds are considered as being compounds that are capable of creating reactive groups at the surface of the skin.
- compound (1 ) that is capable of opening one or more disulfide bonds of keratin when applied to the skin, one or more reactive groups are formed at the surface of the skin, such as thiol groups, thiosulfate groups, mixed disulfide groups and/or sulfonic acid groups.
- reactive groups such as thiol groups, thiosulfate groups, mixed disulfide groups and/or sulfonic acid groups.
- the term "mixed disulfide” means a compound in which the two groups containing two sulfur atoms of the disulfide are different and in particular do not produce the same electron-donating or electron-withdrawing effect. In this asymmetric manner, the mixed disulfide may be more reactive than a symmetrical disulfide.
- compound (1 ) when compound (1 ) is capable of opening one or more peptide bonds, for example by hydrolysing the peptide bonds of protein chains or by hydrolysing the pendent functions of proteins, and in particular the amide functions of glutamine and asparagine, one or more reactive groups are created by especially forming one or more amine and/or acid functions at the surface of the skin.
- Compound (1 ) that is capable of opening one or more disulfide or peptide bonds of the skin may be chosen from reducing agents, acids, bases and oxidizing agents, and a mixture of these compounds.
- the reducing agent(s) that may be used in the cosmetic composition A may be chosen from thiols, sulfinic acids, phosphines, sulfites and hydrides, or a mixture of these compounds.
- thiol reducing agents it is especially possible to use thioglycolic acid, cysteine, homocysteine or thiolactic acid, and also the salts of these thiols.
- sulfinic acids hydroxymethanesulfinic acid is preferably used.
- the cosmetically acceptable salts of the sulfinic acids are especially chosen from alkali metal (Na, K), alkaline-earth metal (Ca) or zinc sulfinates.
- Sodium hydroxymethanesulfinate is particularly preferred among the sulfinic acids that may be envisaged in the composition.
- alkali metal alkaline-earth metal or ammonium salts, and also mixtures thereof. More particularly, mention may be made of sodium sulfite and sodium hydrogen sulfite.
- alkali metal or alkaline-earth metal salts such as sodium hydrides.
- phosphines it is preferred to use tris(hydroxymethyl)phosphine, tris(hydroxypropyl)phosphine and tris(carboxyethyl)phosphine.
- the acid(s) that may be used in the cosmetic composition A may be chosen from mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, and sulfonic acids.
- the base(s) may be chosen from aqueous ammonia, alkali metal carbonates, alkanolamines such as monoethanolamine, diethanolamine or triethanolamine, and also derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula (VI) below:
- W is a propylene residue optionally substituted with a hydroxyl group or a Ci-C 4 alkyl radical
- R a , R b , R c and R d which may be identical or different, represent a hydrogen atom or a Ci-C 4 alkyl or Ci-C 4 hydroxyalkyl radical.
- the oxidizing agent(s) may be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids, and oxidase enzymes (with the possible cofactors thereof), among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases, and 4- electron oxygenases, for instance laccases.
- compound (1 ) that is capable of opening one or more disulfide bonds is chosen from sulfites, in particular sulfite salts, especially alkali metal or alkaline- earth metal sulfites such as sodium sulfite, and thioglycolic acid.
- sulfites in particular sulfite salts, especially alkali metal or alkaline- earth metal sulfites such as sodium sulfite, and thioglycolic acid.
- compound (1 ) is capable of modifying the ionic nature of the skin by creating ionic groups at the surface of the skin, such as anionic, cationic or zwitterionic groups, or by creating hydrophobic groups.
- compound (1 ) is capable of modifying the ionic nature of the skin by creating anionic or cationic groups at the surface of the skin.
- compound (1 ) may be chosen from cysteine salts that modify the ionic nature of the skin by creating anionic groups at the surface of the skin.
- the cysteine salts are cysteine halides, such as cysteine hydrochloride.
- Compound (1 ) that is capable of modifying the ionic nature of the skin by creating cationic groups may also be chosen from alkoxysilanes comprising a substituent including a primary amine function, which are chosen from the compounds of formula:
- radicals R which may be identical different, are selected from C1-C6 alkyl radicals and n is an integer from 1 to 6, preferably from 2 to 4.
- alkoxysilane that is particularly preferred according to this embodiment of the invention is ⁇ -aminopropyltriethoxysilane.
- a compound is sold, for example, under the name Z-601 1 Silane by the company Dow Corning.
- Compound (1 ) may be chosen in particular from cationic polymers.
- the cationic polymer(s) may be chosen from: a) polymers that are formed from repeating units corresponding to formula (IX) below:
- Such polymers may be prepared according to the processes described in US patents 4 157 388, 4 702 906 and 4 719 282. They are especially described in Patent application EP-A-122 324. More particularly, the preferred compounds are the compound of formula (IX) in which Ri 3, Ri 4 , R15 and R16 represent a methyl radical, n is equal to 3 and p is equal to 6 and X " represents a chloride anion (referred to hereinbelow as Mexomer PO) and the compound of formula (IX) in which R13 and Ri 4 represent an ethyl radical, R15 and R16 represent a methyl radical, n and p are equal to 3 and X " represents a bromide anion (referred to hereinbelow as Mexomer PAK).
- Mexomer PAK a bromide anion
- compound (1 ) that is capable of modifying the ionic nature of the skin is preferably chosen from cysteine salts, cationic polymers of formula (IX) and alkoxysilanes comprising a substituent including a primary amine function chosen from the compounds of formula (I) described above.
- the compound (1 ) is capable of removing all or some of the molecules present in the skin.
- compound (1 ) may especially react with water so as to dry out the skin.
- compound (1 ) may be chosen from anhydrides, in particular organic or mineral anhydrides such as phosphate anhydride.
- compound (1 ) may be capable of generating one or more catalytic groups at the surface of the skin.
- compound (1 ) may be chosen from metal salts and enzymes that are grafted to the skin.
- compound (1 ) may be a catalyst that binds to the skin.
- compound (1 ) may be chosen from enzymes, in particular laccases, oxidases, dismutases, catalases, peroxidases and transition metal salts or other metal atoms.
- compound (1 ) that is capable of creating catalytic groups at the surface of the skin is chosen from copper salts and manganese salts such as manganese chloride.
- a compound (1 ) that is capable of grafting to the skin may be combined with one or more compounds (1 ) that are capable of opening the disulfide bonds of keratin, in particular thioglycolic acid.
- Thioglycolic acid makes it possible to create at the surface of the skin reactive groups such as thiols that form a bond with the catalysts bound to the skin, which have been formed from the transition metal salts. The bond obtained is resistant to water and to various washing operations.
- compound (1 ) is capable of treating the skin without involving a chemical reaction with the skin.
- the expression "without involving a chemical reaction with the skin” means that compound (1 ) is capable of treating the skin without exerting a chemical action, i.e. compound (1 ) does not induce any chemical reaction with the skin, either at the time of application of the composition containing it, or thereafter.
- compound (1 ) is capable of modifying the physical properties of the skin in the absence of a chemical reaction therewith.
- compound (1 ) is capable of increasing the retention on the skin of at least one compound (2).
- compound (1 ) is chosen from oils and/or waxes as defined previously, the compounds (1 ) capable of creating physical interactions with one or more compounds (2).
- compound (1 ) is capable of removing on and/or in the skin the agents that are liable to harm the action of compound (2).
- compound (1 ) may be capable of removing elements that may be present in the skin pores.
- compound (1 ) may be capable of improving the distribution and/or penetration of at least one compound (2) on and/or into the skin.
- compound (1 ) may be capable of improving the penetration of at least one compound (2) into the skin or into the sweat ducts.
- compound (1 ) may be chosen from lubricants, agents that modify the surface tension of the skin, solubilizers, or agents capable of removing compounds that may be an obstacle to the action of at least one compound (2).
- the lubricants that may be used in the cosmetic composition A may be chosen from polyethylene glycols (e.g. PEG-14M and PEG-23M) and silicones such as dimethicone, dimethiconol, dimethicone copolyol, stearyl dimethicone, cetyl dimethicone copolyol or cyclomethicone.
- polyethylene glycols e.g. PEG-14M and PEG-23M
- silicones such as dimethicone, dimethiconol, dimethicone copolyol, stearyl dimethicone, cetyl dimethicone copolyol or cyclomethicone.
- the agents that modify the surface tension of the skin may be chosen from surfactants, in particular cationic, nonionic, anionic or amphoteric surfactants.
- surfactants in particular cationic, nonionic, anionic or amphoteric surfactants.
- those bearing cationic functions such as genamine or betaines.
- the solubilizers that may be used in the cosmetic composition A may be water, one or more organic solvents or a mixture of water and organic solvent.
- organic solvents examples include Ci-C 4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2- butoxyethanol, propylene glycol, glycerol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monoethyl ether, and also aromatic alcohols, for instance benzyl alcohol or phenoxyethanol, and mixtures thereof.
- compound (1 ) may be chosen from agents that are capable of removing from the skin compounds that may be an obstacle to the action of at least one compound (2).
- compound (1 ) may be capable of freeing the skin of salts that may be present, such as zinc.
- compound (1 ) may be capable of modifying the porosity of the skin.
- it may be chosen from organic solvents and also products capable of breaking one or more hydrogen bonds, such as urea.
- compound (1 ) may be capable of making the skin reactive.
- it may be chosen from oxidizing agents used under strict operating conditions so as to make the skin reactive.
- compound (1 ) may be an inhibitor chosen in particular from zinc salts whose inhibitory action towards thiol functions prevents these functions from being reductive.
- Compound (1 ) may also be chosen to withstand movements, elongation and friction.
- compound (1 ) may especially facilitate the penetration of at least one compound (2) into the skin, increase its retention on the skin and improve its functioning.
- compound (1 ) is capable of treating the skin by involving a chemical reaction.
- compound (1 ) is chosen from cysteine salts, in particular cysteine hydrochloride, sulfite salts, in particular alkali metal or alkaline-earth metal sulfites such as sodium sulfite, alkoxysilanes of formula (I), in particular 3- aminopropyltriethoxysilane, manganese salts such as manganese chloride, thioglycolic acid, cationic polymers of formula (IX), or a mixture of these compounds.
- cysteine salts in particular cysteine hydrochloride
- sulfite salts in particular alkali metal or alkaline-earth metal sulfites such as sodium sulfite
- alkoxysilanes of formula (I) in particular 3- aminopropyltriethoxysilane
- manganese salts such as manganese chloride, thioglycolic acid, cationic
- Compound (2) is preferably chosen from compounds that are capable of acting on the skin once it has been chemically or physically modified by compound (1 ) to impart an antiperspirant effect.
- the expression "acting on the skin once it has been treated” means that compound (2) is capable of being active on contact with the skin once it has been treated with compound (1 ).
- compound (2) is selected from compounds that are capable of reacting with compound (1 ) grafted to the skin.
- compound (2) when compound (1 ) is capable of opening the disulfide bonds of the skin, thus forming reactive groups such as thiol groups, then compound (2) is capable of reacting with the reactive groups thus formed, to impart an antiperspirant effect.
- compound (2) is a reducing agent such as cysteine.
- compound (2) may be chosen from fluorinated alkoxysilanes.
- compound (2) when compound (1 ) is capable of modifying the ionic nature of the skin by forming one or more ionic groups, then compound (2) is selected from compounds bearing one or more ionic charges of opposite sign to the ionic groups formed on the skin, so as to create an ionic interaction to impart an antiperspirant effect.
- compound (1) when compound (1 ) is capable of modifying the ionic nature of the skin by forming one or more anionic groups, then compound (2) is selected from compounds bearing one or more cationic charges capable of creating an ionic interaction with the negatively charged skin.
- compound (2) is selected so as to be able to react with the negatively charged skin by means of an anion/cation interaction.
- compound (2) is selected from compounds bearing one or more anionic charges that are capable of creating an ionic interaction with the positively charged skin.
- compound (2) is selected so as to be able to react with the positively charged skin by means of a cation/anion interaction.
- compound (2) may be chosen from anionic polymers, metal salts, transition metal salts and/or cellulose esters.
- the preferential anionic polymer(s) comprise at least, as monomers, vinyl acetate, vinyl neodecanoate and crotonic acid, and more particularly the terpolymer of vinyl acetate, vinyl tert-butylbenzoate and crotonic acid is used.
- Such anionic polymers may be partially or totally neutralized with a basifying agent.
- the basifying agent is chosen from alkanolamines such as
- alkali metal or alkaline-earth metal salts that may especially be used are halides, hydroxides, borates or nitrates, and more particularly alkali metal or alkaline-earth metal halides and borates, such as sodium chloride or sodium tetraborate.
- transition metal salts that may especially be used are transition metal halides, such as zinc chloride or manganese chloride.
- compound (1 ) when compound (1 ) is capable of forming catalytic groups on the skin, then compound (2) is selected from compounds that are capable of reacting in the presence of the catalytic groups so as to impart an antiperspirant effect.
- compound (1 ) when compound (1 ) is chosen from manganese salts, these compounds bind to the skin so as to give it catalytic activity that promotes oxidation and compound (2) will then be selected from compounds that are capable of being oxidized, such as indoles, indole derivatives or thiol compounds, so as to impart an antiperspirant effect.
- compound (2) when compound (1 ) is capable of modifying the porosity of the skin, then compound (2) is selected from compounds that are capable of acting within the skin so as to impart an antiperspirant effect.
- compound (1 ) when compound (1 ) is capable of increasing the surface tension of the skin, then compound (2) is selected from compounds that are capable of spreading on skin whose surface tension has been increased, so as to impart an antiperspirant effect.
- compound (2) when the compound is a solubilizing agent, then compound (2) is selected from compounds that are capable of dissolving compound (1 ), so as to impart an antiperspirant effect.
- compound (2) when compound (1 ) is capable of modifying the hydrophobicity of the skin, compound (2) is used in the presence of a volatile hydrophobic solvent and is chosen from compounds that are capable of entering the skin pores, so as to impart an antiperspirant effect.
- compound (2) when compound (1 ) is capable of reducing the surface tension of the skin, then compound (2) is used in the presence of a liquid with a high surface tension and is chosen from compounds that are capable of entering the skin pores, so as to impart an antiperspirant effect.
- Compound (2) may be chosen to withstand movements, elongation and friction.
- compound (2) may be chosen from compounds that are capable of withstanding abrasion, such as boron nitride.
- compound (2) is chosen from one or more fluorinated alkoxysilanes, one or more anionic polymers comprising at least, as monomers, vinyl acetate, vinyl neodecanoate and crotonic acid, cellulose esters, in particular hydroxypropylmethylcellulose phthalate, metal salts, in particular transition metal halides, reducing agents such as cysteine, indoles or derivatives thereof, aluminium chlorohydrate and sodium tetraborate.
- anionic polymers comprising at least, as monomers, vinyl acetate, vinyl neodecanoate and crotonic acid
- cellulose esters in particular hydroxypropylmethylcellulose phthalate
- metal salts in particular transition metal halides
- reducing agents such as cysteine, indoles or derivatives thereof, aluminium chlorohydrate and sodium tetraborate.
- compound (1 ) is chosen from those that are capable of modifying the ionic nature of the skin by creating cationic groups
- compound (2) is chosen from compounds bearing one or more anionic charges capable of reacting with the cationic groups at the surface of the skin.
- compound (1 ) may be chosen from cysteine salts, in particular cysteine hydrochloride, and compound (2) is chosen from metal salts, in particular transition metal salts such as zinc chloride.
- compound (1 ) may be chosen from cysteine salts, in particular cysteine hydrochloride, and compound (2) is chosen from fluorinated alkoxysilanes.
- compound (1 ) may be chosen from sulfites, in particular alkali metal or alkaline-earth metal sulfites such as sodium sulfite, and compound (2) is chosen from fluorinated alkoxysilanes.
- compound (1 ) may be chosen from the alkoxysilanes of formula (I) and compound (2) is chosen from magnesium chloride and anionic polymers comprising at least, as monomers, vinyl acetate, vinyl neodecanoate and crotonic acid.
- compound (1 ) may be chosen from manganese salts, such as manganese chloride, and thioglycolic acid, and compound (2) is cysteine.
- compound (1 ) is chosen from manganese salts, such as manganese chloride, and thioglycolic acid, and compound (2) is dihydroxyindole.
- compositions according to the invention preferably contain at least one water- immiscible organic liquid phase, known as an oily phase.
- This phase generally comprises one or more hydrophobic compounds that make the said phase water immiscible.
- the said phase is liquid (in the absence of a structuring agent) at room temperature (20-25°C) and atmospheric pressure (760 mmHg, i.e. 10 5 Pa).
- the water-immiscible organic-liquid organic phase in accordance with the invention is generally formed from at least one volatile oil and/or nonvolatile non-silicone oil and/or a non-volatile silicone oil.
- oil means a fatty substance that is liquid at room temperature (20-25°C) and atmospheric pressure (760 mmHg, i.e. 10 5 Pa).
- the oil may be volatile or nonvolatile.
- volatile oil means an oil that is capable of evaporating on contact with the skin or the keratin fibre in less than one hour, at room temperature and atmospheric pressure.
- volatile oils of the invention are volatile cosmetic oils, which are liquid at room temperature, having a non-zero vapour pressure, at room temperature and atmospheric pressure, ranging in particular from 0.13 Pa to 40 000 Pa (10 "3 to 300 mmHg), in particular ranging from 1 .3 Pa to 13 000 Pa (0.01 to 100 mmHg) and more particularly ranging from 1 .3 Pa to 1300 Pa (0.01 to 10 mmHg).
- non-volatile oil means an oil that remains on the skin or the keratin fibre at room temperature and atmospheric pressure for at least several hours, and that especially has a vapour pressure of less than 10 "3 mmHg (0.13 Pa).
- oils in accordance with the invention are preferably chosen from any cosmetically acceptable oil, especially mineral, animal, plant or synthetic oils, especially hydrocarbon-based oils, fluoro oils or silicone oils, or mixtures thereof.
- hydrocarbon-based oil means an oil mainly containing carbon and hydrogen atoms and possibly one or more functions chosen from hydroxyl, ester, ether and carboxylic functions.
- the oil has a viscosity of from 0.5 to 100 000 mPa.s, preferably from 50 to 50 000 mPa.s and more preferably from 100 to 300 000 mPa.s.
- silicon oil means an oil comprising in its structure carbon atoms and at least one silicon atom.
- fluoro oil means partially hydrocarbon-based and/or silicone-based oils comprising carbon atoms and fluorine atoms.
- volatile hydrocarbon-based oils that may be used in the invention, mention may be made of:
- hydrocarbon-based oils chosen from hydrocarbon-based oils containing from 8 to 16 carbon atoms, and especially Cs-Ci6 isoalkanes of petroleum origin (also known as isoparaffins), for instance isododecane (also known as 2,2,4,4,6- pentamethylheptane), isodecane and isohexadecane, for example the oils sold under the trade names Isopar or Permethyl, branched Cs-Ci6 esters and isohexyl neopentanoate, and mixtures thereof.
- Cs-Ci6 isoalkanes of petroleum origin also known as isoparaffins
- isododecane also known as 2,2,4,4,6- pentamethylheptane
- isodecane and isohexadecane for example the oils sold under the trade names Isopar or Permethyl, branched Cs-Ci6 esters and isohexyl neopentanoate, and
- volatile hydrocarbon-based oils for instance petroleum distillates, especially those sold under the name Shell Solt by the company Shell, may also be used; volatile linear alkanes, such as those described in patent application DE10 2008 012 457 from the company Cognis.
- non-volatile hydrocarbon-based oils that may be used in the invention, mention may be made of:
- hydrocarbon-based plant oils such as liquid triglycerides of fatty acids of 4 to 24 carbon atoms, for instance heptanoic or octanoic acid triglycerides, or wheatgerm oil, olive oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, alfalfa oil, poppy oil, pumpkin oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil, musk rose oil, sunflower oil, corn oil, soybean oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, castor oil, avocado oil, caprylic/capric acid triglycerides, for instance those sold by the company Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel, jojoba
- - synthetic esters especially of fatty acids, for instance the oils of formula R1COOR2 in which Ri represents a linear or branched higher fatty acid residue containing from 1 to 40 carbon atoms and R2 represents a hydrocarbon-based chain, which is especially branched, containing from 1 to 40 carbon atoms, with Ri + R2 > 10, for instance purcellin oil (cetostearyl octanoate), isononyl isononanoate, isopropyl myristate, isopropyl palmitate, C12-C15 alkyl benzoates, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2-octyldodecyl erucate, isostearyl isostearate or tridecyl trimellitate; alcohol or polyalcohol oct
- - fatty alcohols that are liquid at room temperature, containing a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance octyldodecanol, isostearyl alcohol, 2-butyloctanol, 2-hexyldecanol, 2- undecylpentadecanol or oleyl alcohol,
- fluorosilicone oils examples include fluorosilicone oils, fluoro polyethers and fluorosilicones as described in document EP-A-847 752.
- non-volatile silicone oils mention may be made of linear or cyclic non-volatile polydimethylsiloxanes (PDMS); polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, which are pendant or at the end of a silicone chain, these groups containing from 2 to 24 carbon atoms; phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenyl siloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes and 2- phenylethyl trimethylsiloxy silicates, and mixtures thereof.
- PDMS linear or cyclic non-volatile polydimethylsiloxanes
- the compositions contain less than 2% volatile silicone oil, or even less than 0.5% volatile silicone oil, and are especially free of volatile silicone oil; the volatile silicone oil not being added during the preparation of the composition, but corresponding to the residual volatile silicone oil introduced by the mixed ingredients.
- composition according to the invention comprises at least one solid fatty substance preferably chosen from waxes and pasty fatty substances, and mixtures thereof, and more particularly waxes.
- pasty fatty substance means a lipophilic fatty compound with a reversible solid/liquid change of state, displaying anisotropic crystal organization in the solid state, and comprising a liquid fraction and a solid fraction at a temperature of 23°C.
- the starting melting point of the pasty compound can be less than 23°C.
- the liquid fraction of the pasty compound measured at 23°C can represent 9% to 97% by weight of the compound. This liquid fraction at 23°C preferably represents between 15% and 85% and more preferably between 40% and 85% by weight.
- the melting point corresponds to the temperature of the most endothermic peak observed on thermal analysis (DSC) as described in Standard ISO 1 1357-3; 1999.
- the melting point of a pasty substance or of a wax may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name MDSC 2920 by the company TA Instruments.
- the measuring protocol is as follows:
- a sample of 5 mg of paste or wax (depending on the case) placed in a crucible is subjected to a first temperature rise passing from -20°C to 100°C, at the heating rate of 10°C/minute, then is cooled from 100°C to -20°C at a cooling rate of 10°C/minute and finally subjected to a second temperature rise passing from -20°C to 100°C at a heating rate of 5°C/minute.
- the melting point of the compound is the value of the temperature corresponding to the tip of the peak of the curve representing the variation in the difference in power absorbed as a function of the temperature.
- the liquid fraction by weight of the pasty compound at 23°C is equal to the ratio of the heat of fusion consumed at 23°C to the heat of fusion of the pasty compound.
- the heat of fusion of the pasty compound is the heat consumed by the compound in order to pass from the solid state to the liquid state.
- the pasty compound is said to be in the solid state when all of its mass is in crystalline solid form.
- the pasty compound is said to be in the liquid state when all of its mass is in liquid form.
- the heat of fusion of the pasty compound is equal to the area under the curve of the thermogram obtained using a differential scanning calorimeter (DSC), such as the calorimeter sold under the name MDSC 2920 by the company TA Instrument, with a temperature rise of 5°C or 10°C per minute, according to standard ISO 1 1357-3:1999.
- DSC differential scanning calorimeter
- the heat of fusion of the pasty compound is the amount of energy required to make the compound change from the solid state to the liquid state. It is expressed in J/g.
- the enthalpy of fusion consumed at 23°C is the amount of energy absorbed by the sample to change from the solid state to the state that it has at 23°C, composed of a liquid fraction and a solid fraction.
- the liquid fraction of the pasty compound measured at 32°C preferably represents from 30% to 100% by weight of the compound, preferably from 50% to 100%, more preferably from 60% to 100% by weight of the compound.
- the temperature of the end of the melting range of the pasty compound is less than or equal to 32°C.
- the liquid fraction of the pasty compound measured at 32°C is equal to the ratio of the heat of fusion consumed at 32°C to the heat of fusion of the pasty compound.
- the heat of fusion consumed at 32°C is calculated in the same way as the heat of fusion consumed at 23°C.
- the pasty compound is preferably chosen from synthetic compounds and compounds of plant origin.
- a pasty compound may be obtained by the synthesis from starting materials of plant origin.
- the pasty compound is advantageously chosen from:
- - polyol ethers chosen from ethers of pentaerythritol and of polyalkylene glycol, ethers of fatty alcohol and of sugar, and mixtures thereof, the ethers of pentaerythritol and of polyethylene glycol comprising 5 oxyethylene units (5 OE) (CTFA name: PEG-5 Pentaerythrityl Ether), the polypropylene glycol pentaerythrityl ether comprising 5 oxypropylene (5 OP) units (CTFA name: PPG-5 Pentaerythrityl Ether) and mixtures thereof, and more especially the mixture PEG- 5 Pentaerythrityl Ether, PPG-5 Pentaerythrityl Ether and soybean oil, sold under the name Lanolide by the company Vevy, which is a mixture in which the constituents are in a 46/46/8 weight ratio: 46% PEG-5 Pentaerythrityl Ether, 46% PPG-5 Pentaerythrityl Et
- the pasty compound is preferably a polymer, especially a hydrocarbon-based polymer.
- liposoluble polyethers that are particularly preferred are copolymers of ethylene oxide and/or of propylene oxide with C6-C30 long-chain alkylene oxides, more preferably such that the weight ratio of the ethylene oxide and/or of the propylene oxide to the alkylene oxides in the copolymer is from 5:95 to 70:30.
- copolymers such that the long-chain alkylene oxides are arranged in blocks having an average molecular weight from 1000 to 10 000, for example a polyoxyethylene/polydodecyl glycol block copolymer such as the ethers of dodecanediol (22 mol) and of polyethylene glycol (45 OE) sold under the brand name Elfacos ST9 by Akzo Nobel.
- esters the following are especially preferred:
- - esters of a glycerol oligomer especially diglycerol esters, in particular condensates of adipic acid and of glycerol, for which some of the hydroxyl groups of the glycerols have reacted with a mixture of fatty acids such as stearic acid, capric acid, stearic acid and isostearic acid, and 12-hydroxystearic acid, especially such as those sold under the brand name Softisan 649 by the company Sasol,
- the aliphatic carboxylic acid comprises from 4 to 30 and preferably from 8 to 30 carbon atoms.
- the aliphatic carboxylic acid is preferably branched.
- the aliphatic hydroxycarboxylic acid ester is advantageously derived from a hydroxylated aliphatic carboxylic acid containing from 2 to 40 carbon atoms, preferably from 10 to 34 carbon atoms and better still from 12 to 28 carbon atoms, and from 1 to 20 hydroxyl groups, preferably from 1 to 10 hydroxyl groups and better still from 1 to 6 hydroxyl groups.
- the aliphatic hydroxycarboxylic acid ester is chosen from:
- esters of a diol dimer and of a diacid dimer where appropriate esterified on their free alcohol or acid function(s) with acid or alcohol radicals, especially dimer dilinoleate esters; such esters may be chosen especially from the esters having the following INCI nomenclature: bis-behenyl/isostearyl/phytosteryl dimer dilinoleyl dimer dilinoleate (Plandool G), phytosteryl/isostearyl/cetyl/stearyl/behenyl dimer dilinoleate (Plandool H or Plandool S), and mixtures thereof,
- rosinate esters such as dilinoleyl dimers of hydrogenated rosinate (Lusplan DD-DHR or DD-DHR from Nippon Fine Chemical);
- the composition according to the invention comprises at least one wax.
- the wax under consideration in the context of the present invention is generally a lipophilic compound that is solid at room temperature (25°C), with a solid/liquid reversible change of state, having a melting point of greater than or equal to 30°C, which may be up to 200°C and in particular up to 120°C.
- the waxes that are suitable for the invention may have a melting point of greater than or equal to 45°C and in particular greater than or equal to 55°C.
- the waxes that may be used in the compositions according to the invention are chosen from waxes that are solid at room temperature of animal, plant, mineral or synthetic origin, and mixtures thereof.
- hydrocarbon-based waxes comprising a fatty alkyl chain generally containing from 10 to 60 carbon atoms and preferably from 20 to 40 carbon atoms, the said chain possibly being saturated or unsaturated, substituted or unsubstituted, and linear, branched or cyclic, preferably saturated and linear:
- - fatty acid esters including triglycerides
- fatty alcohols mention may be made of stearyl alcohol and cetearyl alcohol, or mixtures thereof.
- fatty alcohol esters mention may be made of triisostearyl citrate, ethylene glycol bis(12-hydroxystearate), tristearyl citrate, stearyl octanoate, stearyl heptanoate, trilauryl citrate, and mixtures thereof.
- fatty acid esters mention may be made of ester waxes, monoglycerides, diglycerides and triglycerides.
- Ester waxes that may be mentioned include stearyl stearate, stearyl behenate, stearyloctyldodecanol, cetearyl behenate, behenyl behenate, ethylene glycol distearate and ethylene glycol dipalmitate.
- Use may be made in particular of a C 2 0- C 4 o alkyl (hydroxystearyloxy)stearate (the alkyl group containing from 20 to 40 carbon atoms), alone or as a mixture.
- Such a wax is especially sold under the names Kester Wax K 82 P®, Hydroxypolyester K 82 P® and Kester Wax K 80 P® by the company Koster Keunen.
- the triglyceride waxes mention may be made more particularly of Tribehenine, C18-C36 triglycerides, and mixtures thereof.
- waxes that are suitable for the invention, mention may be made especially of hydrocarbon-based waxes, for instance beeswax, lanolin wax, Chinese insect waxes, rice bran wax, carnauba wax, candelilla wax, ouricury wax, esparto grass wax, berry wax, shellac wax, Japan wax and sumach wax; montan wax, orange wax and lemon wax, microcrystalline waxes, paraffins and ozokerite; polyethylene waxes, the waxes obtained by Fischer-Tropsch synthesis and waxy copolymers, and also esters thereof.
- hydrocarbon-based waxes for instance beeswax, lanolin wax, Chinese insect waxes, rice bran wax, carnauba wax, candelilla wax, ouricury wax, esparto grass wax, berry wax, shellac wax, Japan wax and sumach wax; montan wax, orange wax and lemon wax, microcrystalline waxes, paraffins and ozokerite; polyethylene waxe
- waxes obtained by catalytic hydrogenation of animal or plant oils containing linear or branched C8-C32 fatty chains are examples of waxes obtained by catalytic hydrogenation of animal or plant oils containing linear or branched C8-C32 fatty chains.
- isomerized jojoba oil such as the trans- isomerized partially hydrogenated jojoba oil manufactured or sold by the company Desert Whale under the commercial reference lso-Jojoba-50®, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil, hydrogenated lanolin oil and bis(1 ,1 ,1 -trimethylolpropane) tetrastearate sold under the name Hest 2T-4S® by the company Heterene.
- silicone waxes C3o -4 5 alkyl dimethicone
- fluoro waxes C3o -4 5 alkyl dimethicone
- waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol sold under the names Phytowax ricin 16L64® and 22L73® by the company Sophim, may also be used. Such waxes are described in patent application FR-A- 2 792 190.
- microwaxes that may be used in the compositions according to the invention, mention may be made especially of carnauba microwaxes, such as the product sold under the name MicroCare 350® by the company Micro Powders, synthetic microwaxes, such as the product sold under the name MicroEase 1 14S® by the company Micro Powders, microwaxes consisting of a mixture of carnauba wax and polyethylene wax, such as the products sold under the names Micro Care 300® and 310® by the company Micro Powders, microwaxes consisting of a mixture of carnauba wax and of synthetic wax, such as the product sold under the name Micro Care 325® by the company Micro Powders, polyethylene microwaxes, such as the products sold under the names Micropoly 200®, 220®, 220L® and 250S® by the company Micro Powders, and polytetrafluoroethylene microwaxes, such as the products sold under the names Microslip 519® and 519 L® by the company Micro Powders.
- composition according to the invention may comprise a content of solid fatty substance preferably ranging from 1 % to 20% by weight and in particular from 2% to 15% by weight relative to the total weight of the composition.
- composition according to the invention may comprise lipophilic thickeners, gelling agents and/or suspension agents to improve the texture or the homogeneity of the products.
- Mineral thickeners, gelling agents and suspension agents may comprise lipophilic thickeners, gelling agents and/or suspension agents to improve the texture or the homogeneity of the products.
- modified clays that are preferably chosen from hydrophobic-modified montmorillonite clays, for instance hydrophobic-modified bentonites or hectorites.
- CTFA name Stearalkonium Bentonite
- CTFA name Disteardimonium Hectorite
- fumed silica optionally subjected to a hydrophobic surface treatment, the particle size of which is less than 1 ⁇ .
- a hydrophobic surface treatment it is possible to chemically modify the surface of the silica, by chemical reaction generating a reduced number of silanol groups present at the surface of the silica.
- hydrophobic groups may be trimethylsiloxyl groups, which are obtained especially by treating fumed silica in the presence of hexamethyldisilazane.
- Silicas thus treated are known as "silica silylate" according to the CTFA (8th Edition, 2000).
- Silicas thus treated are known as "silica dimethyl silylate" according to the CTFA (8th Edition, 2000). They are sold, for example, under the references Aerosil R972® and Aerosil R974® by the company Degussa, and Cab-O-Sil TS-610® and Cab-O-Sil TS-720® by the company Cabot.
- the hydrophobic fumed silica preferably has a particle size that may be nanometric to micrometric, for example ranging from about 5 to 200 nm.
- Organic thickeners, gelling agents and suspension agents are examples of organic thickeners, gelling agents and suspension agents.
- the organic lipophilic thickeners or gelling agents are, for example, partially or totally crosslinked elastomeric organopolysiloxanes of three-dimensional structure, for instance those sold under the names KSG6®, KSG16® and KSG18® from Shin-Etsu, Trefil E-505C® or Trefil E-506C® from Dow Corning, Gransil SR- CYC®, SR DMF10®, SR-DC556®, SR 5CYC gel®, SR DMF 10 gel® and SR DC 556 gel® from Grant Industries and SF 1204® and JK 1 13® from General Electric; ethylcellulose, for instance the product sold under the name Ethocel® by Dow Chemical; galactomannans comprising from one to six and in particular from two to four hydroxyl groups per saccharide, substituted with a saturated or unsaturated alkyl chain, for instance guar gum alkylated with C1 to C6, and in particular C1 to C3, alkyl chains,
- Block copolymers of "diblock”, “triblock” or “radial” type, of the polystyrene/polyisoprene or polystyrene/polybutadiene type such as the products sold under the name Luvitol HSB® by the company BASF, of the polystyrene/copoly(ethylene-propylene) type, such as the products sold under the name Kraton® by the company Shell Chemical Co., or of the polystyrene/copoly(ethylene-butylene) type, and mixtures of triblock and radial (star) copolymers in isododecane, such as those sold by the company Penreco under the name Versagel®, for instance the mixture of butylene/etnylene/styrene triblock copolymer and of ethylene/propylene/styrene star copolymer in isododecane (Versagel M 5960).
- Lipophilic thickeners or gelling agents that may also be mentioned include polymers with a weight-average molecular mass of less than 100 000, comprising a) a polymer backbone with hydrocarbon-based repeating units containing at least one heteroatom, and optionally b) at least one optionally functionalized pendent fatty chain and/or terminal fatty chain, containing from 6 to 120 carbon atoms and being linked to these hydrocarbon-based units, as described in patent applications WO-A-02/056 847 and WO-A-02/47619, in particular polyamide resins (especially comprising alkyl groups containing from 12 to 22 carbon atoms) such as those described in US-A-5 783 657.
- polymers with a weight-average molecular mass of less than 100 000 comprising a) a polymer backbone with hydrocarbon-based repeating units containing at least one heteroatom, and optionally b) at least one optionally functionalized pendent fatty chain and/or terminal fatty chain, containing from 6 to 120
- lipophilic thickeners or gelling agents that may be used in the compositions according to the invention, mention may also be made of fatty acid esters of dextrin, such as dextrin palmitates, especially the products sold under the name Rheopearl TL® or Rheopearl KL® by the company Chiba Flour.
- Silicone polyamides of the polyorganosiloxane type may also be used, such as those described in documents US-A-5 874 069, US-A-5 919 441 , US-A-6 051 216 and US-A-5 981 680.
- silicone polymers may belong to the following two families:
- - polyorganosiloxanes comprising at least two groups capable of establishing hydrogen interactions, these two groups being located on grafts or branches.
- the thickeners, gelling agents and suspension agents are preferably present in amounts ranging from 0.1 % to 15% by weight and more preferentially from 0.2% to 10% by weight relative to the total weight of the composition.
- the amounts of these various constituents that may be present in the cosmetic composition according to the invention are those conventionally used in compositions for treating perspiration.
- the oily phase may also contain one or more emulsifiers with an HLB (hydrophilic/lipophilic balance) of less than 8, preferably less than or equal to 6 and especially ranging from 4 to 6. They may be soluble or dispersible in the said phase.
- HLB hydrophilic/lipophilic balance
- emulsifiers examples include fatty esters of polyols, especially of glycerol or sorbitol, and especially the isostearic, oleic and ricinoleate esters of polyols, such as the mixture of petrolatum, polyglyceryl-3 oleate, glyceryl isostearate, hydrogenated castor oil and ozokerite, sold under the name Protegin W® by the company Goldschmidt, sorbitan isostearate, polyglyceryl diisostearate, polyglyceryl-2 sesquiisostearate; saccharide esters and ethers such as methyl glucose dioleate; fatty esters such as magnesium lanolate; dimethicone copolyols and alkyl dimethicone copolyols.
- Ri denotes a linear or branched C12-C20 and preferably C12-C18 alkyl group
- R 2 denotes the group: ⁇ CnH2n ⁇ (-OC2H 4 -) x ⁇ (-OC 3 H6-)y ⁇ O— R 3>
- R3 denotes a hydrogen atom or a linear or branched alkyl radical comprising from
- a is an integer ranging from 1 to about 500;
- b is an integer ranging from 1 to about 500;
- n is an integer ranging from 2 to 12 and preferably from 2 to 5;
- x is an integer ranging from 1 to about 50 and preferably from 1 to 30;
- y is an integer ranging from 0 to about 49 and preferably from 0 to 29, with the proviso that when y is other than zero, the ratio x/y is greater than 1 and preferably ranges from 2 to 1 1 .
- alkyl dimethicone copolyol emulsifiers of formula (I) that are preferred, mention will be made more particularly of Cetyl PEG/PPG-10/1 Dimethicone and more particularly the mixture Cetyl PEG/PPG-10/1 Dimethicone and Dimethicone (INCI name), for instance the product sold under the trade name Abil EM90 by the company Goldschmidt, or alternatively the mixture (Polyglyceryl-4 Stearate and Cetyl PEG/PPG-10 (and) Dimethicone (and) Hexyl Laurate), for instance the product sold under the trade name Abil WE09 by the same company.
- R 4 denotes the group: ⁇ C m H 2 m ⁇ (-OC2H 4 -) s ⁇ (-OC 3 H6-)t ⁇ O— R 5 , R 5 denotes a hydrogen atom or a linear or branched alkyl radical comprising from 1 to 12 carbon atoms,
- c is an integer ranging from 1 to about 500;
- d is an integer ranging from 1 to about 500;
- n is an integer ranging from 2 to 12 and preferably from 2 to 5;
- s is an integer ranging from 1 to about 50 and preferably from 1 to 30;
- t is an integer ranging from 0 to about 50 and preferably from 0 to 30; with the proviso that the sum s+t is greater than or equal to 1 .
- PEG-18/PPG-18 Dimethicone and more particularly the mixture Cyclopentasiloxane (and) PEG-18/PPG-18 Dimethicone (INCI name), such as the product sold by the company Dow Corning under the trade name Silicone DC 5225 C or KF-6040 from the company Shin-Etsu.
- Use will be made more particularly of a mixture of PEG-18/PPG-18 Dimethicone and Cetyl PEG/PPG-10/1 Dimethicone and even more particularly a mixture of (Cyclopentasiloxane (and) PEG-18/PPG-18 Dimethicone) and of Cetyl PEG/PPG- 10/1 Dimethicone and Dimethicone or of (Polyglyceryl-4-stearate and Cetyl PEG/PPG-10 (and) Dimethicone (and) Hexyl Laurate).
- water-in-oil emulsifiers mention may also be made of nonionic emulsifiers derived from fatty acids and polyol, alkylpolyglycosides (APG) and sugar esters, and mixtures thereof.
- APG alkylpolyglycosides
- sugar esters and mixtures thereof.
- nonionic emulsifiers derived from fatty acids and polyol use may be made especially of fatty acid esters of polyol, the fatty acid especially containing a Cs-C2 4 alkyl chain, and the polyols being, for example, glycerol and sorbitan.
- Fatty acid esters of polyol that may especially be mentioned include isostearic acid esters of polyols, stearic acid esters of polyols, and mixtures thereof, in particular isostearic acid esters of glycerol and/or sorbitan.
- Stearic acid esters of polyols that may especially be mentioned include the polyethylene glycol esters, for instance PEG-30 Dipolyhydroxystearate, such as the product sold under the name Arlacel P135 by the company ICI.
- Glycerol and/or sorbitan esters that may be mentioned, for example, include polyglyceryl isostearate, such as the product sold under the name Isolan Gl 34 by the company Goldschmidt; sorbitan isostearate, such as the product sold under the name Arlacel 987 by the company ICI; sorbitan glyceryl isostearate, such as the product sold under the name Arlacel 986 by the company ICI, the mixture of sorbitan isostearate and polyglyceryl isostearate (3 mmol) sold under the name Arlacel 1690 by the company Uniqema, and mixtures thereof.
- polyglyceryl isostearate such as the product sold under the name Isolan Gl 34 by the company Goldschmidt
- sorbitan isostearate such as the product sold under the name Arlacel 987 by the company ICI
- sorbitan glyceryl isostearate such as the product sold under the name Arlacel 986 by the
- the emulsifier may also be chosen from alkylpolyglycosides with an HLB of less than 7, for example those represented by the general formula (1 ) below: R-O-(G)x (1 ) in which R represents a branched and/or unsaturated alkyl radical comprising from 14 to 24 carbon atoms, G represents a reduced sugar comprising 5 or 6 carbon atoms, and x is a value ranging from 1 to 10 and preferably from 1 to 4, and G especially denotes glucose, fructose or galactose.
- R-O-(G)x (1 ) in which R represents a branched and/or unsaturated alkyl radical comprising from 14 to 24 carbon atoms, G represents a reduced sugar comprising 5 or 6 carbon atoms, and x is a value ranging from 1 to 10 and preferably from 1 to 4, and G especially denotes glucose, fructose or galactose.
- the unsaturated alkyl radical may comprise one or more ethylenic unsaturations, and in particular one or two ethylenic unsaturations.
- This alkylpolyglucoside may be used as a mixture with a coemulsifier, more especially with a fatty alcohol and especially a fatty alcohol containing the same fatty chain as that of the alkylpolyglucoside, i.e.
- a branched and/or unsaturated chain for example isostearyl alcohol when the alkylpolyglucoside is isostearyl glucoside, and oleyl alcohol when the alkylpolyglucoside is oleyl glucoside, optionally in the form of a self-emulsifying composition, as described, for example, in document WO-A-92/06778.
- Use may be made, for example, of the mixture of isostearyl glucoside and isostearyl alcohol, sold under the name Montanov WO 18 by the company SEPPIC, and also the mixture octyldodecanol and octyldodecyl xyloside sold under the name Fludanov 20X by the company SEPPIC.
- succinic-terminated polyolefins for instance esterified succinic-terminated polyisobutylenes and salts thereof, especially the diethanolamine salts, such as the commercial products sold under the names Lubrizol 2724, Lubrizol 2722 and Lubrizol 5603 by the company Lubrizol or the commercial product Chemcinnate 2000.
- oxyalkylenated especially polyoxyethylenated and/or polyoxypropylenated and more particularly polyoxyethylenated, silicone elastomers such as those described in documents US-A-5 236 986, US-A-5 412 004, US-A-5 837 793 and US-A-5 81 1 487.
- the polyoxyalkylenated silicone elastomer is preferably conveyed in the form of a gel in at least one hydrocarbon-based oil and/or one silicone oil. In these gels, the polyoxyalkylenated elastomer is often in the form of non-spherical particles.
- polyoxyalkylenated silicone elastomers are especially:
- polyoxyethylenated silicone elastomers use may be made of those sold by the company Shin-Etsu under the names:
- KSG-210 (INCI name: dimethicone/PEG-10/15 crosspolymer), which contains about 25% silicone elastomer active material in silicone oil, is preferably used.
- water-in-oil emulsifiers mention may also be made of polyglycerolated silicone elastomers. Such elastomers are described especially in document WO-A- 2004/024 798.
- Polyglycerolated silicone elastomers that may be used include those sold under the names:
- KSG-710 (containing 25% active material. INCI name: Dimethicone/polyglycerine-3 crosspolymer),
- compositions may be in liquid, gel, semi-solid, solid or loose or compact powder form.
- compositions of the invention may especially be conditioned in pressurized form in an aerosol device or in a pump-action bottle; conditioned in a device equipped with a perforated wall, especially a grille; conditioned in a device equipped with a ball applicator ("roll-on”); conditioned in the form of wands (sticks).
- they contain the ingredients generally used in products of this type, which are well known to those skilled in the art.
- compositions according to the invention may be solid, in particular in wand or stick form.
- solid composition means that the maximum force measured by texturometry during the penetration of a probe into the sample of formula must be at least equal to 0.25 newtons, in particular at least equal to 0.30 newtons and especially at least equal to 0.35 newtons, assessed under precise measuring conditions as follows.
- the formulae are poured hot into jars 4 cm in diameter and 3 cm deep. Cooling is performed at room temperature. The hardness of the formulae is measured after an interval of 24 hours.
- the jars containing the samples are characterized in texturometry using a texturometer such as the machine sold by the company Rheo TA-XT2, according to the following protocol: a stainless-steel ball probe 5 mm in diameter is brought into contact with the sample at a speed of 1 mm/s.
- the measuring system detects the interface with the sample, with a detection threshold equal to 0.005 newtons.
- the probe penetrates 0.3 mm into the sample, at a speed of 0.1 mm/s.
- the measuring machine records the change in force measured in compression over time, during the penetration phase.
- the hardness of the sample corresponds to the average of the maximum force values detected during penetration, over at least three measurements.
- compositions according to the invention may also comprise cosmetic adjuvants chosen from softeners, antioxidants, opacifiers, stabilizers, moisturizers, vitamins, bactericides, preserving agents, fragrances, moisture absorbers, deodorants, suspension agents, propellants or any other ingredient usually used in cosmetics for this type of application.
- cosmetic adjuvants chosen from softeners, antioxidants, opacifiers, stabilizers, moisturizers, vitamins, bactericides, preserving agents, fragrances, moisture absorbers, deodorants, suspension agents, propellants or any other ingredient usually used in cosmetics for this type of application.
- moisture absorbers for instance perlites and preferably expanded perlites.
- the perlites that may be used according to the invention are generally aluminosilicates of volcanic origin and have as the composition:
- the perlite is ground, dried and then calibrated in a first step.
- the product obtained, known as perlite ore, is grey-coloured and has a size of about 100 ⁇ .
- the perlite ore is then expanded (1000°C/2 seconds) to give more or less white particles.
- the temperature reaches 850-900°C, the water trapped in the structure of the material evaporates and brings about the expansion of the material relative to its original volume.
- the expanded perlite particles in accordance with the invention may be obtained via the expansion process described in patent US 5 002 698.
- the perlite particles used are ground: in this case, they are known as Expanded Milled Perlite (EMP). They preferably have a particle size defined by a median diameter D 50 ranging from 0.5 to 50 ⁇ and preferably from 0.5 to 40 ⁇ .
- EMP Expanded Milled Perlite
- the perlite particles used have an untamped apparent density at 25°C ranging from 10 to 400 kg/m 3 (standard DIN 53468) and preferably from 10 to 300 kg/m 3 .
- the expanded perlite particles according to the invention have a water- absorbing capacity, measured at the wet point, ranging from 200% to 1500% and preferably from 250% to 800%.
- the wet point corresponds to the amount of water that needs to be added to 1 g of particle in order to obtain a homogeneous paste. This method is derived directly from that of the oil uptake applied to solvents.
- wet point mass expressed in grams per 100 g of product corresponding to the production of a homogeneous paste during the addition of a solvent to a powder
- flow point mass expressed in grams per 100 g of product at and above which the amount of solvent is greater than the capacity of the powder to retain it. This is reflected by the production of a more or less homogeneous mixture that flows on a glass plate.
- the wet point and the flow point are measured according to the following protocol:
- Spatula wooden and partly metallic handle, 15 x 2.7 mm
- the glass plate is placed on the balance and 1 g of perlite particles is weighed out.
- the beaker containing the solvent and the sampling pipette is placed on the balance.
- the solvent is gradually added to the powder, the whole being regularly blended (every 3 to 4 drops) with the spatula.
- the mass of solvent needed to obtain the wet point is noted. Further solvent is added and the mass required to reach the flow point is noted. The average of three tests is determined.
- compositions of the invention may also contain deodorants.
- deodorant active agent refers to any substance that is capable of masking, absorbing, improving and/or reducing the unpleasant odour resulting from the decomposition of human sweat by bacteria.
- the deodorant active agents may be bacteriostatic agents or bactericides that act on underarm odour microorganisms, such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether ( ⁇ Triclosan), 2,4-dichloro-2'-hydroxydiphenyl ether, 3',4',5'- trichlorosalicylanilide, 1 -(3',4'-dichlorophenyl)-3-(4'-chlorophenyl)urea
- 2,4,4'-trichloro-2'-hydroxydiphenyl ether ⁇ Triclosan
- 2,4-dichloro-2'-hydroxydiphenyl ether 2,4-dichloro-2'-hydroxydiphenyl ether
- 3',4',5'- trichlorosalicylanilide 1 -(3',4'-dichlorophenyl)-3-(4'-chlorophenyl)urea
- ⁇ Triclocarban or 3,7,1 1 -trimethyldodeca-2, 5,10-trienol ( ⁇ Farnesol); quaternary ammonium salts such as cetyltrimethylammonium salts, cetylpyridinium salts, DPTA (1 ,3-diaminopropanetetraacetic acid), 1 ,2-decanediol (Symclariol from the company Symrise), glycerol derivatives, for instance caprylic/capric glycerides (Capmul MCM from Abitec), glyceryl caprylate or caprate (Dermosoft GMCY and Dermosoft GMC, respectively from Straetmans), Polyglyceryl-2 caprate (Dermosoft DGMC from Straetmans), and biguanide derivatives, for instance polyhexamethylene biguanide salts. - chlorhexidine and salts thereof; 4-phenyl- 4,4-dimethyl-2-butan
- deodorant active agents in accordance with the invention, mention may also be made of - zinc salts, for instance zinc salicylate, zinc gluconate, zinc pidolate; zinc sulfate, zinc chloride, zinc lactate, zinc phenolsulfonate; salicylic acid and derivatives thereof such as 5-n-octanoylsalicylic acid.
- the deodorant active agents may be odour absorbers such as zinc ricinoleate, sodium bicarbonate; metallic or non-metallic zeolites, cyclodextrins or alum.
- It may also be a chelating agent such as Dissolvine GL-47-S from Akzo Nobel, EDTA; DPTA.
- It may also be a polyol such as glycerol or propane-1 ,3-diol (Zemea Propane diol sold by Dupont Tate and Lyle Bioproducts).
- the deodorant agents may preferably be present in the compositions according to the invention in weight concentrations ranging from 0.01 % to 15% by weight relative to the total weight of composition A or B.
- compositions according to the invention will also contain an organic powder.
- organic powder means any solid that is insoluble in the medium at room temperature (25°C).
- compositions according to the invention may also be pressurized and may be conditioned in an aerosol device formed by:
- the propellants generally used in products of this type and that are well known to those skilled in the art are, for instance, dimethyl ether (DME); volatile hydrocarbons such as n-butane, propane, isobutane and mixtures thereof, optionally with at least one chlorohydrocarbon and/or fluorohydrocarbon; among these derivatives, mention may be made of the compounds sold by the company DuPont de Nemours under the names Freon® and Dymel®, and in particular monofluorotrichloromethane, difluorodichloromethane, tetrafluorodichloroethane and 1 ,1 -difluoroethane sold especially under the trade name Dymel 152 A by the company DuPont. Carbon dioxide, nitrous oxide, nitrogen or compressed air may also be used as propellant.
- DME dimethyl ether
- volatile hydrocarbons such as n-butane, propane, isobutane and mixtures thereof, optionally with at least one chlorohydrocarbon and/or
- compositions containing perlite particles as defined previously and the propellant(s) may be in the same compartment or in different compartments in the aerosol container.
- concentration of propellant generally ranges from 5% to 95% by weight of pressurized composition, and more preferentially from 50% to 85% by weight relative to the total weight of the pressurized composition.
- the dispensing means which forms a part of the aerosol device, is generally formed by a dispensing valve controlled by a dispensing head, which itself comprises a nozzle via which the aerosol composition is vaporized.
- the container containing the pressurized composition may be opaque or transparent. It may be made of glass, a polymer or a metal, optionally coated with a protective varnish coat.
- the salts are dispersed in the mixture of the other starting materials using a paddle.
- the mixture is pressurized in an aerosol can with isobutane.
- the cydomethicone is heated to 65°C.
- the other ingredients are added one by one, while keeping the temperature at 65-70°C.
- the whole is homogenized for 15 minutes.
- the product is cooled to about 55°C (a few degrees above the thickening point of the mixture) and is poured into sticks. The sticks are kept at 4°C for 30 minutes.
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Abstract
The present invention relates to a cosmetic process for treating human perspiration and possibly the body odour resulting from perspiration, which comprises the application to the skin of an anhydrous composition comprising, in a cosmetically acceptable medium, at least one compound (1) and at least one compound (2) that together produce an antiperspirant effect in situ on the skin; the said compounds (1) and (2) being capable of: - (i) reacting together via one or more physical interactions to form an antiperspirant salt or complex in situ on the skin, or - (ii) reacting together via one or more covalent bonds to impart an antiperspirant effect in situ on the skin, or - (iii) interacting together on contact with the skin to impart an antiperspirant effect, in particular the said composition not containing any antiperspirant halogenated aluminium and/or zirconium salt. The present invention also relates to an anhydrous composition comprising, in a cosmetically acceptable medium, a salt of an inorganic multivalent cation (1) and a salt of an inorganic anion (2), the said compounds (1) and (2) forming an antiperspirant salt in situ on the skin, via a cation/anion ionic interaction.
Description
PROCESS FOR TREATING PERSPIRATION USING AN ANHYDROUS COMPOSITION COMPRISING TWO REAGENTS THAT TOGETHER PRODUCE AN ANTIPERSPIRANT EFFECT IN SITU ON THE SKIN The present invention relates to a cosmetic process for treating human perspiration and possibly the body odour resulting from perspiration, which comprises the application to the skin of an anhydrous composition comprising, in a cosmetically acceptable medium, at least one compound (1 ) and at least one compound (2) that together produce an antiperspirant effect in situ on the skin; the said compounds (1 ) and (2) being capable of:
- (i) reacting together via one or more physical interactions to form an antiperspirant salt or complex in situ on the skin, or
- (ii) reacting together via one or more covalent bonds to impart an antiperspirant effect in situ on the skin, or
- (iii) interacting together on contact with the skin to impart an antiperspirant effect, in particular the said composition not containing any antiperspirant halogenated aluminium and/or zirconium salt.
The present invention also relates to an anhydrous composition comprising, in a cosmetically acceptable medium, a salt of an inorganic multivalent cation (1 ) and a salt of an inorganic anion (2) forming in situ on the skin a salt that produces an antiperspirant effect.
The armpits and also certain other parts of the body are generally the site of much discomfort that may arise directly or indirectly from perspiration. This discomfort often leads to unpleasant and disagreeable sensations that are mainly due to the presence of sweat resulting from perspiration, which may, in certain cases, make the skin and clothing wet, especially in the region of the armpits or on the back, thus leaving visible marks. Moreover, the presence of sweat may give rise to the production of body odour, which is generally unpleasant. Finally, during its evaporation, sweat may also leave salts and/or proteins at the surface of the skin, which may result in whitish marks on clothing. Such discomfort should be dealt with, including in the case of moderate perspiration. In the cosmetic field, it is thus well known to use, in topical application, antiperspirant products containing substances that have the effect of limiting or even preventing the flow of sweat in order to overcome the problems mentioned above. These products are generally available in the form of roll-ons, sticks, aerosols or sprays.
Antiperspirant substances generally consist of a halogenated aluminium and/or zirconium salt, especially aluminium and/or zirconium chlorohyd rates. These substances reduce the flow of sweat by forming a plug in the sweat duct. However, these substances may cause discomfort in the case of certain users, in relation with the acidic pH of the formulations.
Finally, these antiperspirant substances may also leave marks during their application, which has the consequence of staining clothing.
To overcome all of the drawbacks mentioned above, it has been proposed to seek other effective active substances, which are well tolerated by the skin and easy to formulate, in order to replace all or some of the aluminium and/or aluminium and zirconium chlorohydrates.
It has already been proposed in patent application US 2007/0 196 303 to use cations of calcium type and/or of strontium type in the presence of a buffer consisting of an amino acid and a betaine to reinforce the activity of aluminium chlorohydrates.
It has also already been proposed in patent application WO 00/10512 to use cations of the calcium type in the presence of an acidic solution based on an amino acid and/or a hydroxy acid to reinforce the activity of aluminium and/or zirconium salts. The presence of aluminium and/or zirconium salts remains obligatory in these antiperspirant formulations.
As an alternative to aluminium and/or zirconium chlorohydrates, patent FR 2 940 062 has already disclosed a multi-component agent for treating human perspiration, comprising two components that are intended to be mixed together before application to the skin or to be applied to the skin simultaneously, separately or sequentially over time; the said components being capable of reacting together to form one or more physical interactions in order to impart an antiperspirant effect. As an alternative to aluminium and/or zirconium chlorohydrates, patent WO 2010/070 143 has already disclosed a multi-component agent for treating human perspiration, comprising two components that are intended to be mixed together before application to the skin or to be applied to the skin simultaneously, separately or sequentially over time; one of the components being capable of treating the skin and the other component being capable of acting on the skin once treated, the said combination imparting an antiperspirant effect.
As an alternative to aluminium and/or zirconium chlorohydrates, patent WO 2010/070 139 has already disclosed a multi-component agent for treating human perspiration, comprising two components that are intended to be mixed together before application to the skin or to be applied to the skin simultaneously, separately or sequentially over time; the said components being capable of reacting together to form covalent bonds. The antiperspirant efficacy of these three processes is not entirely satisfactory. Furthermore, the systems proposed in these patent applications require the use of a twofold action or of extemporaneous preparation, which are a constraint on consumers. Several patents describe anhydrous compositions containing calcium salts.
Patent JP61 183208 from Kobayashi Kose KK describes anhydrous aerosols containing calcium carbonate particles.
Patents JP1 1278816 and JP2000219505 from Sekisui Plastics describe aerosols containing amorphous calcium phosphate particles optionally in combination with aluminium salts. The cited compositions are only deodorant when they do not contain aluminium salts. They are made antiperspirant by the addition of aluminium salts.
Thus, there is a real need to use on the skin an agent intended for treating human perspiration in replacement for the standard halogenated aluminium and/or zirconium salts, which does not have all the drawbacks described above, i.e. which gives a satisfactory antiperspirant effect, especially in terms of efficacy and resistance to sweat, and which is well tolerated by the skin.
The Applicant has discovered that this objective may be achieved by using an anhydrous composition comprising, in a cosmetically acceptable medium, at least one compound (1 ) and at least one compound (2) that together produce an antiperspirant effect in situ on the skin; the said compounds (1 ) and (2) being capable of:
- (i) reacting together via one or more physical interactions to form an antiperspirant salt or complex in situ on the skin, or
- (ii) reacting together via one or more covalent bonds to impart an antiperspirant effect in situ on the skin, or
- (iii) interacting together on contact with the skin to impart an antiperspirant effect,
in particular the said composition not containing any antiperspirant halogenated aluminium and/or zirconium salt.
This discovery forms the basis of the invention. The present invention relates to a cosmetic process for treating human perspiration and possibly the body odour resulting from perspiration, which comprises the application to the skin of an anhydrous composition comprising, in a cosmetically acceptable medium, at least one compound (1 ) and at least one compound (2) that together produce an antiperspirant effect in situ on the skin; the said compounds (1 ) and (2) being capable of:
- (i) reacting together via one or more physical interactions to form an antiperspirant salt or complex in situ on the skin, or
- (ii) reacting together via one or more covalent bonds to impart an antiperspirant effect in situ on the skin, or
- (iii) interacting together on contact with the skin to impart an antiperspirant effect, in particular the said composition not containing any antiperspirant halogenated aluminium and/or zirconium salt.
The present invention also relates to an anhydrous composition comprising, in a cosmetically acceptable medium, a salt of an inorganic or multivalent cation (1 ) and a salt of an inorganic anion (2); the said compounds (1 ) and (2) producing an antiperspirant effect; in particular, the said composition does not contain any antiperspirant halogenated aluminium and/or zirconium salt. Other subjects of the invention will emerge later in the description.
The term "anhydrous composition" means a composition containing less than 1 % by weight of added water, or even less than 0.5% of added water, and especially free of water, the water not being added during the preparation of the composition but corresponding to the residual water provided by the mixed ingredients.
The term "cosmetically acceptable" means compatible with the skin and/or its integuments or mucous membranes, having a pleasant colour, odour and feel and not causing any unacceptable discomfort (stinging, tautness or redness) liable to discourage the consumer from using this composition.
The term "antiperspirant" means any substance which has the effect of reducing the flow of sweat and/or of reducing the sensation of moisture associated with human sweat, and/or of masking human sweat.
The term "multivalent cations" means any monoatomic or polyatomic ion bearing at least two positive electrical charges and having a valency of at least 2 and preferably 2 or 3. The term "anion" means any monoatomic or polyatomic ion bearing one or more negative electrical charges.
The term "composition not containing any antiperspirant aluminium and/or zirconium salt" means any composition containing less than 1 % or even less than 0.5% by weight, relative to the total weight of the composition, of antiperspirant aluminium and/or zirconium salt comprising in its structure at least one halogen atom (for example aluminium and/or zirconium chlorohydrate), and especially free of the said salt. Compounds (1 ) and (2) of the invention are preferably dispersed in the anhydrous composition in powder form. The mean particle size is preferably less than 100 μιτι.
The concentration of each of the compounds (1 ) and (2) of the invention in the composition preferably ranges from 0.1 % to 20% by weight and more preferentially from 0.5% to 15% by weight relative to the total weight of the composition.
According to one particular form of the invention, at least one of the compounds (1 ) and (2) may be encapsulated according to the known encapsulation techniques.
COMPOUNDS CAPABLE OF REACTING VIA PHYSICAL INTERACTIONS According to one form of the invention, compounds (1 ) and (2) are capable of reacting together by means of one or more physical interactions, i.e. by forming together one or more non-covalent bonds chosen from ionic bonds, hydrogen bonds, Van der Waals bonds and hydrophobic bonds.
In particular, compounds (1 ) and (2) are capable of reacting together by means of one or more hydrogen bonds to impart an antiperspirant effect.
Thus, the combination of the two compounds (1 ) and (2) interacting by means of one or more hydrogen bonds may lead to the formation on the skin of complexes with antiperspirant activity.
According to a first embodiment, compound (1 ) may be chosen from oxyalkylenated polymers, polyvinylpyrrolidone, polyvinyl acetates and copolymers thereof, and compound (2) may be chosen from mineral fillers bearing a free hydrogen bond.
In accordance with this embodiment, compound (1 ) is preferably chosen from oxyalkylenated polymers. The oxyalkylenated polymers may comprise ethylene oxide groups (oxyethylenated compounds), propylene oxide groups (oxypropylenated compounds) or both (oxyethylenated/oxypropylenated compounds).
For the purposes of the invention, the term "mineral filler bearing a free hydrogen bond" means that the mineral fillers contain one or more free chemical groups capable of inducing one or more hydrogen bonds.
The oxyalkylenated polymers and the mineral fillers containing one or more free chemical groups capable of inducing one or more hydrogen bonds will be chosen from those described in patent FR 2 940 062.
Preferably, the oxyalkylenated polymer(s) are polyethylene glycols and ethoxylated alkyl or acyl derivatives of polyols, in particular the oxyethylenated (120 OE) methyl glucose dioleate sold under the name Glucamate DOE-120 Vegetal® by the company Amerchol.
The mineral filler(s) bearing a free hydrogen bond are preferably chosen from metal oxides, hydrophilic silicas and natural silica-based minerals such as perlite or diatomaceous earth.
Among the metal oxides that may be used, mention may be made especially of titanium, cerium, iron and/or zinc oxides.
For the purposes of the present invention, the term "hydrophilic silica" means a silica that is compatible with water or a polar solvent and that forms a homogeneous phase, for example a colloidal solution or a gel.
The term "hydrophilic silica" covers both pure silicas and silica-coated particles. Fumed silicas and in particular fumed silicas with a specific surface area of between 180 and 350 m2 g, with a number-average particle size of between 10 and 20 nm and with a density of between 50 and 150 g/l are preferably used as hydrophilic silica. Such fumed silicas are sold under the names Aerosil 200 and Aerosil 300 by the company Degussa-Huls.
Among the natural silica-based minerals that may be used, mention may be made especially of perlite and diatomaceous earth.
The perlites that may be used in the cosmetic composition B are generally aluminosilicates of volcanic origin and have as composition:
70.0-75.0% by weight of silica SiO2,
12.0-15.0% by weight of aluminium oxide AI2O3,
3.0-5.0% by weight of sodium oxide Na2O,
3.0-5.0% by weight of potassium oxide K2O,
0.5-2% by weight of iron oxide Fe2O3,
0.2-0.7% by weight of magnesium oxide MgO,
0.5-1 .5% by weight of calcium oxide CaO, and
0.05-0.15% by weight of titanium oxide ΤΊΟ2.
The perlite may be ground, dried and then calibrated to obtain perlite particles with a size of about 100 m.
A compound (1 ) chosen from oxyalkylenated polymers combined with a compound (2) chosen from hydrophilic silicas will preferably be used. Advantageously, the cosmetic composition A comprises one or more compounds chosen from oxyalkylenated polymers and ethoxylated alkyl or acyl derivatives of polyols, in particular oxyethylenated (120 OE) methyl glucose dioleate, and the cosmetic composition B comprises one or more compounds chosen from hydrophilic silica.
Specifically, the hydrophilic silica particles may combine with the oxyalkylenated groups by forming one or more hydrogen bonds in order to form a viscous gel having satisfactory antiperspirant activity. According to a second embodiment, compound (1 ) is chosen from polymers comprising one or more vicinal diols and compound (1 ) is a crosslinking agent.
The polymers comprising vicinal diols may be synthetic or natural. Such polymers are chosen from polymers of polyvinyl alcohol type, galactomannans such as guar gum or locust bean gum, and glucomannans such as konjac gum.
Use will be made in particular of polymers of polyvinyl alcohol type, galactomannans such as guar gum or locust bean gum, glucomannans such as konjac gum and the crosslinking agents described in patent FR 2 940 062.
Preferably, the crosslinking agent is sodium borate.
Preferably, the weight ratio between the crosslinking agent and the polymer comprising one or more vicinal diols is between 0.025 and 2.
Advantageously, compound (1 ) is a guar gum and compound (2) is sodium borate.
According to a third embodiment, compound (1 ) is chosen from polyethylene glycol derivatives such as those described in patent FR 2 940 062 and compound
(2) is chosen from organic acids and derivatives thereof such as acrylic acid polymers or copolymers such as those described in patent FR 2 940 062.
According to another particular form of the invention, compounds (1 ) and (2) are capable of reacting together by means of a hydrogen bond so as to impart an antiperspirant effect.
According to a first embodiment, compound (1 ) is capable of reacting with compound (2) via an acid-base reaction.
In accordance with this first embodiment, compound (1 ) may be chosen from polymers based on (meth)acrylic acid such as those described in patent FR 2 940 062. In accordance with this first embodiment, compound (2) may be chosen from organic bases, in particular organic amines.
Preferably, the organic amine(s) comprise one or two primary, secondary or tertiary amine functions, and one or more linear or branched Ci -Cs alkyl groups bearing one or more hydroxyl radicals.
Organic amines chosen from alkanolamines such as monoalkanolamines, dialkanolamines or trialkanolamines comprising one to three identical or different Ci -C4 hydroxyalkyl radicals are in particular suitable for use.
Among compounds of this type, mention may be made of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N- dimethylaminoethanolamine, 2-amino-2-methyl-1 -propanol, triisopropanolamine, 2-amino-2-methyl-1 ,3-propanediol, 3-amino-1 ,2-propanediol, 3-dimethylamino-1 ,2- propanediol and tris(hydroxymethylamino)methane.
Also suitable are the organic amines of the following formula:
RX \ / RZ
^ N W - N
Ry N Rt
in which W is a C1 -C6 alkylene residue optionally substituted with a hydroxyl group or a C1 -C6 alkyl radical; Rx, Ry, Rz and Rt, which may be identical or different, represent a hydrogen atom or a C1 -C6 alkyl, C1 -C6 hydroxyalkyl or C1 -C6 aminoalkyl radical, are also suitable for use.
Examples of such amines that may be mentioned include 1 ,3-diaminopropane, 1 ,3-diamino-2-propanol, spermine and spermidine.
Preferably, the organic amine is monoethanolamine.
Advantageously, compound (1 ) is chosen from crosslinked methacrylic acid or acrylic acid homopolymers and compound (2) is an organic amine, in particular monoethanolamine.
According to a second embodiment, compound (1 ) and compound (2) are capable of reacting by means of a cation/anion reaction.
The term "cation" means any monoatomic or polyatomic ion bearing one or more positive electrical charges.
The term "anion" means any monoatomic or polyatomic ion bearing one or more negative electrical charges. For the purposes of the present invention, the expression "capable of reacting by means of an anion/cation reaction" means that compound (1 ) and compound (2) are capable of reacting by forming one or more ionic bonds of cation/anion type, i.e. involving a reaction between a compound (1 ) containing at least one cationic charge and a compound (2) containing at least one anionic charge.
Thus, compound (1 ) comprises in its structure one or more cationic charges and compound (2) comprises in its structure one or more anionic charges.
In accordance with this second embodiment, compound (1 ) may be chosen from cationic surfactants, cationic polymers, cationic particles, inorganic cation salts or mixtures thereof and compound (2) may be chosen from anionic surfactants, anionic polymers, anionic particles and crosslinking agents, or mixtures thereof.
Use will be made for compound (1 ) of cationic surfactants, cationic polymers, cationic particles, inorganic cation salts or mixtures thereof such as those described in patent FR 2 940 062, and compound (2) may be chosen from anionic surfactants, anionic polymers, anionic particles and crosslinking agents or mixtures thereof such as those described in patent FR 2 940 062. According to a first aspect of this embodiment, compound (1 ) is chosen from cationic surfactants and compound (2) is chosen from anionic surfactants.
According to a second aspect of this embodiment, compound (1 ) is chosen from cationic polymers and compound (2) is chosen from anionic polymers.
Preferably, the cationic polymer(s) are chosen from cyclopolymers, in particular diallyldimethylammonium salt homopolymers, quaternized or non-quaternized copolymers of vinylpyrrolidone and of dialkylaminoalkyl acrylate or methacrylate, quaternary polymers of vinylpyrrolidone and of vinylimidazole, cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and/or guar gums modified with a hydroxypropyltrimethylammonium salt.
Preferably, the anionic polymer(s) may be chosen from terpolymers of vinyl acetate, vinyl tert-butylbenzoate and crotonic acid, methyl vinyl ether/monoesterified maleic anhydride copolymers and/or diblock polymers comprising a nonionic hydrophilic polymeric block and a hydrophobic polymeric block.
According to a third aspect of this embodiment, compound (1 ) is chosen from cationic polymers and compound (2) is chosen from anionic particles preferably in the form of a colloidal particle dispersion. Preferably, the cationic polymers are chosen from cyclopolymers such as diallyldimethylammonium salt homopolymers and polyalkyleneimines, in particular polyethyleneimine.
The weight ratio between the cationic polymer(s) and the anionic silica(s) ranges from 0.7 to 0.14. According to a fourth aspect of this embodiment, compound (1 ) is chosen from cationic particles, especially cationic silicas, and compound (2) is chosen from anionic polymers, preferably chosen from non-crosslinked copolymers of AMPS and of an ethoxylated C12-C14 alkyl methacrylate. According to a fifth aspect of this embodiment, compound (1 ) is chosen from cationic polymers and compound (2) is chosen from anionic surfactants.
According to a sixth aspect of this embodiment, compound (1 ) is chosen from cationic surfactants and compound (2) is chosen from anionic polymers.
According to a seventh aspect of this embodiment, compound (1 ) is chosen from alkali metal or alkaline-earth metal salts and compound (2) is chosen from anionic polymers comprising a sugar unit, especially alginates and derivatives thereof such as propylene glycol alginate, or salts thereof such as sodium alginate or calcium alginate. Preferably, the alkali metal or alkaline-earth metal salt(s) are chosen from the chlorides of these metals, in particular calcium chloride.
According to a third embodiment, compound (1 ) and compound (2) are capable of reacting together by precipitation or flocculation.
Thus, compound (1 ) is capable of precipitating or flocculating in the presence of a compound (2) by forming one or more ionic bonds.
In accordance with this embodiment, compound (1 ) may be chosen from cationic polymers chosen from guar gums such as hydroxypropyl guar, salts of an inorganic cation, and organic acids.
In accordance with this embodiment, compound (2) may be chosen from salts of an inorganic anion, amino acids, in particular cystine, crosslinking agents, anionic polymers chosen from polystyrene and terpolymers based on vinyl acetate, vinyl tert-butylbenzoate and crotonic acid, or a mixture of these compounds.
According to one particular form of this embodiment, compound (1 ) may be an organic acid such as citric acid, and compound (2) is an amino acid, in particular cystine.
According to one particular form of this embodiment, compound (1 ) may be polystyrene and compound (2) is an alkali metal salt, in particular sodium chloride.
According to one particular form of this embodiment, compound (1 ) may be an alkaline-earth metal salt, in particular a mixture of zinc chloride and magnesium chloride, and compound (2) is an anionic polymer chosen from terpolymers based on vinyl acetate, vinyl tert-butylbenzoate and crotonic acid.
According to one particular form of this embodiment, compound (1 ) may be a cationic polymer chosen from guar gums modified with a hydroxypropyltrimethylammonium salt, in particular the chloride, and compound (2) is a crosslinking agent, in particular sodium tetraborate.
According to one particularly preferred form of this embodiment, compound (1 ) may be a salt of a multivalent inorganic cation, and compound (2) is a salt of an inorganic anion. The cations in accordance with the invention are preferably chosen from multivalent inorganic cations whose valency n is by definition at least 2.
The multivalent cations are chosen from
- alkaline-earth metal cations such as beryllium, magnesium, calcium, strontium and barium;
- transition metal cations such as titanium (Ti2+, Ti3+, Ti4+), manganese (Mn2+, Mn3+, Mn4+, Mn7+), zinc (Zn2+), zirconium (Zr4+), hafnium (Hf4+) and aluminum (Al3+). The preferential alkaline-earth metal cations will be chosen from strontium, magnesium and calcium.
The transition metal cations will preferably be chosen from zinc, manganese and aluminium.
The multivalent cation salts that may be used according to the invention are preferably chosen from those with a solubility in water of greater than 2%, between 15°C and 30°C and at a pH of between 6 and 8. Among the cation salts that may be used according to the invention, mention may be made of halides. Halogens are a chemical series consisting of the chemical elements of group 17 of the Periodic Table, also known as group VII or group VIIA. Use will be made, as halides, of fluorides (fluorine), chlorides (chlorine), bromides (bromine) and iodides (iodine) and more particularly chlorides.
Mention may also be made of carboxylic acid salts such as acetates, propionates, pyrrol idonecarboxylates (or pidolates) or sorbates; polyhydroxylated carboxylic acid salts such as gluconates, heptagluconates, ketogluconates, lactate- gluconates, ascorbates or pentothenates; mono- or polycarboxylic hydroxy acid salts such as citrates or lactates; amino acid salts such as aspartates or glutamates; fulvate salts.
Mention may also be made of bicarbonates, also known as hydrogen carbonates. Mention may also be made of nitrates such as calcium nitrate; Ca(NOs)2.
Mention may also be made of sulfates such as magnesium sulfate or aluminium double sulfates such as alum: (KAI(SO4)2 12 H2O. Use will be made more preferentially of acetate salts, lactate salts, aspartate salts, pentothenate salts, ascorbate salts, pidolate salts, bicarbonate salts, propionate salts, sorbate salts or fulvate salts.
As examples of cation salts in accordance with the invention, mention may be made of calcium chloride, calcium pidolate, calcium aspartate, calcium gluconate, calcium glutamate, calcium heptagluconate, calcium propionate, calcium 2- ketogluconate, calcium lactate, calcium ascorbate, calcium citrate, calcium pentothenate, calcium bicarbonate, calcium sorbate, calcium lactate gluconate, calcium fulvate, magnesium chloride, magnesium sulfate, magnesium acetate, magnesium pidolate, magnesium gluconate, magnesium glutamate, magnesium heptagluconate, magnesium 2-ketogluconate, magnesium lactate, magnesium ascorbate, magnesium citrate, magnesium aspartate, manganese gluconate, magnesium pentothenate, magnesium bicarbonate, magnesium sorbate, magnesium lactate gluconate, magnesium fulvate, manganese chloride and manganese gluconate.
Magnesium chloride, manganese chloride, calcium chloride, calcium aspartate, calcium lactate, calcium propionate, calcium pidolate, calcium pentothenate, calcium bicarbonate, calcium sorbate, calcium lactate gluconate or calcium fulvate will preferably be chosen, and even more particularly calcium chloride.
The anions in accordance with the invention are preferably chosen from carbonate (CO32"), hydrogen carbonate (HCO3"), phosphate (PO4 3"), polyphosphates such as diphosphate P2O74" (also known as pyrophosphate), triphosphate P3O105", phosphonate (PO33"), hydrogen phosphate (HPO4 2"), sulfate (SO4 2"), sulfonate (SO3 ), hydrogen sulfate (HSO4 "), and hydrogen sulfonate (HSO3"). Hydrogen phosphate or hydrogen carbonate will be used more particularly.
The inorganic anion salt may be chosen, for example, from:
- the alkaline-earth metal salts as defined previously,
- salts of an alkali metal such as potassium or sodium,
- ammonium salts, salts of an amine, in particular of mono-, di- or trialkanolamines; comprising one to three identical or different Ci-C4 hydroxyalkyl radicals.
Among the alkanolamine compounds, mention may be made of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N-dimethylaminoethanolamine, 2-amino-2-methyl-1 -propanol, triisopropanolamine, 2-amino-2-methyl-1 ,3-propanediol, 3-amino-1 ,2-propanediol, 3-dimetnylamino-1 ,2-propanediol and tris(hydroxymethylamino)methane.
Use will preferentially be made of an alkali metal salt, in particular a sodium or potassium salt.
Among the preferential non-halogenated anion salts, mention may be made of Na2CO3, K2CO3, NaHCOs, KHCO3, Na3PO3, Na2HPO4, NaH2PO4, Na2H2P2O7, Na4P2O7, K2HPO4, KH2PO4, K2H2P2O7, K4P2O7, Na2SO4, MgSO4 and K2SO4. Use will preferably be made of sodium hydrogen carbonate NaHCO3.
In general, the cation and the anion form, when they are placed in contact, a salt having a solubility product in water at 25°C of less than 10"3 and preferably less than 10"5.
The term "solubility product in water at 25°C" means the equilibrium constant at 25°C corresponding to the dissolution of the salt XnYm in water.
The dissociation reaction in water of the ionic solid compound XnYm in which n and m are the respective valencies of the cation X and of the anion Y is:
XnYm - nX + mY
The solubility product is written Ks and is equal to:
Ks = x
As examples of antiperspirant salts formed after application of composition A and of composition B, mention may be made of the following salts and of their solubility product: CaSO4 (7.1 .10"5), CaCO3 (4.96x10"9), Ca3(PO4)2 (2.07x10"33), MgCO3 (6.82x10"6), Mg3fPO4)2 (9.86x10"25), MnCO3 (2.24x.10"11), SrCO3 (5.6x10"10), ZnCO3 (1 .19*10 ). The cited values are those referenced in the Handbook of Chemistry and Physics (70th Edition) CRC Press, page b207-b208. The cited values are those referenced in the Handbook of Chemistry and Physics (70th Edition) CRC Press, page b207-b208.
Preferentially, the composition of the invention is a water/oil/water emulsion comprising two or three components, in which compound (1 ): multivalent cation salt and compound (2): anion salt are present separately in each of the inner and outer aqueous phases.
The mole ratio between the cation and the anion preferably ranges from 10/1 to 1/10 and more preferentially from 4/1 to 1/4.
The total concentration of cation and anion preferably ranges from 2% to 25%, and more preferentially from 5% to 20% by weight relative to the total weight of the composition.
COMPOUNDS CAPABLE OF REACTING VIA CHEMICAL INTERACTION
According to a first embodiment, compound (1 ) comprises one or more functions capable of reacting with one or more functions borne by compound (2) so as to impart an antiperspirant effect.
Preferably, compound (1 ) and compound (2) bear one or more complementary chemical functions.
For the purposes of the present invention, the term "complementary chemical function" means that compound (1 ) comprises one or more functions that are capable of reacting with one or more functions borne by compound (2) by means, for example, of a condensation reaction by forming one or more covalent bonds.
In accordance with this embodiment, compound (1 ) may comprise one or more functions chosen from the following:
epoxide,
aziridine,
vinyl and activated vinyl, in particular acrylonitrile and acrylic and methacrylic esters,
crotonic acid and crotonic esters, cinnamic acid and cinnamic esters, styrene and derivatives thereof, and butadiene,
vinyl ethers, vinyl ketone, maleic esters, vinyl sulfones and maleimides,
anhydride, acid chloride and carboxylic acid esters,
aldehydes,
acetals, hemiacetals,
aminals, hemiaminals,
ketones, alpha-hydroxy ketones, alpha-halo ketones,
lactones, thiolactones,
isocyanate,
thiocyanate,
imines,
imides, in particular succinimide and glutimide,
N-hydroxysuccinimide esters,
imidates,
thiosulfate,
oxazine and oxazoline,
oxazinium and oxazolinium,
C1-C30 alkyl halides or C6-C30 aryl or aralkyl halides of formula RX with X = I, Br or CI,
halide of unsaturated carbon-based ring or heterocycle, especially chlorotriazine, chloropyrimidine, chloroquinoxaline or chlorobenzotriazole,
sulfonyl halide: RSO2CI or F, R being a C1-C30 alkyl.
For the purposes of the present invention, the term "activated vinyl" means that the vinyl function has an asymmetrical electronic distribution and is thus more reactive.
Preferably, compound (1 ) comprises one or more functions chosen from epoxide, anhydride, chlorotriazine and/or thiosulfate functions.
Even more preferably, compound (1 ) comprises one or more functions chosen from epoxide, anhydride and aldehyde functions.
In accordance with this embodiment, compound (2) may comprise one or more functions chosen from the functions of formula XHn in which X represents an oxygen, nitrogen or sulfur atom or a group COO and n = 1 or 2. In particular, compound (2) comprises one or more functions chosen from alcohol, amine, thiol and/or carboxylic acid functions.
The chemical function(s) of compound (1 ) may react with the chemical function(s) of compound (2) either spontaneously or by activation by temperature, the pH, a co-reagent, a chemical or biochemical catalyst, for instance metal salts such as the metal salts chosen from manganese, copper, iron and/or titanium salts, or enzymes such as oxidases or laccases.
In accordance with this embodiment, compound (1 ) and compound (2) are preferably polymers such as those described in patent application WO 2010/070 139.
According to a second embodiment, compound (1 ) is capable of reacting with compound (2) via a radical chemical reaction.
In accordance with this embodiment, compounds (1 ) and (2) respectively present may be ethylenic compounds.
In particular, compounds (1 ) and (2) may be chosen from ethylenic compounds comprising acrylate, acrylic acid, acrylamide, methacrylate, methacrylic acid, methacrylamide and/or styrene functions.
In general, the radical reaction between compound (1 ) and compound (2) involves an external form of activation.
In particular, the radical reaction between the compound(s) (1 ) and the compound(s) (2) may be activated by light, heat, one or more catalysts or a composition comprising one or more photoinitiators and optionally one or more photosensitizers.
Photopolyme zable and/or photocrosslinkable compositions are described in particular, for example, in patents CA 1 306 954 and US 5 456 905.
The ethylenic compound(s) may be chosen from polymers comprising ethylenic double bonds such as those described in patent application WO 2010/070 139.
According to a third embodiment, compound (1 ) is capable of reacting with compound (2) via an oxidation reaction. In accordance with this embodiment, compounds (1 ) and (2) that are capable of reacting together via an oxidation reaction may be chosen from aromatic compounds, such as those bearing at least two hydroxyl functions or one hydroxyl function and one amine function or alternatively only a hydroxyl function.
The oxidation reaction between compound (1 ) and compound (2) involves the presence of one or more oxidizing agents.
In this case, the oxidizing agent is preferably aqueous hydrogen peroxide solution or may originate from atmospheric oxygen.
In accordance with this embodiment, compounds (1 ) and (2) may be chosen from catechol, dihydroxyindole and 4-hydroxyindole. According to a particularly preferred form of this embodiment, compound (1 ) will be a polyphenol precursor of an antiperspirant agent and compound (2) is an enzymatic oxidation catalytic system and/or a chemical oxidation catalytic system.
The term "polyphenol" means any molecule comprising one or more aromatic rings, in particular benzene rings or fused aromatic rings bearing one or more hydroxyl functions.
The term "precursor of an antiperspirant agent" means any substance or any chemical compound that is capable via an oxidation reaction of forming a material constituting an antiperspirant agent.
Thus, a polyphenol compound (1 ) and in particular an ortho-diphenol, namely a compound comprising at least one aromatic ring bearing at least two hydroxyl groups borne by two consecutive carbon atoms of the aromatic ring as defined below, proves to be capable of polymerizing in situ when it is placed in contact with a suitable catalytic system, in the presence of oxygen, and of forming an efficient, advantageously biocompatible polymeric antiperspirant agent, which is capable of reducing the flow of sweat and of reducing or even eliminating the body odour associated with human perspiration.
According to a fourth embodiment, compound (1 ) is capable of reacting with compound (2) via a crosslinking reaction.
In this case, highly hydrophobic coatings may thus be produced, especially for treating the parts of the body that perspire the most, for instance the chest or the armpits. The coatings thus obtained show improved resistance to water and moisture.
By way of example, compound (1 ) may be chosen from polyols, for instance a cellulose derivative, and compound (2) may be chosen from compounds of perfluoroalkyltriethoxysilane type.
The composition according to the invention may also contain one or more crosslinking agents in order to produce coatings that are rendered solid on elongation or tearing. Such improvements may be useful for applications to the parts of the body that are the most subject to movements, such as the lips, the hands, the armpits, the neck or any area close to the joints.
Coatings that are rendered more resistant to abrasion may also be produced. These improvements may be useful for applications to the covered body. Specifically, these areas may be subject to friction from clothing. In this case, lubricant active agents and especially solid lubricant active agents (for example boron nitride or aluminium nitride) may be incorporated into the composition of the invention. Solid fillers, and especially fillers that are hydrophilic or that have been rendered hydrophilic, may also be incorporated, such as metal oxide, metal hydroxide or metal carbonate particles or organic particles.
REAGENTS THAT INTERACT ON THE SKIN
According to one form of the invention, compound (1 ) in accordance with the invention is capable of chemically or physically modifying the skin such that compound (2) can become active or such that its activity is reinforced on the pretreated skin in order to impart an antiperspirant effect.
According to one embodiment, compound (1 ) is capable of treating the skin by involving a chemical reaction.
For the purposes of the present invention, the expression "compounds that are capable of treating the skin by involving a chemical reaction" means that the cosmetic composition A comprises one or more compounds that are capable of inducing a chemical reaction with the skin, for example a chemical reaction with the skin proteins or with other compounds such as water or body fats in order thereafter to react with the skin.
Compound (1 ) may be chosen especially from:
(i) compounds that are capable of grafting to the skin,
(ii) compounds that are capable of opening one or more bonds of the skin,
(iii) compounds that are capable of modifying the ionic nature of the skin,
(iv) compounds that are capable of removing all or some of the molecules present in the skin,
(v) compounds that are capable of creating catalytic groups on the skin, or a mixture of these compounds.
According to a first aspect of this embodiment, compound (1 ) is capable of grafting to the skin. In particular, compound (1 ) includes one or more functions capable of grafting to the skin, especially by reacting with the nucleophilic functions of the skin, such as the hydroxyl, mercaptan and amine functions of the skin.
In accordance with this embodiment, compound (1 ) may include one or more functions capable of grafting to the skin, which may be chosen from the following functions:
epoxides,
aziridine,
vinyl and activated vinyl, in particular acrylonitrile and acrylic and methacrylic esters,
crotonic acid and crotonic esters, cinnamic acid and cinnamic esters, styrene and derivatives thereof, and butadiene,
vinyl ethers, vinyl ketone, maleic esters, vinyl sulfones and maleimides,
anhydride, acid chloride and carboxylic acid esters,
aldehydes,
acetals, hemiacetals,
aminals, hemiaminals,
ketones, alpha-hydroxy ketones, alpha-halo ketones,
lactones, thiolactones,
isocyanate,
thiocyanate,
imines,
imides, in particular succinimide and glutimide,
N-hydroxysuccinimide esters,
imidates,
thiosulfate,
oxazine and oxazoline,
oxazinium and oxazolinium,
C1-C30 alkyl halides or C6-C30 aryl or aralkyl halides of formula RX with X = I, Br or CI,
halide of unsaturated carbon-based ring or heterocycle, especially chlorotriazine, chloropyrimidine, chloroquinoxaline or chlorobenzotriazole,
sulfonyl halide: RSO2CI or F, R being a C1-C30 alkyl,
siloxane.
For the purposes of the present invention, the term "activated vinyl" means that the vinyl function has an asymmetrical electronic distribution and is thus more reactive. In particular, compound (1 ) may include one or more siloxane functions that may react, for example, with one or more hydroxyl or amine functions of the skin.
According to a second aspect of this embodiment, compound (1 ) is capable of opening one or more bonds of the skin, in particular the disulfide bonds or the peptide bonds of the keratin constituting the skin.
For the purposes of the present invention, the expression "opening the disulfide or peptide bonds of the keratin constituting the skin" means that compound (1 ) comprises one or more compounds that are capable of breaking the disulfide bonds (S-S) or the peptide bonds (carbon/nitrogen bonds between two amino acids) of keratin.
Compound (1 ) that is capable of opening one or more disulfide or peptide bonds of keratin may generate one or more reactive groups at the surface of the skin. In other words, such compounds are considered as being compounds that are capable of creating reactive groups at the surface of the skin.
Thus, when compound (1 ) that is capable of opening one or more disulfide bonds of keratin is applied to the skin, one or more reactive groups are formed at the surface of the skin, such as thiol groups, thiosulfate groups, mixed disulfide groups
and/or sulfonic acid groups. The term "mixed disulfide" means a compound in which the two groups containing two sulfur atoms of the disulfide are different and in particular do not produce the same electron-donating or electron-withdrawing effect. In this asymmetric manner, the mixed disulfide may be more reactive than a symmetrical disulfide.
Alternatively, when compound (1 ) is capable of opening one or more peptide bonds, for example by hydrolysing the peptide bonds of protein chains or by hydrolysing the pendent functions of proteins, and in particular the amide functions of glutamine and asparagine, one or more reactive groups are created by especially forming one or more amine and/or acid functions at the surface of the skin.
Compound (1 ) that is capable of opening one or more disulfide or peptide bonds of the skin may be chosen from reducing agents, acids, bases and oxidizing agents, and a mixture of these compounds.
The reducing agent(s) that may be used in the cosmetic composition A may be chosen from thiols, sulfinic acids, phosphines, sulfites and hydrides, or a mixture of these compounds.
As thiol reducing agents, it is especially possible to use thioglycolic acid, cysteine, homocysteine or thiolactic acid, and also the salts of these thiols. Among the sulfinic acids, hydroxymethanesulfinic acid is preferably used. The cosmetically acceptable salts of the sulfinic acids are especially chosen from alkali metal (Na, K), alkaline-earth metal (Ca) or zinc sulfinates.
Sodium hydroxymethanesulfinate is particularly preferred among the sulfinic acids that may be envisaged in the composition.
Among the sulfites, it is especially preferred to use alkali metal, alkaline-earth metal or ammonium salts, and also mixtures thereof. More particularly, mention may be made of sodium sulfite and sodium hydrogen sulfite.
Among the hydrides, it is preferred to use alkali metal or alkaline-earth metal salts such as sodium hydrides.
Among the phosphines, it is preferred to use tris(hydroxymethyl)phosphine, tris(hydroxypropyl)phosphine and tris(carboxyethyl)phosphine.
The acid(s) that may be used in the cosmetic composition A may be chosen from mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, and sulfonic acids.
The base(s) may be chosen from aqueous ammonia, alkali metal carbonates, alkanolamines such as monoethanolamine, diethanolamine or triethanolamine, and also derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula (VI) below:
(VI)
in which W is a propylene residue optionally substituted with a hydroxyl group or a Ci-C4 alkyl radical; and Ra, Rb, Rc and Rd, which may be identical or different, represent a hydrogen atom or a Ci-C4 alkyl or Ci-C4 hydroxyalkyl radical.
The oxidizing agent(s) may be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids, and oxidase enzymes (with the possible cofactors thereof), among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases, and 4- electron oxygenases, for instance laccases.
Preferably, compound (1 ) that is capable of opening one or more disulfide bonds is chosen from sulfites, in particular sulfite salts, especially alkali metal or alkaline- earth metal sulfites such as sodium sulfite, and thioglycolic acid.
According to a third aspect of this embodiment, compound (1 ) is capable of modifying the ionic nature of the skin by creating ionic groups at the surface of the skin, such as anionic, cationic or zwitterionic groups, or by creating hydrophobic groups.
Preferably, compound (1 ) is capable of modifying the ionic nature of the skin by creating anionic or cationic groups at the surface of the skin.
In particular, compound (1 ) may be chosen from cysteine salts that modify the ionic nature of the skin by creating anionic groups at the surface of the skin. Preferably, the cysteine salts are cysteine halides, such as cysteine hydrochloride. Compound (1 ) that is capable of modifying the ionic nature of the skin by creating cationic groups may also be chosen from alkoxysilanes comprising a substituent including a primary amine function, which are chosen from the compounds of formula:
✓OR
HjN ( CHj)„ - Si— OR
X°R (I)
in which the radicals R, which may be identical different, are selected from C1-C6 alkyl radicals and n is an integer from 1 to 6, preferably from 2 to 4.
An alkoxysilane that is particularly preferred according to this embodiment of the invention is γ-aminopropyltriethoxysilane. Such a compound is sold, for example, under the name Z-601 1 Silane by the company Dow Corning.
Compound (1 ) may be chosen in particular from cationic polymers.
Preferably, the cationic polymer(s) may be chosen from:
a) polymers that are formed from repeating units corresponding to formula (IX) below:
R10 R12
- N+(CH2)n- ljH (CH2)p — (IX)
R1 1 X R13 X
in which Rio, Rn, R12 and R13, which may be identical or different, denote an alkyl or hydroxyalkyl radical containing from 1 to 4 carbon atoms approximately, n and p are integers ranging from 2 to 20 approximately, and X" is an anion derived from a mineral or organic acid. b) poly(quaternary ammonium) polymers consisting of repeating units of formula (X):
CH- x x CH- i + i + (X) N— (CH2) -NH-CO-D-NH (CH2)C N - (CH2)2 - 0— (CH2 2)/2
i
CH3 in which p denotes an integer ranging from 1 to 6 approximately, D may be zero or may represent a group -(CH2)r-CO- in which r denotes a number equal to 4 or 7, and X- is an anion;
Such polymers may be prepared according to the processes described in US patents 4 157 388, 4 702 906 and 4 719 282. They are especially described in Patent application EP-A-122 324. More particularly, the preferred compounds are the compound of formula (IX) in which Ri 3, Ri4, R15 and R16 represent a methyl radical, n is equal to 3 and p is equal to 6 and X" represents a chloride anion (referred to hereinbelow as Mexomer PO) and the compound of formula (IX) in which R13 and Ri4 represent an ethyl radical, R15 and R16 represent a methyl radical, n and p are equal to 3 and X" represents a bromide anion (referred to hereinbelow as Mexomer PAK).
Thus, compound (1 ) that is capable of modifying the ionic nature of the skin is preferably chosen from cysteine salts, cationic polymers of formula (IX) and alkoxysilanes comprising a substituent including a primary amine function chosen from the compounds of formula (I) described above.
According to a fourth aspect of this embodiment, the compound (1 ) is capable of removing all or some of the molecules present in the skin. In this case, compound (1 ) may especially react with water so as to dry out the skin. By way of example, compound (1 ) may be chosen from anhydrides, in particular organic or mineral anhydrides such as phosphate anhydride.
According to a fifth aspect of this embodiment, compound (1 ) may be capable of generating one or more catalytic groups at the surface of the skin.
For example, compound (1 ) may be chosen from metal salts and enzymes that are grafted to the skin.
Thus, compound (1 ) may be a catalyst that binds to the skin.
In particular, compound (1 ) may be chosen from enzymes, in particular laccases, oxidases, dismutases, catalases, peroxidases and transition metal salts or other metal atoms. Preferably, compound (1 ) that is capable of creating catalytic groups at the surface of the skin is chosen from copper salts and manganese salts such as manganese chloride.
In accordance with the present invention, a compound (1 ) that is capable of grafting to the skin, chosen in particular from copper salts and manganese salts such as manganese chloride, may be combined with one or more compounds (1 ) that are capable of opening the disulfide bonds of keratin, in particular thioglycolic acid. Thioglycolic acid makes it possible to create at the surface of the skin reactive groups such as thiols that form a bond with the catalysts bound to the skin, which have been formed from the transition metal salts. The bond obtained is resistant to water and to various washing operations. According to another embodiment, compound (1 ) is capable of treating the skin without involving a chemical reaction with the skin.
For the purposes of the present invention, the expression "without involving a chemical reaction with the skin" means that compound (1 ) is capable of treating the skin without exerting a chemical action, i.e. compound (1 ) does not induce any chemical reaction with the skin, either at the time of application of the composition containing it, or thereafter. In other words, compound (1 ) is capable of modifying the physical properties of the skin in the absence of a chemical reaction therewith. According to a first aspect of this embodiment, compound (1 ) is capable of increasing the retention on the skin of at least one compound (2).
In accordance with this first aspect of this embodiment, compound (1 ) is chosen from oils and/or waxes as defined previously, the compounds (1 ) capable of creating physical interactions with one or more compounds (2).
According to a second aspect of this embodiment, compound (1 ) is capable of removing on and/or in the skin the agents that are liable to harm the action of compound (2).
Thus, compound (1 ) may be capable of removing elements that may be present in the skin pores.
According to a third aspect of this embodiment, compound (1 ) may be capable of improving the distribution and/or penetration of at least one compound (2) on and/or into the skin. In particular, compound (1 ) may be capable of improving the penetration of at least one compound (2) into the skin or into the sweat ducts.
Thus, compound (1 ) may be chosen from lubricants, agents that modify the surface tension of the skin, solubilizers, or agents capable of removing compounds that may be an obstacle to the action of at least one compound (2).
The lubricants that may be used in the cosmetic composition A may be chosen from polyethylene glycols (e.g. PEG-14M and PEG-23M) and silicones such as dimethicone, dimethiconol, dimethicone copolyol, stearyl dimethicone, cetyl dimethicone copolyol or cyclomethicone.
The agents that modify the surface tension of the skin may be chosen from surfactants, in particular cationic, nonionic, anionic or amphoteric surfactants. In particular those bearing cationic functions, such as genamine or betaines.
The solubilizers that may be used in the cosmetic composition A may be water, one or more organic solvents or a mixture of water and organic solvent.
Examples of organic solvents that may be mentioned include Ci-C4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2- butoxyethanol, propylene glycol, glycerol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monoethyl ether, and also aromatic alcohols, for instance benzyl alcohol or phenoxyethanol, and mixtures thereof. According to a fourth aspect of this embodiment, compound (1 ) may be chosen from agents that are capable of removing from the skin compounds that may be an obstacle to the action of at least one compound (2).
In particular, compound (1 ) may be capable of freeing the skin of salts that may be present, such as zinc.
According to a fifth aspect of this embodiment, compound (1 ) may be capable of modifying the porosity of the skin. In particular, it may be chosen from organic solvents and also products capable of breaking one or more hydrogen bonds, such as urea.
According to a sixth aspect of this embodiment, compound (1 ) may be capable of making the skin reactive. For example, it may be chosen from oxidizing agents used under strict operating conditions so as to make the skin reactive.
In particular, use is made of an oxidizing agent referred to as a "mild oxidizing agent" that is not capable of fully oxidizing a third compound, unlike a "strong oxidizing agent", which will fully degrade the third element. In the latter case, the oxidation product is degraded so much that it will no longer react.
According to a seventh aspect of this embodiment, compound (1 ) may be an inhibitor chosen in particular from zinc salts whose inhibitory action towards thiol functions prevents these functions from being reductive. Compound (1 ) may also be chosen to withstand movements, elongation and friction.
Thus, compound (1 ) may especially facilitate the penetration of at least one compound (2) into the skin, increase its retention on the skin and improve its functioning.
Preferably, compound (1 ) is capable of treating the skin by involving a chemical reaction. More preferentially, compound (1 ) is chosen from cysteine salts, in particular cysteine hydrochloride, sulfite salts, in particular alkali metal or alkaline-earth metal sulfites such as sodium sulfite, alkoxysilanes of formula (I), in particular 3- aminopropyltriethoxysilane, manganese salts such as manganese chloride, thioglycolic acid, cationic polymers of formula (IX), or a mixture of these compounds.
Compound (2) is preferably chosen from compounds that are capable of acting on the skin once it has been chemically or physically modified by compound (1 ) to impart an antiperspirant effect.
For the purposes of the present invention, the expression "acting on the skin once it has been treated" means that compound (2) is capable of being active on contact with the skin once it has been treated with compound (1 ). According to a first embodiment, when compound (1 ) is capable of grafting to the skin, then compound (2) is selected from compounds that are capable of reacting with compound (1 ) grafted to the skin.
According to a second embodiment, when compound (1 ) is capable of opening the disulfide bonds of the skin, thus forming reactive groups such as thiol groups, then compound (2) is capable of reacting with the reactive groups thus formed, to impart an antiperspirant effect.
In accordance with this embodiment, compound (2) is a reducing agent such as cysteine.
Alternatively, in accordance with this embodiment, compound (2) may be chosen from fluorinated alkoxysilanes. According to a third embodiment, when compound (1 ) is capable of modifying the ionic nature of the skin by forming one or more ionic groups, then compound (2) is selected from compounds bearing one or more ionic charges of opposite sign to the ionic groups formed on the skin, so as to create an ionic interaction to impart an antiperspirant effect.
Thus, when compound (1 ) is capable of modifying the ionic nature of the skin by forming one or more anionic groups, then compound (2) is selected from compounds bearing one or more cationic charges capable of creating an ionic interaction with the negatively charged skin.
In other words, in this case, compound (2) is selected so as to be able to react with the negatively charged skin by means of an anion/cation interaction.
Conversely, when compound (1 ) is capable of modifying the ionic nature of the skin by forming cationic groups, then compound (2) is selected from compounds bearing one or more anionic charges that are capable of creating an ionic interaction with the positively charged skin.
In other words, in this case, compound (2) is selected so as to be able to react with the positively charged skin by means of a cation/anion interaction.
In accordance with this embodiment, compound (2) may be chosen from anionic polymers, metal salts, transition metal salts and/or cellulose esters.
Preferably, the preferential anionic polymer(s) comprise at least, as monomers, vinyl acetate, vinyl neodecanoate and crotonic acid, and more particularly the terpolymer of vinyl acetate, vinyl tert-butylbenzoate and crotonic acid is used.
Such anionic polymers may be partially or totally neutralized with a basifying agent.
Preferably, the basifying agent is chosen from alkanolamines such as
mono-, di- and triethanolamines, and also derivatives thereof.
Among the alkali metal or alkaline-earth metal salts that may especially be used are halides, hydroxides, borates or nitrates, and more particularly alkali metal or alkaline-earth metal halides and borates, such as sodium chloride or sodium tetraborate.
Among the transition metal salts that may especially be used are transition metal halides, such as zinc chloride or manganese chloride.
Among the cellulose esters, it is particularly preferred to use hydroxypropylmethylcellulose phthalate. According to another embodiment, when compound (1 ) is capable of forming catalytic groups on the skin, then compound (2) is selected from compounds that are capable of reacting in the presence of the catalytic groups so as to impart an antiperspirant effect. Thus, when compound (1 ) is chosen from manganese salts, these compounds bind to the skin so as to give it catalytic activity that promotes oxidation and compound (2) will then be selected from compounds that are capable of being oxidized, such as indoles, indole derivatives or thiol compounds, so as to impart an antiperspirant effect.
According to another embodiment, when compound (1 ) is capable of modifying the porosity of the skin, then compound (2) is selected from compounds that are capable of acting within the skin so as to impart an antiperspirant effect. According to another embodiment, when compound (1 ) is capable of increasing the surface tension of the skin, then compound (2) is selected from compounds that are capable of spreading on skin whose surface tension has been increased, so as to impart an antiperspirant effect. According to another embodiment, when the compound is a solubilizing agent, then compound (2) is selected from compounds that are capable of dissolving compound (1 ), so as to impart an antiperspirant effect.
According to another embodiment, when compound (1 ) is capable of modifying the hydrophobicity of the skin, compound (2) is used in the presence of a volatile hydrophobic solvent and is chosen from compounds that are capable of entering the skin pores, so as to impart an antiperspirant effect.
According to another embodiment, when compound (1 ) is capable of reducing the surface tension of the skin, then compound (2) is used in the presence of a liquid with a high surface tension and is chosen from compounds that are capable of entering the skin pores, so as to impart an antiperspirant effect.
Compound (2) may be chosen to withstand movements, elongation and friction.
For example, compound (2) may be chosen from compounds that are capable of withstanding abrasion, such as boron nitride.
Preferably, compound (2) is chosen from one or more fluorinated alkoxysilanes, one or more anionic polymers comprising at least, as monomers, vinyl acetate, vinyl neodecanoate and crotonic acid, cellulose esters, in particular hydroxypropylmethylcellulose phthalate, metal salts, in particular transition metal halides, reducing agents such as cysteine, indoles or derivatives thereof, aluminium chlorohydrate and sodium tetraborate.
Preferably, compound (1 ) is chosen from those that are capable of modifying the ionic nature of the skin by creating cationic groups, and compound (2) is chosen from compounds bearing one or more anionic charges capable of reacting with the cationic groups at the surface of the skin.
According to one aspect of this embodiment, compound (1 ) may be chosen from cysteine salts, in particular cysteine hydrochloride, and compound (2) is chosen from metal salts, in particular transition metal salts such as zinc chloride. According to one aspect of this embodiment, compound (1 ) may be chosen from cysteine salts, in particular cysteine hydrochloride, and compound (2) is chosen from fluorinated alkoxysilanes.
According to another aspect of this embodiment, compound (1 ) may be chosen from sulfites, in particular alkali metal or alkaline-earth metal sulfites such as sodium sulfite, and compound (2) is chosen from fluorinated alkoxysilanes. According to another aspect of this embodiment, compound (1 ) may be chosen from the alkoxysilanes of formula (I) and compound (2) is chosen from magnesium chloride and anionic polymers comprising at least, as monomers, vinyl acetate, vinyl neodecanoate and crotonic acid. According to another aspect of this embodiment, compound (1 ) may be chosen from manganese salts, such as manganese chloride, and thioglycolic acid, and compound (2) is cysteine.
According to another aspect of this embodiment, compound (1 ) is chosen from manganese salts, such as manganese chloride, and thioglycolic acid, and compound (2) is dihydroxyindole.
OILY PHASE The compositions according to the invention preferably contain at least one water- immiscible organic liquid phase, known as an oily phase. This phase generally comprises one or more hydrophobic compounds that make the said phase water immiscible. The said phase is liquid (in the absence of a structuring agent) at room temperature (20-25°C) and atmospheric pressure (760 mmHg, i.e. 105 Pa). Preferentially, the water-immiscible organic-liquid organic phase in accordance with the invention is generally formed from at least one volatile oil and/or nonvolatile non-silicone oil and/or a non-volatile silicone oil.
The term "oil" means a fatty substance that is liquid at room temperature (20-25°C) and atmospheric pressure (760 mmHg, i.e. 105 Pa). The oil may be volatile or nonvolatile.
For the purposes of the invention, the term "volatile oil" means an oil that is capable of evaporating on contact with the skin or the keratin fibre in less than one hour, at room temperature and atmospheric pressure. The volatile oils of the invention are volatile cosmetic oils, which are liquid at room temperature, having a non-zero vapour pressure, at room temperature and atmospheric pressure, ranging in particular from 0.13 Pa to 40 000 Pa (10"3 to 300 mmHg), in particular ranging from 1 .3 Pa to 13 000 Pa (0.01 to 100 mmHg) and more particularly ranging from 1 .3 Pa to 1300 Pa (0.01 to 10 mmHg).
The term "non-volatile oil" means an oil that remains on the skin or the keratin fibre at room temperature and atmospheric pressure for at least several hours, and that especially has a vapour pressure of less than 10"3 mmHg (0.13 Pa).
The oils in accordance with the invention are preferably chosen from any cosmetically acceptable oil, especially mineral, animal, plant or synthetic oils, especially hydrocarbon-based oils, fluoro oils or silicone oils, or mixtures thereof.
The term "hydrocarbon-based oil" means an oil mainly containing carbon and hydrogen atoms and possibly one or more functions chosen from hydroxyl, ester, ether and carboxylic functions. Generally, the oil has a viscosity of from 0.5 to 100 000 mPa.s, preferably from 50 to 50 000 mPa.s and more preferably from 100 to 300 000 mPa.s.
The term "silicone oil" means an oil comprising in its structure carbon atoms and at least one silicon atom. The term "fluoro oil" means partially hydrocarbon-based and/or silicone-based oils comprising carbon atoms and fluorine atoms.
As examples of volatile hydrocarbon-based oils that may be used in the invention, mention may be made of:
- volatile hydrocarbon-based oils chosen from hydrocarbon-based oils containing from 8 to 16 carbon atoms, and especially Cs-Ci6 isoalkanes of petroleum origin (also known as isoparaffins), for instance isododecane (also known as 2,2,4,4,6- pentamethylheptane), isodecane and isohexadecane, for example the oils sold under the trade names Isopar or Permethyl, branched Cs-Ci6 esters and isohexyl neopentanoate, and mixtures thereof. Other volatile hydrocarbon-based oils, for instance petroleum distillates, especially those sold under the name Shell Solt by the company Shell, may also be used; volatile linear alkanes, such as those described in patent application DE10 2008 012 457 from the company Cognis. As examples of non-volatile hydrocarbon-based oils that may be used in the invention, mention may be made of:
- hydrocarbon-based oils of animal origin, such as perhydrosqualene;
- hydrocarbon-based plant oils such as liquid triglycerides of fatty acids of 4 to 24 carbon atoms, for instance heptanoic or octanoic acid triglycerides, or wheatgerm oil, olive oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, alfalfa oil, poppy oil, pumpkin oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil, musk rose oil, sunflower oil, corn oil, soybean oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, castor oil, avocado oil, caprylic/capric acid triglycerides, for instance those sold by the company Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel, jojoba oil and shea butter oil,
- linear or branched hydrocarbons, of mineral or synthetic origin, such as liquid paraffins and derivatives thereof, petroleum jelly, polydecenes, polybutenes, hydrogenated polyisobutene such as Parleam, and squalane,
- synthetic ethers containing from 10 to 40 carbon atoms;
- synthetic esters, especially of fatty acids, for instance the oils of formula R1COOR2 in which Ri represents a linear or branched higher fatty acid residue containing from 1 to 40 carbon atoms and R2 represents a hydrocarbon-based chain, which is especially branched, containing from 1 to 40 carbon atoms, with Ri + R2 > 10, for instance purcellin oil (cetostearyl octanoate), isononyl isononanoate, isopropyl myristate, isopropyl palmitate, C12-C15 alkyl benzoates, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2-octyldodecyl erucate, isostearyl isostearate or tridecyl trimellitate; alcohol or polyalcohol octanoates, decanoates or ricinoleates, for instance
propylene glycol dioctanoate; hydroxylated esters, for instance isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, and fatty alcohol heptanoates, octanoates or decanoates; polyol esters, for instance propylene glycol dioctanoate, neopentyl glycol diheptanoate or diethylene glycol diisononanoate; and pentaerythritol esters, for instance pentaerythrityl tetraisostearate,
- fatty alcohols that are liquid at room temperature, containing a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance octyldodecanol, isostearyl alcohol, 2-butyloctanol, 2-hexyldecanol, 2- undecylpentadecanol or oleyl alcohol,
- higher fatty acids such as oleic acid, linoleic acid or linolenic acid;
- carbonates;
- acetates;
- citrates.
As examples of partially hydrocarbon-based and/or silicone-based fluoro oils, mention may be made of fluorosilicone oils, fluoro polyethers and fluorosilicones as described in document EP-A-847 752. As examples of non-volatile silicone oils, mention may be made of linear or cyclic non-volatile polydimethylsiloxanes (PDMS); polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, which are pendant or at the end of a silicone chain, these groups containing from 2 to 24 carbon atoms; phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenyl siloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes and 2- phenylethyl trimethylsiloxy silicates, and mixtures thereof.
According to one particularly preferred form of the invention, the compositions contain less than 2% volatile silicone oil, or even less than 0.5% volatile silicone oil, and are especially free of volatile silicone oil; the volatile silicone oil not being added during the preparation of the composition, but corresponding to the residual volatile silicone oil introduced by the mixed ingredients.
SOLID FATTY SUBSTANCES The composition according to the invention comprises at least one solid fatty substance preferably chosen from waxes and pasty fatty substances, and mixtures thereof, and more particularly waxes.
Pasty fatty substances
For the purposes of the present invention, the term "pasty fatty substance" (also known as a paste) means a lipophilic fatty compound with a reversible solid/liquid change of state, displaying anisotropic crystal organization in the solid state, and comprising a liquid fraction and a solid fraction at a temperature of 23°C.
In other words, the starting melting point of the pasty compound can be less than 23°C. The liquid fraction of the pasty compound measured at 23°C can represent 9% to 97% by weight of the compound. This liquid fraction at 23°C preferably represents between 15% and 85% and more preferably between 40% and 85% by weight.
Within the meaning of the invention, the melting point corresponds to the temperature of the most endothermic peak observed on thermal analysis (DSC) as described in Standard ISO 1 1357-3; 1999. The melting point of a pasty substance or of a wax may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name MDSC 2920 by the company TA Instruments.
The measuring protocol is as follows:
A sample of 5 mg of paste or wax (depending on the case) placed in a crucible is subjected to a first temperature rise passing from -20°C to 100°C, at the heating rate of 10°C/minute, then is cooled from 100°C to -20°C at a cooling rate of 10°C/minute and finally subjected to a second temperature rise passing from -20°C to 100°C at a heating rate of 5°C/minute. During the second temperature rise, the variation in the difference between the power absorbed by the empty crucible and the crucible containing the sample of paste or wax as a function of the temperature is measured. The melting point of the compound is the value of the temperature corresponding to the tip of the peak of the curve representing the variation in the difference in power absorbed as a function of the temperature.
The liquid fraction by weight of the pasty compound at 23°C is equal to the ratio of the heat of fusion consumed at 23°C to the heat of fusion of the pasty compound.
The heat of fusion of the pasty compound is the heat consumed by the compound in order to pass from the solid state to the liquid state. The pasty compound is said to be in the solid state when all of its mass is in crystalline solid form. The pasty compound is said to be in the liquid state when all of its mass is in liquid form.
The heat of fusion of the pasty compound is equal to the area under the curve of the thermogram obtained using a differential scanning calorimeter (DSC), such as the calorimeter sold under the name MDSC 2920 by the company TA Instrument, with a temperature rise of 5°C or 10°C per minute, according to standard ISO 1 1357-3:1999. The heat of fusion of the pasty compound is the amount of energy required to make the compound change from the solid state to the liquid state. It is expressed in J/g.
The enthalpy of fusion consumed at 23°C is the amount of energy absorbed by the sample to change from the solid state to the state that it has at 23°C, composed of a liquid fraction and a solid fraction.
The liquid fraction of the pasty compound measured at 32°C preferably represents from 30% to 100% by weight of the compound, preferably from 50% to 100%, more preferably from 60% to 100% by weight of the compound. When the liquid fraction of the pasty compound measured at 32°C is equal to 100%, the temperature of the end of the melting range of the pasty compound is less than or equal to 32°C.
The liquid fraction of the pasty compound measured at 32°C is equal to the ratio of the heat of fusion consumed at 32°C to the heat of fusion of the pasty compound. The heat of fusion consumed at 32°C is calculated in the same way as the heat of fusion consumed at 23°C.
The pasty compound is preferably chosen from synthetic compounds and compounds of plant origin. A pasty compound may be obtained by the synthesis from starting materials of plant origin. The pasty compound is advantageously chosen from:
- lanolin and derivatives thereof,
- polyol ethers chosen from ethers of pentaerythritol and of polyalkylene glycol, ethers of fatty alcohol and of sugar, and mixtures thereof, the ethers of pentaerythritol and of polyethylene glycol comprising 5 oxyethylene units (5 OE) (CTFA name: PEG-5 Pentaerythrityl Ether), the polypropylene glycol pentaerythrityl ether comprising 5 oxypropylene (5 OP) units (CTFA name: PPG-5 Pentaerythrityl Ether) and mixtures thereof, and more especially the mixture PEG- 5 Pentaerythrityl Ether, PPG-5 Pentaerythrityl Ether and soybean oil, sold under the name Lanolide by the company Vevy, which is a mixture in which the constituents are in a 46/46/8 weight ratio: 46% PEG-5 Pentaerythrityl Ether, 46% PPG-5 Pentaerythrityl Ether and 8% soybean oil;
- polymeric or non-polymeric silicone compounds,
- polymeric or non-polymeric fluoro compounds,
- vinyl polymers, especially:
- olefin homopolymers and copolymers,
- hydrogenated diene homopolymers and copolymers,
- linear or branched oligomers, homopolymers or copolymers of alkyl (meth)acrylates preferably containing a C8-C30 alkyl group,
- oligomers, homopolymers and copolymers of vinyl esters containing C8-C30 alkyl groups,
- oligomers, homopolymers and copolymers of vinyl ethers containing C8-C30 alkyl groups,
- liposoluble polyethers resulting from the polyetherification between one or more C2-C100 and preferably C2-C5o diols,
- esters,
and/or mixtures thereof.
The pasty compound is preferably a polymer, especially a hydrocarbon-based polymer.
Among the liposoluble polyethers that are particularly preferred are copolymers of ethylene oxide and/or of propylene oxide with C6-C30 long-chain alkylene oxides, more preferably such that the weight ratio of the ethylene oxide and/or of the propylene oxide to the alkylene oxides in the copolymer is from 5:95 to 70:30. In this family, mention will be made especially of copolymers such that the long-chain alkylene oxides are arranged in blocks having an average molecular weight from 1000 to 10 000, for example a polyoxyethylene/polydodecyl glycol block copolymer such as the ethers of dodecanediol (22 mol) and of polyethylene glycol (45 OE) sold under the brand name Elfacos ST9 by Akzo Nobel.
Among the esters, the following are especially preferred:
- esters of a glycerol oligomer, especially diglycerol esters, in particular condensates of adipic acid and of glycerol, for which some of the hydroxyl groups of the glycerols have reacted with a mixture of fatty acids such as stearic acid, capric acid, stearic acid and isostearic acid, and 12-hydroxystearic acid, especially such as those sold under the brand name Softisan 649 by the company Sasol,
- the arachidyl propionate sold under the brand name Waxenol 801 by Alzo,
- phytosterol esters,
- fatty acid triglycerides and derivatives thereof,
- pentaerythritol esters,
- non-crosslinked polyesters resulting from polycondensation between a linear or branched C4-C5o dicarboxylic acid or polycarboxylic acid and a C2-C50 diol or polyol,
- aliphatic esters of an ester, resulting from the esterification of an aliphatic hydroxycarboxylic acid ester with an aliphatic carboxylic acid. Preferably, the aliphatic carboxylic acid comprises from 4 to 30 and preferably from 8 to 30 carbon atoms. It is preferably chosen from hexanoic acid, heptanoic acid, octanoic acid, 2- ethylhexanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, hexyldecanoic acid, heptadecanoic acid, octadecanoic acid, isostearic acid, nonadecanoic acid, eicosanoic acid, isoarachidic acid, octyldodecanoic acid, heneicosanoic acid and docosanoic acid, and mixtures thereof. The aliphatic carboxylic acid is preferably branched. The aliphatic hydroxycarboxylic acid ester is advantageously derived from a hydroxylated aliphatic carboxylic acid containing from 2 to 40 carbon atoms, preferably from 10 to 34 carbon atoms and better still from 12 to 28 carbon atoms, and from 1 to 20 hydroxyl groups, preferably from 1 to 10 hydroxyl groups and better still from 1 to 6 hydroxyl groups.
The aliphatic hydroxycarboxylic acid ester is chosen from:
a) partial or total esters of saturated linear mono-hydroxylated aliphatic monocarboxylic acids;
b) partial or total esters of unsaturated monohydroxylated aliphatic monocarboxylic acids;
c) partial or total esters of saturated monohydroxylated aliphatic polycarboxylic acids;
d) partial or total esters of saturated polyhydroxylated aliphatic polycarboxylic acids;
e) partial or total esters of C2 to C16 aliphatic polyols that have reacted with a monohydroxylated or polyhydroxylated aliphatic monocarboxylic or polycarboxylic acid,
and mixtures thereof.
- esters of a diol dimer and of a diacid dimer, where appropriate esterified on their free alcohol or acid function(s) with acid or alcohol radicals, especially dimer dilinoleate esters; such esters may be chosen especially from the esters having the following INCI nomenclature: bis-behenyl/isostearyl/phytosteryl dimer dilinoleyl dimer dilinoleate (Plandool G), phytosteryl/isostearyl/cetyl/stearyl/behenyl dimer dilinoleate (Plandool H or Plandool S), and mixtures thereof,
- hydrogenated rosinate esters, such as dilinoleyl dimers of hydrogenated rosinate (Lusplan DD-DHR or DD-DHR from Nippon Fine Chemical);
and mixtures thereof.
Wax(es)
According to one preferred embodiment, the composition according to the invention comprises at least one wax.
The wax under consideration in the context of the present invention is generally a lipophilic compound that is solid at room temperature (25°C), with a solid/liquid reversible change of state, having a melting point of greater than or equal to 30°C, which may be up to 200°C and in particular up to 120°C.
In particular, the waxes that are suitable for the invention may have a melting point of greater than or equal to 45°C and in particular greater than or equal to 55°C. The waxes that may be used in the compositions according to the invention are chosen from waxes that are solid at room temperature of animal, plant, mineral or synthetic origin, and mixtures thereof.
Examples that may be mentioned include the following hydrocarbon-based waxes comprising a fatty alkyl chain generally containing from 10 to 60 carbon atoms and preferably from 20 to 40 carbon atoms, the said chain possibly being saturated or unsaturated, substituted or unsubstituted, and linear, branched or cyclic, preferably saturated and linear:
- fatty alcohols;
- fatty alcohol esters;
- fatty acids;
- fatty acid amides;
- fatty acid esters including triglycerides;
- fatty acid ethers;
- ethoxylated fatty alcohols;
- ethoxylated fatty acids and the corresponding salts thereof.
Among the fatty alcohols, mention may be made of stearyl alcohol and cetearyl alcohol, or mixtures thereof.
Among the fatty alcohol esters, mention may be made of triisostearyl citrate, ethylene glycol bis(12-hydroxystearate), tristearyl citrate, stearyl octanoate, stearyl heptanoate, trilauryl citrate, and mixtures thereof. Among the fatty acid esters, mention may be made of ester waxes, monoglycerides, diglycerides and triglycerides.
Ester waxes that may be mentioned include stearyl stearate, stearyl behenate, stearyloctyldodecanol, cetearyl behenate, behenyl behenate, ethylene glycol distearate and ethylene glycol dipalmitate. Use may be made in particular of a C20- C4o alkyl (hydroxystearyloxy)stearate (the alkyl group containing from 20 to 40 carbon atoms), alone or as a mixture. Such a wax is especially sold under the names Kester Wax K 82 P®, Hydroxypolyester K 82 P® and Kester Wax K 80 P® by the company Koster Keunen.
Among the triglyceride waxes, mention may be made more particularly of Tribehenine, C18-C36 triglycerides, and mixtures thereof.
As illustrations of waxes that are suitable for the invention, mention may be made especially of hydrocarbon-based waxes, for instance beeswax, lanolin wax, Chinese insect waxes, rice bran wax, carnauba wax, candelilla wax, ouricury wax, esparto grass wax, berry wax, shellac wax, Japan wax and sumach wax; montan wax, orange wax and lemon wax, microcrystalline waxes, paraffins and ozokerite; polyethylene waxes, the waxes obtained by Fischer-Tropsch synthesis and waxy copolymers, and also esters thereof.
Mention may also be made of waxes obtained by catalytic hydrogenation of animal or plant oils containing linear or branched C8-C32 fatty chains. Among these waxes that may especially be mentioned are isomerized jojoba oil such as the trans- isomerized partially hydrogenated jojoba oil manufactured or sold by the company Desert Whale under the commercial reference lso-Jojoba-50®, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil, hydrogenated lanolin oil and bis(1 ,1 ,1 -trimethylolpropane) tetrastearate sold under the name Hest 2T-4S® by the company Heterene.
Mention may also be made of silicone waxes (C3o-45 alkyl dimethicone) and fluoro waxes.
The waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol, sold under the names Phytowax ricin 16L64® and 22L73® by the company Sophim, may also be used. Such waxes are described in patent application FR-A- 2 792 190.
As microwaxes that may be used in the compositions according to the invention, mention may be made especially of carnauba microwaxes, such as the product sold under the name MicroCare 350® by the company Micro Powders, synthetic microwaxes, such as the product sold under the name MicroEase 1 14S® by the company Micro Powders, microwaxes consisting of a mixture of carnauba wax and polyethylene wax, such as the products sold under the names Micro Care 300® and 310® by the company Micro Powders, microwaxes consisting of a mixture of carnauba wax and of synthetic wax, such as the product sold under the name Micro Care 325® by the company Micro Powders, polyethylene microwaxes, such as the products sold under the names Micropoly 200®, 220®, 220L® and 250S® by the company Micro Powders, and polytetrafluoroethylene microwaxes, such as the products sold under the names Microslip 519® and 519 L® by the company Micro Powders.
The composition according to the invention may comprise a content of solid fatty substance preferably ranging from 1 % to 20% by weight and in particular from 2% to 15% by weight relative to the total weight of the composition.
The composition according to the invention may comprise lipophilic thickeners, gelling agents and/or suspension agents to improve the texture or the homogeneity of the products.
Mineral thickeners, gelling agents and suspension agents
As lipophilic mineral thickener, gelling agent or suspension agent, use may be made of modified clays that are preferably chosen from hydrophobic-modified montmorillonite clays, for instance hydrophobic-modified bentonites or hectorites. Examples that may be mentioned include the product Stearalkonium Bentonite (CTFA name) (product of reaction of bentonite and the quaternary ammonium stearalkonium chloride) such as the commercial product sold under the name Tixogel MP 250 by the company Sud Chemie Rheologicals, United Catalysts Inc. or the product Disteardimonium Hectorite (CTFA name) (product of reaction of hectorite and distearyldimonium chloride) sold under the name Bentone 38 or Bentone Gel by the company Elementis Specialities.
Mention may also be made of fumed silica optionally subjected to a hydrophobic surface treatment, the particle size of which is less than 1 μιτι. Specifically, it is possible to chemically modify the surface of the silica, by chemical reaction generating a reduced number of silanol groups present at the surface of the silica. It is especially possible to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained. The hydrophobic groups may be trimethylsiloxyl groups, which are obtained especially by treating fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are known as "silica silylate" according to the CTFA (8th Edition, 2000). They are sold, for example, under the references Aerosil R812® by the company Degussa, Cab-O-Sil TS- 530® by the company Cabot, dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained especially by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are known as "silica dimethyl silylate" according to the CTFA (8th Edition, 2000). They are sold, for example, under the references Aerosil R972® and Aerosil R974® by the company Degussa, and Cab-O-Sil TS-610® and Cab-O-Sil TS-720® by the company Cabot.
The hydrophobic fumed silica preferably has a particle size that may be nanometric to micrometric, for example ranging from about 5 to 200 nm. Organic thickeners, gelling agents and suspension agents
The organic lipophilic thickeners or gelling agents are, for example, partially or totally crosslinked elastomeric organopolysiloxanes of three-dimensional structure, for instance those sold under the names KSG6®, KSG16® and KSG18® from Shin-Etsu, Trefil E-505C® or Trefil E-506C® from Dow Corning, Gransil SR- CYC®, SR DMF10®, SR-DC556®, SR 5CYC gel®, SR DMF 10 gel® and SR DC 556 gel® from Grant Industries and SF 1204® and JK 1 13® from General Electric; ethylcellulose, for instance the product sold under the name Ethocel® by Dow Chemical; galactomannans comprising from one to six and in particular from two to four hydroxyl groups per saccharide, substituted with a saturated or unsaturated alkyl chain, for instance guar gum alkylated with C1 to C6, and in particular C1 to C3, alkyl chains, and mixtures thereof. Block copolymers of "diblock", "triblock" or "radial" type, of the polystyrene/polyisoprene or polystyrene/polybutadiene type, such as the products sold under the name Luvitol HSB® by the company BASF, of
the polystyrene/copoly(ethylene-propylene) type, such as the products sold under the name Kraton® by the company Shell Chemical Co., or of the polystyrene/copoly(ethylene-butylene) type, and mixtures of triblock and radial (star) copolymers in isododecane, such as those sold by the company Penreco under the name Versagel®, for instance the mixture of butylene/etnylene/styrene triblock copolymer and of ethylene/propylene/styrene star copolymer in isododecane (Versagel M 5960).
Lipophilic thickeners or gelling agents that may also be mentioned include polymers with a weight-average molecular mass of less than 100 000, comprising a) a polymer backbone with hydrocarbon-based repeating units containing at least one heteroatom, and optionally b) at least one optionally functionalized pendent fatty chain and/or terminal fatty chain, containing from 6 to 120 carbon atoms and being linked to these hydrocarbon-based units, as described in patent applications WO-A-02/056 847 and WO-A-02/47619, in particular polyamide resins (especially comprising alkyl groups containing from 12 to 22 carbon atoms) such as those described in US-A-5 783 657.
Among the lipophilic thickeners or gelling agents that may be used in the compositions according to the invention, mention may also be made of fatty acid esters of dextrin, such as dextrin palmitates, especially the products sold under the name Rheopearl TL® or Rheopearl KL® by the company Chiba Flour.
Silicone polyamides of the polyorganosiloxane type may also be used, such as those described in documents US-A-5 874 069, US-A-5 919 441 , US-A-6 051 216 and US-A-5 981 680.
These silicone polymers may belong to the following two families:
- polyorganosiloxanes comprising at least two groups capable of establishing hydrogen interactions, these two groups being in the chain of the polymer, and/or
- polyorganosiloxanes comprising at least two groups capable of establishing hydrogen interactions, these two groups being located on grafts or branches.
The thickeners, gelling agents and suspension agents are preferably present in amounts ranging from 0.1 % to 15% by weight and more preferentially from 0.2% to 10% by weight relative to the total weight of the composition.
The amounts of these various constituents that may be present in the cosmetic composition according to the invention are those conventionally used in compositions for treating perspiration.
EMULSIFIERS
The oily phase may also contain one or more emulsifiers with an HLB (hydrophilic/lipophilic balance) of less than 8, preferably less than or equal to 6 and especially ranging from 4 to 6. They may be soluble or dispersible in the said phase. Examples of emulsifiers that may be mentioned include fatty esters of polyols, especially of glycerol or sorbitol, and especially the isostearic, oleic and ricinoleate esters of polyols, such as the mixture of petrolatum, polyglyceryl-3 oleate, glyceryl isostearate, hydrogenated castor oil and ozokerite, sold under the
name Protegin W® by the company Goldschmidt, sorbitan isostearate, polyglyceryl diisostearate, polyglyceryl-2 sesquiisostearate; saccharide esters and ethers such as methyl glucose dioleate; fatty esters such as magnesium lanolate; dimethicone copolyols and alkyl dimethicone copolyols.
Examples that may be mentioned include the alkyl dimethicone copolyols corresponding to formula (I) below
CH,
I CH,
CH3 - Si Si ■Si - O- ■Si - CHQ (I)
I
CHQ
R in which:
Ri denotes a linear or branched C12-C20 and preferably C12-C18 alkyl group;
R2 denotes the group: ~CnH2n~(-OC2H4-)x~(-OC3H6-)y~O— R3>
R3 denotes a hydrogen atom or a linear or branched alkyl radical comprising from
1 to 12 carbon atoms;
a is an integer ranging from 1 to about 500;
b is an integer ranging from 1 to about 500;
n is an integer ranging from 2 to 12 and preferably from 2 to 5;
x is an integer ranging from 1 to about 50 and preferably from 1 to 30;
y is an integer ranging from 0 to about 49 and preferably from 0 to 29, with the proviso that when y is other than zero, the ratio x/y is greater than 1 and preferably ranges from 2 to 1 1 .
Among the alkyl dimethicone copolyol emulsifiers of formula (I) that are preferred, mention will be made more particularly of Cetyl PEG/PPG-10/1 Dimethicone and more particularly the mixture Cetyl PEG/PPG-10/1 Dimethicone and Dimethicone (INCI name), for instance the product sold under the trade name Abil EM90 by the company Goldschmidt, or alternatively the mixture (Polyglyceryl-4 Stearate and Cetyl PEG/PPG-10 (and) Dimethicone (and) Hexyl Laurate), for instance the product sold under the trade name Abil WE09 by the same company.
Among the water-in-oil emulsifiers, mention may also be made of the dimethicone copolyols corresponding to formula (II) below
CH,
CHQ CH3
CHQ
CH3 - Si -Si -O ■Si - 0 Si CH, (N)
CHQ CH,
CH, R„ in which:
R4 denotes the group: ~CmH2m~(-OC2H4-)s~(-OC3H6-)t~O— R5,
R5 denotes a hydrogen atom or a linear or branched alkyl radical comprising from 1 to 12 carbon atoms,
c is an integer ranging from 1 to about 500;
d is an integer ranging from 1 to about 500;
m is an integer ranging from 2 to 12 and preferably from 2 to 5;
s is an integer ranging from 1 to about 50 and preferably from 1 to 30;
t is an integer ranging from 0 to about 50 and preferably from 0 to 30; with the proviso that the sum s+t is greater than or equal to 1 . Among these preferential dimethicone copolyol emulsifiers of formula (II), use will particularly be made of PEG-18/PPG-18 Dimethicone and more particularly the mixture Cyclopentasiloxane (and) PEG-18/PPG-18 Dimethicone (INCI name), such as the product sold by the company Dow Corning under the trade name Silicone DC 5225 C or KF-6040 from the company Shin-Etsu.
According to one particularly preferred form, use will be made of a mixture of at least one emulsifier of formula (I) and of at least one emulsifier of formula (II).
Use will be made more particularly of a mixture of PEG-18/PPG-18 Dimethicone and Cetyl PEG/PPG-10/1 Dimethicone and even more particularly a mixture of (Cyclopentasiloxane (and) PEG-18/PPG-18 Dimethicone) and of Cetyl PEG/PPG- 10/1 Dimethicone and Dimethicone or of (Polyglyceryl-4-stearate and Cetyl PEG/PPG-10 (and) Dimethicone (and) Hexyl Laurate). Among the water-in-oil emulsifiers, mention may also be made of nonionic emulsifiers derived from fatty acids and polyol, alkylpolyglycosides (APG) and sugar esters, and mixtures thereof.
As nonionic emulsifiers derived from fatty acids and polyol, use may be made especially of fatty acid esters of polyol, the fatty acid especially containing a Cs-C24 alkyl chain, and the polyols being, for example, glycerol and sorbitan.
Fatty acid esters of polyol that may especially be mentioned include isostearic acid esters of polyols, stearic acid esters of polyols, and mixtures thereof, in particular isostearic acid esters of glycerol and/or sorbitan.
Stearic acid esters of polyols that may especially be mentioned include the polyethylene glycol esters, for instance PEG-30 Dipolyhydroxystearate, such as the product sold under the name Arlacel P135 by the company ICI.
Glycerol and/or sorbitan esters that may be mentioned, for example, include polyglyceryl isostearate, such as the product sold under the name Isolan Gl 34 by the company Goldschmidt; sorbitan isostearate, such as the product sold under the name Arlacel 987 by the company ICI; sorbitan glyceryl isostearate, such as the product sold under the name Arlacel 986 by the company ICI, the mixture of sorbitan isostearate and polyglyceryl isostearate (3 mmol) sold under the name Arlacel 1690 by the company Uniqema, and mixtures thereof.
The emulsifier may also be chosen from alkylpolyglycosides with an HLB of less than 7, for example those represented by the general formula (1 ) below:
R-O-(G)x (1 ) in which R represents a branched and/or unsaturated alkyl radical comprising from 14 to 24 carbon atoms, G represents a reduced sugar comprising 5 or 6 carbon atoms, and x is a value ranging from 1 to 10 and preferably from 1 to 4, and G especially denotes glucose, fructose or galactose.
The unsaturated alkyl radical may comprise one or more ethylenic unsaturations, and in particular one or two ethylenic unsaturations.
As alkylpolyglycosides of this type, mention may be made of alkylpolyglucosides (G = glucose in formula (I)), and especially the compounds of formula (I) in which R more particularly represents an oleyl radical (unsaturated C18 radical) or isostearyl (saturated C18 radical), G denotes glucose, x is a value ranging from 1 to 2, especially isostearyl glucoside or oleyl glucoside, and mixtures thereof. This alkylpolyglucoside may be used as a mixture with a coemulsifier, more especially with a fatty alcohol and especially a fatty alcohol containing the same fatty chain as that of the alkylpolyglucoside, i.e. comprising from 14 to 24 carbon atoms and containing a branched and/or unsaturated chain, for example isostearyl alcohol when the alkylpolyglucoside is isostearyl glucoside, and oleyl alcohol when the alkylpolyglucoside is oleyl glucoside, optionally in the form of a self-emulsifying composition, as described, for example, in document WO-A-92/06778. Use may be made, for example, of the mixture of isostearyl glucoside and isostearyl alcohol, sold under the name Montanov WO 18 by the company SEPPIC, and also the mixture octyldodecanol and octyldodecyl xyloside sold under the name Fludanov 20X by the company SEPPIC.
Mention may also be made of succinic-terminated polyolefins, for instance esterified succinic-terminated polyisobutylenes and salts thereof, especially the diethanolamine salts, such as the commercial products sold under the names Lubrizol 2724, Lubrizol 2722 and Lubrizol 5603 by the company Lubrizol or the commercial product Chemcinnate 2000. Among the water-in-oil emulsifiers, mention may also be made of oxyalkylenated, especially polyoxyethylenated and/or polyoxypropylenated and more particularly polyoxyethylenated, silicone elastomers such as those described in documents US-A-5 236 986, US-A-5 412 004, US-A-5 837 793 and US-A-5 81 1 487. The polyoxyalkylenated silicone elastomer is preferably conveyed in the form of a gel in at least one hydrocarbon-based oil and/or one silicone oil. In these gels, the polyoxyalkylenated elastomer is often in the form of non-spherical particles.
Examples of polyoxyalkylenated silicone elastomers are especially: As polyoxyethylenated silicone elastomers, use may be made of those sold by the company Shin-Etsu under the names:
- KSG21 (containing 27% active material. INCI name: Dimethicone/PEG-10 dimethicone vinyl dimethicone crosspolymer),
- KSG-20 (containing 95% active material. INCI name: PEG-10 Dimethicone crosspolymer),
- KSG-30 (containing 100% active material. INCI name: Lauryl PEG-15 dimethicone vinyl dimethicone crosspolymer),
- KSG-31 (containing 25% active material. INCI name: Lauryl PEG-15 dimethicone vinyl dimethicone crosspolymer),
- KSG-32 or KSG-42 or KSG-320 or KSG-30 (containing 25% active material. INCI name: Lauryl PEG-15 dimethicone vinyl dimethicone crosspolymer),
- KSG-33 (containing 20% active material),
- KSG-210 (containing 25% active material. INCI name: Dimethicone/PEG-10/15 crosspolymer),
-KSG-310: Lauryl-modified crosslinked polyoxyethylenated polydimethylsiloxane in mineral oil,
- KSG-330,
- KSG-340,
- X-226146 (containing 32% active material. INCI name: Dimethicone/PEG-10 dimethicone vinyl dimethicone crosspolymer),
or those sold by the company Dow Corning under the names:
- DC9010 (containing 9% active material. INCI name: PEG-12 dimethicone crosspolymer)
- DC901 1 (containing 1 1 % active material).
These products are generally in the form of oily gels containing silicone elastomers particles.
KSG-210 (INCI name: dimethicone/PEG-10/15 crosspolymer), which contains about 25% silicone elastomer active material in silicone oil, is preferably used.
Among the water-in-oil emulsifiers, mention may also be made of polyglycerolated silicone elastomers. Such elastomers are described especially in document WO-A- 2004/024 798.
Polyglycerolated silicone elastomers that may be used include those sold under the names:
KSG-710 (containing 25% active material. INCI name: Dimethicone/polyglycerine-3 crosspolymer),
- KSG-810,
- KSG-820,
- KSG-830,
- KSG-840.
by the company Shin-Etsu.
GALENICAL FORMS
The compositions may be in liquid, gel, semi-solid, solid or loose or compact powder form.
The compositions of the invention may especially be conditioned in pressurized form in an aerosol device or in a pump-action bottle; conditioned in a device equipped with a perforated wall, especially a grille; conditioned in a device equipped with a ball applicator ("roll-on"); conditioned in the form of wands (sticks).
In this regard, they contain the ingredients generally used in products of this type, which are well known to those skilled in the art.
According to another particular form of the invention, the compositions according to the invention may be solid, in particular in wand or stick form.
The term "solid composition" means that the maximum force measured by texturometry during the penetration of a probe into the sample of formula must be at least equal to 0.25 newtons, in particular at least equal to 0.30 newtons and especially at least equal to 0.35 newtons, assessed under precise measuring conditions as follows.
The formulae are poured hot into jars 4 cm in diameter and 3 cm deep. Cooling is performed at room temperature. The hardness of the formulae is measured after an interval of 24 hours. The jars containing the samples are characterized in texturometry using a texturometer such as the machine sold by the company Rheo TA-XT2, according to the following protocol: a stainless-steel ball probe 5 mm in diameter is brought into contact with the sample at a speed of 1 mm/s. The measuring system detects the interface with the sample, with a detection threshold equal to 0.005 newtons. The probe penetrates 0.3 mm into the sample, at a speed of 0.1 mm/s. The measuring machine records the change in force measured in compression over time, during the penetration phase. The hardness of the sample corresponds to the average of the maximum force values detected during penetration, over at least three measurements.
ADDITIVES
The compositions according to the invention may also comprise cosmetic adjuvants chosen from softeners, antioxidants, opacifiers, stabilizers, moisturizers, vitamins, bactericides, preserving agents, fragrances, moisture absorbers, deodorants, suspension agents, propellants or any other ingredient usually used in cosmetics for this type of application.
Needless to say, a person skilled in the art will take care to select this or these optional additional compounds such that the advantageous properties intrinsically associated with the cosmetic composition in accordance with the invention are not, or are not substantially, adversely affected by the envisaged addition(s).
It is also possible to add moisture absorbers, for instance perlites and preferably expanded perlites.
The perlites that may be used according to the invention are generally aluminosilicates of volcanic origin and have as the composition:
70.0-75.0% by weight of silica SiO2
12.0-15.0% by weight of oxide of aluminium oxide AI2O3
3.0-5.0% of sodium oxide Na2O
3.0-5.0% of potassium oxide K2O
0.5-2% of iron oxide Fe2O3 ->
0.2-0.7% of magnesium oxide MgO
0.5-1 .5% of calcium oxide CaO
0.05-0.15% of titanium oxide TiO2
The perlite is ground, dried and then calibrated in a first step. The product obtained, known as perlite ore, is grey-coloured and has a size of about 100 μιτι.
The perlite ore is then expanded (1000°C/2 seconds) to give more or less white particles. When the temperature reaches 850-900°C, the water trapped in the structure of the material evaporates and brings about the expansion of the material relative to its original volume. The expanded perlite particles in accordance with the invention may be obtained via the expansion process described in patent US 5 002 698.
Preferably, the perlite particles used are ground: in this case, they are known as Expanded Milled Perlite (EMP). They preferably have a particle size defined by a median diameter D50 ranging from 0.5 to 50 μιτι and preferably from 0.5 to 40 μιτι.
Preferably, the perlite particles used have an untamped apparent density at 25°C ranging from 10 to 400 kg/m3 (standard DIN 53468) and preferably from 10 to 300 kg/m3.
Preferably, the expanded perlite particles according to the invention have a water- absorbing capacity, measured at the wet point, ranging from 200% to 1500% and preferably from 250% to 800%. The wet point corresponds to the amount of water that needs to be added to 1 g of particle in order to obtain a homogeneous paste. This method is derived directly from that of the oil uptake applied to solvents. The measurements are taken in the same manner by means of the wet point and the flow point, which have, respectively, the following definition: wet point: mass expressed in grams per 100 g of product corresponding to the production of a homogeneous paste during the addition of a solvent to a powder; flow point: mass expressed in grams per 100 g of product at and above which the amount of solvent is greater than the capacity of the powder to retain it. This is reflected by the production of a more or less homogeneous mixture that flows on a glass plate.
The wet point and the flow point are measured according to the following protocol:
Protocol for measuring the water absorption
1 ) Materials used
Glass plate (25 x 25 mm)
Spatula (wooden and partly metallic handle, 15 x 2.7 mm)
Silk-bristled brush
Balance
2) Procedure
The glass plate is placed on the balance and 1 g of perlite particles is weighed out. The beaker containing the solvent and the sampling pipette is placed on the balance. The solvent is gradually added to the powder, the whole being regularly blended (every 3 to 4 drops) with the spatula.
The mass of solvent needed to obtain the wet point is noted. Further solvent is added and the mass required to reach the flow point is noted. The average of three tests is determined.
The expanded perlite particles sold under the trade names Optimat 1430 OR or Optimat 2550 by the company World Minerals will be used in particular.
DEODORANTS
The compositions of the invention may also contain deodorants.
The term "deodorant active agent" refers to any substance that is capable of masking, absorbing, improving and/or reducing the unpleasant odour resulting from the decomposition of human sweat by bacteria.
The deodorant active agents may be bacteriostatic agents or bactericides that act on underarm odour microorganisms, such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether (©Triclosan), 2,4-dichloro-2'-hydroxydiphenyl ether, 3',4',5'- trichlorosalicylanilide, 1 -(3',4'-dichlorophenyl)-3-(4'-chlorophenyl)urea
(©Triclocarban) or 3,7,1 1 -trimethyldodeca-2, 5,10-trienol (©Farnesol); quaternary ammonium salts such as cetyltrimethylammonium salts, cetylpyridinium salts, DPTA (1 ,3-diaminopropanetetraacetic acid), 1 ,2-decanediol (Symclariol from the company Symrise), glycerol derivatives, for instance caprylic/capric glycerides (Capmul MCM from Abitec), glyceryl caprylate or caprate (Dermosoft GMCY and Dermosoft GMC, respectively from Straetmans), Polyglyceryl-2 caprate (Dermosoft DGMC from Straetmans), and biguanide derivatives, for instance polyhexamethylene biguanide salts. - chlorhexidine and salts thereof; 4-phenyl- 4,4-dimethyl-2-butanol (Symdeo MPP from Symrise).
Among the deodorant active agents in accordance with the invention, mention may also be made of - zinc salts, for instance zinc salicylate, zinc gluconate, zinc pidolate; zinc sulfate, zinc chloride, zinc lactate, zinc phenolsulfonate; salicylic acid and derivatives thereof such as 5-n-octanoylsalicylic acid. The deodorant active agents may be odour absorbers such as zinc ricinoleate, sodium bicarbonate; metallic or non-metallic zeolites, cyclodextrins or alum.
It may also be a chelating agent such as Dissolvine GL-47-S from Akzo Nobel, EDTA; DPTA.
It may also be a polyol such as glycerol or propane-1 ,3-diol (Zemea Propane diol sold by Dupont Tate and Lyle Bioproducts).
Alternatively, it may be an enzyme inhibitor such as triethyl citrate.
In the event of incompatibility or to stabilize them, some of the agents mentioned above may be incorporated into spherules, especially ionic or nonionic vesicles and/or nanoparticles (capsules and/or spheres). The deodorant agents may preferably be present in the compositions according to the invention in weight concentrations ranging from 0.01 % to 15% by weight relative to the total weight of composition A or B.
ORGANIC POWDERS
According to one particular form of the invention, the compositions according to the invention will also contain an organic powder.
In the present patent application, the term "organic powder" means any solid that is insoluble in the medium at room temperature (25°C).
As organic powders that may be used in the composition of the invention, examples that may be mentioned include polyamide particles and especially those sold under the name Orgasol by the company Atochem; nylon-6,6 fibres, especially the polyamide fibres sold by Etablissements P Bonte under the name Polyamide 0.9 Dtex 0.3 mm (INCI name: Nylon-6,6 or Polyamide 6,6) with a mean diameter of 6 μιτι, a weight of about 0.9 dtex and a length ranging from 0.3 mm to 1 .5 mm; polyethylene powders; microspheres based on acrylic copolymers, such as those made of ethylene glycol dimethacrylate/lauryl methacrylate copolymer, sold by the company Dow Corning under the name Polytrap; polymethyl methacrylate microspheres, sold under the name Microsphere M-100 by the Company Matsumoto or under the name Covabead LH85 by the Company Wackherr; hollow polymethyl methacrylate microspheres (particle size: 6.5-10.5 μιτι) sold under the name Ganzpearl GMP 0800 by Ganz Chemical; methyl methacrylate/ethylene glycol dimethacrylate copolymer microbeads (size: 6.5-10.5 μιτι) sold under the name Ganzpearl GMP 0820 by Ganz Chemical or Microsponge 5640 by the company Amcol Health & Beauty Solutions; ethylene- acrylate copolymer powders, such as those sold under the name Flobeads by the company Sumitomo Seika Chemicals; expanded powders such as hollow microspheres and especially microspheres formed from a terpolymer of vinylidene chloride, acrylonitrile and methacrylate and sold under the name Expancel by the company Kemanord Plast under the references 551 DE 12 (particle size of about 12 μιτι and mass per unit volume of 40 kg/m3), 551 DE 20 (particle size of about 30 μιτι and mass per unit volume of 65 kg/m3), 551 DE 50 (particle size of about 40 μιτι), or the microspheres sold under the name Micropearl F 80 ED by the company Matsumoto; powders of natural organic materials such as starch powders, especially of crosslinked or non-crossl inked corn, wheat or rice starch, such as the powders of starch crosslinked with octenylsuccinic anhydride, sold under the name Dry-Flo by the company National Starch; silicone resin microbeads such as those sold under the name Tospearl by the company Toshiba Silicone, especially Tospearl 240; amino acid powders such as the lauroyllysine powder sold under the name Amihope LL-1 1 by the company Ajinomoto; particles of wax microdispersion, which preferably have mean sizes of less than 1 μιτι and especially ranging from 0.02 μιτι to 1 μιτι, and which are formed essentially from a wax or a mixture of waxes, such as the products sold under the name Aquacer by
the company Byk Cera, and especially: Aquacer 520 (mixture of synthetic and natural waxes), Aquacer 514 or 513 (polyethylene wax), Aquacer 51 1 (polymeric wax), or such as the products sold under the name Jonwax 120 by the company Johnson Polymer (mixture of polyethylene wax and paraffin wax) and under the name Ceraflour 961 by the company Byk Cera (micronized modified polyethylene wax); and mixtures thereof.
AEROSOLS The compositions according to the invention may also be pressurized and may be conditioned in an aerosol device formed by:
(A) a container comprising an antiperspirant composition as defined previously,
(B) at least one propellant and a means for dispensing the said aerosol composition.
The propellants generally used in products of this type and that are well known to those skilled in the art are, for instance, dimethyl ether (DME); volatile hydrocarbons such as n-butane, propane, isobutane and mixtures thereof, optionally with at least one chlorohydrocarbon and/or fluorohydrocarbon; among these derivatives, mention may be made of the compounds sold by the company DuPont de Nemours under the names Freon® and Dymel®, and in particular monofluorotrichloromethane, difluorodichloromethane, tetrafluorodichloroethane and 1 ,1 -difluoroethane sold especially under the trade name Dymel 152 A by the company DuPont. Carbon dioxide, nitrous oxide, nitrogen or compressed air may also be used as propellant.
The compositions containing perlite particles as defined previously and the propellant(s) may be in the same compartment or in different compartments in the aerosol container. According to the invention, the concentration of propellant generally ranges from 5% to 95% by weight of pressurized composition, and more preferentially from 50% to 85% by weight relative to the total weight of the pressurized composition.
The dispensing means, which forms a part of the aerosol device, is generally formed by a dispensing valve controlled by a dispensing head, which itself comprises a nozzle via which the aerosol composition is vaporized. The container containing the pressurized composition may be opaque or transparent. It may be made of glass, a polymer or a metal, optionally coated with a protective varnish coat.
The examples that follow serve to illustrate the present invention. The amounts indicated are expressed as weight percentages relative to the total weight of the composition. Examples 1 to 3: anhydrous aerosols
Ingredients Example 1 Example 2 Example 3
CaCI2-2H2O 7.5 5 -
Calcium pidolate - 2 8
NaHCOs 3 2
NaH2PO4 - 4
Triethyl citrate Citroflex 2 (Reilly 1 - 1
Chemicals)
Isopropyl palmitate 0.9 0.9 0.9
Dimethicone 9 9 9
(Dow Corning SH 200 C Fluid 10 CS)
Cyclopentasiloxane (and) 1 .3 1 .3 1 .3
Dimethiconol
Dow Corning 1501 Fluid (Dow
Corning)
Stearalkonium bentonite Tixogel MP 0.2 0.2 0.2
250
(Sud Chemie Rheolog.)
Isobutane (A-31 - Aeropres) qs 100 qs 100 qs 100
Procedure The salts are dispersed in the mixture of the other starting materials using a paddle. The mixture is pressurized in an aerosol can with isobutane.
Example 2: anhydrous stick
Procedure
The cydomethicone is heated to 65°C. The other ingredients are added one by one, while keeping the temperature at 65-70°C. The whole is homogenized for 15 minutes. The product is cooled to about 55°C (a few degrees above the thickening point of the mixture) and is poured into sticks. The sticks are kept at 4°C for 30 minutes.
Claims
1. Cosmetic process for treating human perspiration and possibly the body odour resulting from perspiration, which comprises the application to the skin of an anhydrous composition comprising, in a cosmetically acceptable medium, at least one compound (1 ) and at least one compound (2) that together produce an antiperspirant effect in situ on the skin; the said compounds (1 ) and (2) being capable of:
- (i) reacting together via one or more physical interactions to form an antiperspirant salt or complex in situ on the skin, or
- (ii) reacting together via one or more covalent bonds to impart an antiperspirant effect in situ on the skin, or
- (iii) interacting together on contact with the skin to impart an antiperspirant effect, in particular the said composition does not contain any antiperspirant halogenated aluminium and/or zirconium salt.
2. Process according to Claim 1 , in which compounds (1 ) and (2) are dispersed in the composition in the form of a powder whose mean particle size is preferably less than 100 μιτι.
3. Process according to Claim 1 or 2, in which at least one of the compounds (1 ) and (2) is encapsulated.
4. Process according to any one of Claims 1 to 3, in which compounds (1 ) and (2) that react together by means of one or more covalent bonds are chosen from the following combinations:
(i) compound (1 ) comprises one or more functions capable of reacting with one or more functions borne by compound (2), the said compounds reacting especially via a condensation reaction;
(ii) compound (1 ) reacts with compound (2) via a radical chemical reaction, the said compounds (1 ) and (2) especially being ethylenic compounds;
(iii) compound (1 ) reacts with compound (2) via an oxidation reaction involving an oxidizing agent;
(iv) compound (1 ) reacts with compound (2) via a crosslinking reaction.
5. Process according to any one of Claims 1 to 3, in which compounds (1 ) and (2) interact together on contact with the skin to impart an antiperspirant effect, characterized in that compound (1 ) is capable of treating the skin by involving a chemical reaction and compound (2) acts on the skin once it has been chemically modified; the said compound (1 ) being chosen more particularly from:
(i) compounds that are capable of grafting to the skin,
(ii) compounds that are capable of opening one or more bonds of the skin,
(iii) compounds that are capable of modifying the ionic nature of the skin,
(iv) compounds that are capable of removing all or some of the molecules present in the skin,
(v) compounds that are capable of creating catalytic groups on the skin.
6. Process according to any one of Claims 1 to 3, in which compounds (1 ) and (2) interact together on contact with the skin to impart an antiperspirant effect, characterized in that compound (1 ) is capable of treating the skin by involving a physical reaction and compound (2) acts on the skin once it has been physically modified; the said compound (1 ) being chosen more particularly from:
(i) compounds that are capable of increasing the retention on the skin of at least one compound (2);
(ii) compounds that are capable of removing on and/or in the skin agents that are liable to harm the action of compound (2);
(iii) compounds that are capable of improving the distribution and/or penetration of at least one compound (2) on and/or into the skin;
(iv) compounds that are capable of modifying the porosity of the skin;
(v) compounds that are capable of making the skin reactive, in particular chosen from oxidizing agents;
(vi) compounds that are capable of withstanding movements, elongation and friction.
7. Process according to any one of Claims 1 to 3, in which compounds (1 ) and (2) react together via one or more physical interactions chosen from ionic bonds, hydrogen bonds, Van der Waals bonds and hydrophobic bonds.
8. Process according to Claim 7, in which compound (1 ) and compound (2) are capable of reacting via an acid/base reaction or via a cation/anion reaction and are more particularly capable of reacting together by precipitation or flocculation.
9. Process according to Claim 8, in which compound (1 ) is a salt of a multivalent inorganic cation, and compound (2) is a salt of an inorganic anion.
10. Process according to Claim 9, in which the multivalent cation is chosen from:
(i) alkaline-earth metal cations
(ii) transition metal cations.
11. Process according to Claim 10, in which
- the multivalent alkaline-earth metal cations are chosen from strontium, magnesium and calcium;
- the multivalent transition metal cations are chosen from zinc, manganese and aluminium.
12. Process according to any one of Claims 9 to 1 1 , in which the multivalent inorganic cation salt is chosen from salts with a solubility in water of greater than 2%, between 15°C and 30°C at a pH of between 6 and 8, and preferably chosen from:
- halides;
- carboxylic acid salts such as acetates, propionates, pyrrol idonecarboxylates (or pidolates) or sorbates;
- polyhydroxylated carboxylic acid salts such as gluconates, heptagluconates, ketogluconates, lactate-gluconates, ascorbates or pentothenates;
- mono- or polycarboxylic hydroxy acid salts such as citrates or lactates;
- amino acid salts such as aspartates or glutamates;
- fulvate salts;
- bicarbonate salts;
- nitrates; - sulfates such as magnesium sulfate or aluminium double sulfates such as alum: (KAI(SO4)2 12 H2O.
13. Process according to any one of Claims 9 to 12, in which the multivalent inorganic cation salt is chosen from magnesium chloride, manganese chloride, calcium chloride, calcium aspartate, calcium lactate, calcium propionate, calcium pidolate, calcium pentothenate, calcium bicarbonate, calcium sorbate, calcium lactate gluconate and calcium fulvate and even more particularly calcium chloride and/or calcium pidolate.
14. Process according to any one of Claims 9 to 13, in which the inorganic anion is chosen from carbonate (CO32"), hydrogen carbonate (HCO3"), phosphate (PO4 3"), polyphosphates such as diphosphate P2O7 4" (also known as pyrophosphate), triphosphate P3O105", phosphonate (PO33"), hydrogen phosphate (HPO4 2"), sulfate (SO4 2"), sulfonate (SO32"), hydrogen sulfate (HSO4 ~), and hydrogen sulfonate (HSO3") and more particularly hydrogen phosphate or hydrogen carbonate.
15. Process according to any one of Claims 9 to 14, in which the anion salt is chosen from:
- alkaline-earth metal salts;
- salts of an alkali metal such as potassium or sodium;
- ammonium salts, salts of an amine, in particular of mono-, di- or trialkanolamines; comprising one to three identical or different Ci-C4 hydroxyalkyl radicals;
and more preferentially alkali metal salts, in particular a sodium or potassium salt.
16. Anhydrous composition comprising, in a cosmetically acceptable medium, a salt of an inorganic multivalent cation (1 ) and a salt of an inorganic anion (2) as defined in any one of Claims 9 to 15; the said compounds (1 ) and (2) forming an antiperspirant salt in situ on the skin, by cation/anion ionic interaction; in particular, the said composition does not contain any antiperspirant halogenated aluminium and/or zirconium salt.
17. Composition according to Claim 16, in which the mole ratio between the cation and the anion ranges from 10/1 to 1/10 and more preferentially from 4/1 to 1/4.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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FR1156659 | 2011-07-22 | ||
FR1156659A FR2978036B1 (en) | 2011-07-22 | 2011-07-22 | PROCESS FOR TREATING TRANSPIRATION USING AN ANHYDROUS COMPOSITION COMPRISING TWO REAGENTS PRODUCING IN-SITU ASSEMBLY ON THE SKIN A TRANSPIRING EFFECT |
US201161511715P | 2011-07-26 | 2011-07-26 | |
US61/511,715 | 2011-07-26 |
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WO2013013903A1 true WO2013013903A1 (en) | 2013-01-31 |
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PCT/EP2012/061884 WO2013013903A1 (en) | 2011-07-22 | 2012-06-20 | Process for treating perspiration using an anhydrous composition comprising two reagents that together produce an antiperspirant effect in situ on the skin |
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US10350151B2 (en) | 2014-12-26 | 2019-07-16 | Colgate-Palmolive Company | Zinc phosphate complex |
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US11213466B2 (en) | 2014-12-26 | 2022-01-04 | Colgate-Palmolive Company | Personal care compositions with zinc phosphate active |
US11844853B2 (en) | 2018-08-09 | 2023-12-19 | Conopco, Inc. | Antiperspirant composition |
US12005076B2 (en) | 2014-12-26 | 2024-06-11 | Colgate-Palmolive Company | Zinc phosphate complex |
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FR3036285B1 (en) | 2015-05-21 | 2017-06-02 | Laboratoires M&L | ANHYDROUS DEODORANT COMPOSITION BASED ON BICARBONATE |
FR3142342A1 (en) * | 2022-11-30 | 2024-05-31 | L'oreal | Method for treating human sweat and associated kit |
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WO2010070143A1 (en) | 2008-12-19 | 2010-06-24 | L'oreal | Multi-component antiperspirant agent comprising two components capable of cooperating, and two-step process for treating human perspiration |
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- 2011-07-22 FR FR1156659A patent/FR2978036B1/en not_active Expired - Fee Related
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US20170333308A1 (en) * | 2014-12-15 | 2017-11-23 | Conopco, Inc., D/B/A Unilever | Antiperspirant compositions comprising alums |
US10342749B2 (en) | 2014-12-15 | 2019-07-09 | Conopco, Inc. | Antiperspirant compositions comprising alums |
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US11213466B2 (en) | 2014-12-26 | 2022-01-04 | Colgate-Palmolive Company | Personal care compositions with zinc phosphate active |
US12005076B2 (en) | 2014-12-26 | 2024-06-11 | Colgate-Palmolive Company | Zinc phosphate complex |
US11690791B2 (en) | 2014-12-26 | 2023-07-04 | Colgate-Palmolive Company | Zinc phosphate complex |
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CN108367172B (en) * | 2015-12-16 | 2021-09-21 | 高露洁-棕榄公司 | Occlusive personal care compositions |
WO2017105438A1 (en) * | 2015-12-16 | 2017-06-22 | Colgate-Palmolive Company | Occlusive personal care composition |
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CN110072594A (en) * | 2016-12-14 | 2019-07-30 | 高露洁-棕榄公司 | Without aluminium antiperspirant/deodorant compositions |
US11844853B2 (en) | 2018-08-09 | 2023-12-19 | Conopco, Inc. | Antiperspirant composition |
WO2020144056A1 (en) | 2019-01-11 | 2020-07-16 | Unilever N.V. | An antiperspirant composition comprising inorganic polyionic cluster |
WO2020187686A1 (en) | 2019-03-18 | 2020-09-24 | Unilever N.V. | An antiperspirant composition comprising reactive salts |
WO2020187699A1 (en) | 2019-03-18 | 2020-09-24 | Unilever N.V. | An antiperspirant composition comprising reactive salts |
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FR2978036B1 (en) | 2013-07-19 |
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