WO2016050788A1 - Procédé cosmétique pour atténuer les rides - Google Patents

Procédé cosmétique pour atténuer les rides Download PDF

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Publication number
WO2016050788A1
WO2016050788A1 PCT/EP2015/072465 EP2015072465W WO2016050788A1 WO 2016050788 A1 WO2016050788 A1 WO 2016050788A1 EP 2015072465 W EP2015072465 W EP 2015072465W WO 2016050788 A1 WO2016050788 A1 WO 2016050788A1
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Prior art keywords
benzene
bis
grafted
thiol
tris
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PCT/EP2015/072465
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English (en)
Inventor
Xavier Schultze
Andrew Greaves
Bertrand Lion
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L'oreal
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Publication of WO2016050788A1 publication Critical patent/WO2016050788A1/fr

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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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/08—Anti-ageing preparations

Definitions

  • the present invention relates to a process, in particular a cosmetic process, for caring for the skin, intended to attenuate wrinkles, comprising the application to the skin of the mixture of a composition comprising a grafted polysaccharide polymer and of a particular crosslinking thiol compound, and to the use of this mixture as a skin tensioning agent.
  • the inventors have discovered that a polysaccharide polymer grafted with (meth)acrylate groups combined with a particular thiol compound, applied to the skin, has a good tensioning effect on the skin and thus makes it possible to immediately attenuate wrinkles on the skin. Furthermore, this tensioning effect exhibits good water resistance, and therefore good persistence with respect to water. The tensioning effect is also resistant to sweat, and to the mechanical stresses created by movement of the skin.
  • Dextran polymers grafted with methacrylate groups are described in document WO 2010/083039. They are used in combination with riboflavin and arginine or chitosan for forming, after crosslinking under UV exposure or exposure to visible light, hydrogels which are applied to the skin.
  • Carrageenans are known for their skin tensioning properties, in particular in document FR-A-2838343.
  • a subject of the present invention is a process, in particular a cosmetic process, for caring for the skin, more particularly facial skin, in particular wrinkled skin, comprising:
  • composition in particular a cosmetic composition, comprising at least one, preferably one, polysaccharide polymer grafted with (meth)acrylate groups and of at least one, preferably one, crosslinking thiol compound having one or more thiol groups;
  • composition in particular a cosmetic composition
  • A comprising at least one, preferably one, polysaccharide polymer grafted with (meth)acrylate groups, followed by the application of at least one, preferably one, crosslinking thiol compound having one or more thiol groups, or of a composition, in particular a cosmetic composition, B containing same.
  • a subject of the invention is also the use, in particular cosmetic use, as a skin, in particular wrinkled skin, tensioning agent, of a grafted polysaccharide polymer as previously defined, or of a composition, in particular a cosmetic composition, containing same, mixed with the crosslinking thiol compound as previously defined.
  • a subject of the invention is also a composition, in particular a cosmetic composition, obtained by mixing a composition, in particular a cosmetic composition, comprising a grafted polysaccharide polymer as previously defined and a crosslinking thiol compound as previously defined or a composition, in particular a cosmetic composition, containing same.
  • a subject of the invention is also a kit comprising a first composition (composition A), which is in particular a cosmetic composition, comprising a grafted polysaccharide polymer as previously defined and a second composition (composition B), which is in particular a cosmetic composition, comprising a crosslinking thiol compound as previously defined, the first and second compositions each being packaged in a distinct packaging assembly.
  • composition A which is in particular a cosmetic composition, comprising a grafted polysaccharide polymer as previously defined
  • composition B which is in particular a cosmetic composition, comprising a crosslinking thiol compound as previously defined
  • composition packaging assembly is, in a known manner, any packaging that is suitable for storing cosmetic compositions (in particular a bottle, tube, spray bottle or aerosol bottle).
  • Such a kit allows the skin treatment process according to the invention to be performed.
  • the process according to the invention is in particular intended for smoothing out wrinkled human facial and/or body skin, in particular for reducing or effacing wrinkles and/or fine lines on the skin.
  • the tensioning effect may be characterized by means of an in vitro retraction test as described in Examples 1 to 4.
  • polysaccharide grafted with (meth)acrylate groups is intended to mean a polysaccharide of which all or some free hydroxyl groups have been esterified so as to form (meth)acrylate ester groups.
  • the grafted polysaccharide used according to the invention may be chosen from (meth)acrylate-grafted hyaluronic acid, (meth)acrylate-grafted dextran and (meth)acrylate-grafted carrageenan, such as those described hereinafter.
  • the (meth)acrylate-grafted polysaccharide has a weight-average molecular weight ranging from 5000 to 1 000 000 daltons, preferably ranging from 10 000 to 500 000 daltons, and even more preferentially ranging from 15 000 to 350 000 daltons.
  • the grafted polysaccharide may be a (meth)acrylate-grafted hyaluronic acid.
  • Hyaluronic acid is a linear glycosaminoglycan composed of repeating D-glucuronic acid and N-acetyl-D-glucosamine units linked together via alternating beta-1 ,4 and beta-1 ,3 glycosidic linkages.
  • the grafted hyaluronic acid polymer has a weight-average molecular weight ranging from 5000 to 1 000 000 daltons, more preferentially ranging from 10 000 to
  • the molecular weight can be determined in particular by liquid chromatography, the eluent being 0.1 M sodium chloride and 330 mg/l of sodium azide in water, with dextran as standard, and Wyatt Optilab T-Rex refractometer and Wyatt Dawn-Heleos II light scattering detectors.
  • the grafted hyaluronic acid polymer has a degree of grafting with (meth)acrylate groups ranging from 10% to 80% or 20% to 80%, preferably ranging from 40% to 70%, and preferentially ranging from 45% to 65%.
  • the degree of grafting corresponds to the mole percentage of hydroxyl groups of the hyaluronic acid which are grafted with a (meth)acrylate group.
  • a degree of grafting of 50% corresponds to 2 acrylate groups grafted onto the 4 hydroxyls of the repeating unit of the hyaluronic acid.
  • the grafting of hyaluronic acid with (meth)acrylate groups results from the presence of a (meth)acrylate ester group formed with the free hydroxyls of hyaluronic acid.
  • the hyaluronic acid is grafted with acrylate groups.
  • the hyaluronic acid grafted with (meth)acrylate groups can be obtained by reaction of the hyaluronic acid with (meth)acrylic anhydride.
  • the reaction is advantageously carried out in a basic aqueous medium, in particular in the presence of an organic or inorganic base such as, for example, sodium hydroxide.
  • an organic or inorganic base such as, for example, sodium hydroxide.
  • the reaction is carried out at a temperature ranging from 5 to 10°C, in particular for a period of time ranging from 24 hours to 48 hours.
  • the grafted polysaccharide may be a (meth)acrylate-grafted dextran.
  • Dextran is a branched polysaccharide of d-glucose (dextrose) which has a linear backbone, the glucoses of which are linked to one another by alpha-1 ,6 linkages; it has branched chains consisting of d-glucose linked to one another by alpha-1 ,2 or -1 ,3 or - 1 ,4 linkages.
  • the grafted dextran polymer is a weight-average molecular weight ranging from 10 000 to 1 000 000 daltons, more preferentially ranging from 10 000 to 500 000 daltons, and even more preferentially ranging from 15 000 to 350 000 daltons.
  • the weight-average molecular weight can in particular be determined by the liquid chromatography by gel permeation or by size exclusion chromatography.
  • the grafted dextran polymer has a degree of grafting with (meth)acrylate groups ranging from 2% to 70%, preferably ranging from 3% to 65%, and preferentially ranging from 5% to 60%.
  • the degree of grafting corresponds to the mole percentage of hydroxyl groups of the dextran which are grafted with a (meth)acrylate group.
  • a degree of grafting of 50% corresponds to 1 .5 acrylate groups grafted onto the 3 hydroxyls of the repeating unit of the dextran.
  • the dextran is grafted with methacrylate groups.
  • the dextran grafted with (meth)acrylate groups can be obtained by reaction of the dextran with (meth)acrylic anhydride.
  • the reaction is advantageously carried out in an aprotic polar solvent (example dimethylformamide, N-methylpyrrolidone, N- ethylpyrrolidone), in particular in the presence of a non-nucleophilic organic or inorganic base, for instance tertiary amines (such as triethanolamine).
  • the reaction is carried out at a temperature ranging from 20 to 100°C, in particular for a period of time ranging from 1 to 12 hours
  • the grafted polysaccharide may be a (meth)acrylate-grafted carrageenan.
  • Carrageenans are sulfated polysaccharides which constitute the cell walls of various red algae, from which they can be obtained.
  • red algae mention may be made, in a non-limiting manner, of Kappaphycus alvarezii, Eucheuma denticulatum, Eucheuma spinosum, Chondrus crispus, Betaphycus gelatinum, Gigartina skottsbergii, Gigartina canaliculata, Sarcothalia crispata, Mazzaella laminaroides, Hypnea musciformis, Mastocarpus stellatus and Iridaea cordata.
  • the polysaccharides comprise long galactan chains, made up of disaccharide units. These polysaccharides are composed of alternating (1 ⁇ 3) ⁇ -D-galactopyranose (G unit) and (1 ⁇ 4) a-galactopyranose (D unit) or 3,6-anhydro-a-galactopyranose (AnGal unit). Each sugar unit can be sulfated one or more times in position 2, 3, 4 or 6. Methyl and pyruvic acid groups and also other sugar units grafted onto the base structures previously described can also be found.
  • the carrageenans were initially subdivided into subfamilies according to their solubility in KCI, then according to the number and position of the sulfate groups and the presence of 3',6'-anhydro bridges on the galactopyranosyl residues. There are at least about 15 carrageenans listed, the structure of which depends on the alga of origin and the extraction method. Among the most common, mention may be made of the carrageenans below:
  • carrageenans are thus often obtained in the form of mixtures of different structures such as, and in a non-limiting manner, mixtures of ⁇ , ⁇ , ⁇ forms.
  • the carrageenans that can be used may in particular be chosen from carrageenans of ⁇ , K, v, i, ⁇ and ⁇ type.
  • Carrageenans that are particularly suitable for implementing the invention are carrageenans of ⁇ , v and ⁇ type.
  • Lambda carrageenan is preferably used.
  • the carrageenans of the present invention can be used in acid form or in salified form.
  • acceptable salts mention may be made, in a non-limiting manner, of lithium, sodium, potassium, calcium, zinc or ammonium salts.
  • the grafted carrageenan polymer has a weight-average molecular weight ranging from 10 000 to 1 000 000 daltons, more preferentially ranging from 10 000 to 500 000 daltons, and even more preferentially ranging from 15 000 to 350 000 daltons.
  • the molecular weight can be determined in particular by liquid chromatography, the eluent being 0.1 M sodium chloride and 330 mg/l of sodium azide in water, with dextran as standard, and Wyatt Optilab T-Rex refractometer and Wyatt Dawn-Heleos II light scattering detectors.
  • the grafted carrageenan polymer has a degree of grafting with (meth)acrylate groups ranging from 2% to 60%, preferably ranging from 2% to 50%, and preferentially ranging from 5% to 30%.
  • the degree of grafting corresponds to the mole percentage of hydroxyl groups of the carrageenan which are grafted with a (meth)acrylate group.
  • a degree of grafting of 50% corresponds to 1 .5 acrylate groups grafted onto the 3 hydroxyls of the repeating unit of the carrageenan.
  • the grafting of the carrageenan with (meth)acrylate groups results from the presence of a (meth)acrylate ester group formed with the free hydroxyls of the carrageenan.
  • the carrageenan is grafted with acrylate groups.
  • the carrageenan grafted with (meth)acrylate groups can be obtained by reaction of the carrageenan with (meth)acrylic anhydride.
  • the reaction is advantageously carried out in a basic aqueous medium, in particular in the presence of an organic or inorganic base such as, for example, sodium hydroxide.
  • an organic or inorganic base such as, for example, sodium hydroxide.
  • the reaction is carried out at a temperature ranging from 5 to 10°C, in particular for a period of time ranging from 24 hours to 48 hours.
  • a carrageenan chosen from ⁇ -carrageenan, ⁇ -carrageenan, v- carrageenans, and preferably ⁇ -carrageenan, is used.
  • the grafted polysaccharide polymer as previously defined may be present in the composition used according to the invention (in particular composition A) in a content ranging from 0.1 % to 10% by weight, relative to the total weight of the composition, preferably from 0.5% to 10% by weight of active material, preferentially ranging from 1 % to 8% by weight, and more preferentially ranging from 1 % to 6% by weight.
  • the grafted polysaccharide is chosen from acrylate-grafted hyaluronic acid, (meth)acrylate-grafted dextran and acrylate-grafted carrageenan.
  • the crosslinking thiol used in the invention is a compound comprising one or more thiol groups (SH) and optionally another function capable of reacting with the ethylenic unsaturation of the (meth)acrylate groups grafted onto the polysaccharide, such as a primary or secondary amine function, preferably a primary amine function.
  • the crosslinking thiol may be a crosslinking polythiol or monothiol as described hereinafter.
  • polythiol is intended to mean any compound bearing two or more than two thiol groups SH. It may be a non-polymeric organic molecule bearing two or more than two thiol groups, or a polymer bearing two or more than two thiol groups.
  • the polythiol compound may be aromatic or heteroaromatic or may contain an aromatic radical.
  • the polythiol compound used according to the invention may also contain one or more heteroatoms chosen from O, N and S and/or one or more functions chosen from ester, ketone, amide, urea and isocyanurate functions.
  • the polythiol compound used according to the invention may also contain one or more heteroatoms chosen from O, N and S and/or one or more functions chosen from ester and ketone functions.
  • the polythiol compound used according to the invention denotes a non-polymeric organic compound and can be represented by formula (I)
  • n denotes an integer greater than or equal to 2, preferably between 2 and 10, preferably between 2 and 5,
  • W denotes a linear or branched or (hetero)cyclic, saturated C 2 -C 8 o multivalent (at least divalent) radical, an aromatic radical or a heteroaromatic cyclic radical, it being possible for W to also contain one or more heteroatoms such as O, N or S, and/or one or more functions chosen from ester, ketone, amide or urea functions and/or to be substituted with one or more linear or branched C-I-C-IO alkyl, hydroxyl, amino, (CrC 6 alkyl) amino, carboxylic, carboxylate, or linear or branched C-I-C-IO alkoxy groups, it being understood that, when the W radical is substituted, the thiol functions can be borne by the substituent(s).
  • cyclic radical is intended to mean a hydrocarbon-based saturated monocyclic or heterocyclic radical, a saturated or aromatic polycyclic radical, for example biphenyl, or condensed rings, for instance the naph
  • the molar mass of the compounds of formula (I) is generally between 70 and 1500 g/mol and preferably between 70 and 500 g/mol.
  • the polythiol compound of the invention denotes, for example
  • the compound comprising a thiol unit can be chosen, for example, from 1 ,1 ,1 -tris(mercaptomethyl)ethane, 2-ethyl-2-mercaptomethyl-1 ,3- propanedithiol, and 1 ,2,3-propanetrithiol.
  • the compound comprising a thiol unit can be chosen, for example, from
  • the compound (I) is chosen from 1 ,2-bis(2- mercaptoethylthio)propanethiol, 1 ,2,3-tris(2-mercaptoethylthio)propane and tetrakis(2- mercaptoethylthiomethyl)methane.
  • the compound comprising a thiol unit, of formula (I) is such that n denotes an integer greater than or equal to 2 and W denotes a linear or branched C 3 -C 20 , preferably linear or branched C 2 -Ci 2 , hydrocarbon-based saturated multivalent (at least divalent) radical, said radical containing at least one ester function.
  • the compound comprising a thiol unit can be chosen, for example, from
  • esters of polyols (glycols, triols, tetraols, pentaols, hexaols) and of Ci-C 6 mercaptocarboxylic acid, such as ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), thylene glycol bis(thioglycolate), trimethylolpropane tris(thioglycolate), trimethylolpropane tris(beta- mercaptopropionate), pentaerythritol tetrakis(thioglycolate), pentaerythritol tetrakis(beta-mercaptopropionate), dipentaerylthritol hexakis(beta- mercaptoproprionate), trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate),
  • the compound comprising a thiol unit is chosen from trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3- mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutanate) and dipentaerythritol hex-3-mercaptopropionate.
  • the compound comprising a thiol unit is pentaerythritol tetrakis(3- mercaptopropionate).
  • the compound comprising a thiol unit can be chosen, for example, from tetrakis(2-mercaptoethylthiomethyl)methane and bis-(2-mercaptoethylthio- 3-mercaptopropane)sulfide.
  • the compound comprising a thiol unit can be chosen, for example, from 1 ,4-cyclohexanedithiol, 1 ,4-bis(mercaptomethyl)cyclohexane, 1 ,1 - cyclohexanedithiol, 1 ,2-cyclohexanedithiol, 1 ,1 -bis(mercaptomethyl)cyclohexane, and 2,5-dimercapto-1 ,4-dithiane.
  • the compound comprising a thiol unit can be chosen, for example, from polythiols of the isocyanurate class, described in patents US 3 676 440 and US 201 1 023 0585, such as tris((mercaptopropionyloxy)ethyl)isocyanurate.
  • the compound comprising a thiol unit denotes tris((mercaptopropionyloxy)ethyl)isocyanurate.
  • the compound comprising a thiol unit can be chosen, for example, from
  • the compound (I) is chosen from 1 ,2,3- trimercaptobenzene, 1 ,2,4-trimercaptobenzene, 1 ,3,5-trimercaptobenzene, 1 ,2,3- tris(mercaptomethyl)benzene, 1 ,2,4-tris(mercaptomethyl)benzene, 1 ,3,5- tris(mercaptomethyl)benzene, 1 ,2,3-tris(2-mercaptoethyl)benzene, 1 ,2,4-tris(2- mercaptoethyl)benzene, 1 ,3,5-tris(2-mercaptoethyl)benzene, 1 ,2,3-tris(2- mercaptoethyleneoxy)benzene, 1 ,2,4-tris(2-mercaptoethyleneoxy)benzene, 1 ,3,5-tris(2-mercaptoethyleneoxy)benzene, 1 ,2,3,4-tris(2-mercaptoethyleneoxy)benzene, 1
  • the compound comprising a thiol unit can be chosen, for example, from triglycerides of fatty acids or vegetable oils modified with thiol groups by chemical reaction, for instance thiolated soybean oils and hydroxylated and thiolated soybean oils, in particular the polymercaptan® products from the company Chevron Phillips, such as polymercaptan 358 (mercaptanized soybean oil) and polymercaptan 407 (mercapto hydroxy soybean oil).
  • the compound comprising a thiol unit can be chosen, for example, from dithiothreitol and 2,3-dimercapto-1 -propanol.
  • the compound comprising a thiol unit, of formula (I) may be meso-2,3-dimercaptosuccinic acid or Ci-C 4 alcohol esters thereof.
  • n denotes an integer ranging from 2 to 4.
  • the compounds of formula (I) are chosen from the compounds of the fourth embodiment, such as, in particular, trimethylolpropane tris(2- mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutanate) or dipentaerythritol hex-3- mercaptopropionate, and more particularly pentaerythritol tetrakis(3- mercaptopropionate); or from the compounds of the tenth embodiment, such as, in particular, dithiothreitol.
  • the compounds of formula (I) denote pentaerythritol tetrakis(2- mercaptoacetate), trimethylolpropane tri
  • the polythiol compound used according to the invention denotes a polymeric compound and can be represented by formula (II) POL(SH)n (II)
  • n denotes an integer greater than or equal to 5, preferably between 5 and 5000, preferably between 5 and 1000,
  • POL denotes a multivalent (at least pentavalent) carbon-based or silicone polymeric radical, it being possible for POL to also contain one or more heteroatoms such as O, N or S, and/or one or more functions chosen from ester, ketone, amide, urea and carbamate functions, and/or to be substituted with one or more linear or branched C-I-C-IO alkyl or linear or branched C-I-C-IO alkoxy groups, it being understood that, when POL is substituted, the thiol functions can be borne by the substituent(s).
  • the molar mass of the compounds of formula (I I) is generally between 500 and 400 000 g/mol and preferably between 500 and 150 000 g/mol.
  • POL can denote a multivalent radical of homopolymer or copolymer type
  • POL can denote a polymeric radical of star, comb, brush or dendritic type.
  • the POL radical may be of natural origin (such as polysaccharides, peptides) or synthetic origin (such as acrylic polymers, polyesters, polyglycols).
  • the thiol functions (-SH) may be end and/or pendant groups.
  • the thiolated compound of formula (I I) is such that POL denotes a hydrocarbon-based polymeric radical.
  • the compounds of formula (II) also denote proteins and peptides with thiol units, for instance the structures re resented in the following table:
  • the thiolated compound of formula (II) also denotes the compounds of formula (II) such that POL denotes a radical termed dendrimer or polymer which is branched or hyperbranched, and the thiol groups are end groups.
  • POL denotes a radical termed dendrimer or polymer which is branched or hyperbranched
  • thiol groups are end groups.
  • the compound comprising a thiol unit, of formula (II), may also denote a hyperbranched or dendritic polymer modified with thiol functions, as described in application FR 2 761 691 .
  • Polymers of polypropylene ether glycol bis(beta-mercaptopropionate) type can also be used. They are prepared from polypropylene ether glycol (e.g., Pluracol P201 , Wyandotte Chemical Corp.) and beta-mercaptopropionic acid by esterification reaction and are known to those skilled in the art.
  • Some polymers comprising a thiol unit, of formula (II), are also commercially available, such as the Thiocure® products from the company Bruno Brock, Thiocure® ETTMP 1300 (Ethoxylated-Trimethylolpropane Tri-3-Mercaptopropionate (CAS# 345352-19-4) and Thiocure® ETTMP 700 (Ethoxylated-Trimethylolpropane Tri-3-Mercaptopropionate (CAS# 345352-19-4);
  • the compound of formula (II) is such that POL denotes a silicone-based polymeric radical.
  • silicone polythiols examples include silicone polythiols.
  • the silicone polythiols are in particular polydimethylsiloxanes comprising two or more than two thiol groups such as, for example, the SMS-022, SMS-042 and SMS-992 products sold by the company Gelest Inc.
  • the crosslinking thiol may also be a monothiol compound comprising another function capable of reacting with the ethylenic unsaturation of the (meth)acrylate groups grafted onto the polysaccharide, such as a primary or secondary amine function, preferably a primary amine function.
  • the crosslinking thiol may in particular be an aminothiol, in particular a compound of formula (III):
  • b denotes an integer ranging from 1 to 5, preferably ranging from 1 to 3 and more preferentially equal to 1 .
  • L denotes a linear or branched or (hetero)cyclic, saturated C 2 -C 8 o multivalent (at least divalent) radical, an aromatic radical or a heteroaromatic cyclic radical, it being possible for W to also contain one or more non-adjacent heteroatoms such as O, N or S, and/or one or more functions chosen from ester, ketone, amide, urea and carbamate functions, preferably ester and ketone functions, and/or to be substituted with one or more linear or branched C1-C1 0 alkyl, hydroxyl, carboxylic, carboxylate, or linear or branched C1-C1 0 alkoxy groups, it being understood that, when the W radical is substituted, the thiol functions can be borne by the substituent(s);
  • R denotes a hydrogen atom or a Ci-C 6 alkyl, or CH 3 CO- or C 2 H 5 -CO- radical, and preferably a hydrogen atom.
  • aminothiol compound mention may be made of cysteamine, N-acetyl cysteamine, cysteine, N-acetyl cysteine, homocysteine, the compounds of formula
  • n and m being integers ranging from 1 to 4,
  • ortho-aminothiophenol meta-aminothiophenol and para-aminothiophenol.
  • the crosslinking thiol is chosen from cysteamine, dithiothreitol, and pentaerythritol tetra(3-mercaptopropionate).
  • the crosslinking thiol is cysteamine.
  • the process according to the invention is carried out with hyaluronic acid grafted with acrylate groups and cysteamine.
  • composition (in particular composition B) comprising the crosslinking thiol used in the process according to the invention is an aqueous composition having a pH ranging from 5 to 10.5, preferably ranging from 6 to 9, and preferentially ranging from 7 to 8.5.
  • an extemporaneous mixture of the polysaccharide polymer grafted with (meth)acrylate groups and of a crosslinking thiol compound is prepared and the mixture is applied to the skin. It is also possible to carry out a sequential application to the skin, on the one hand, of the saccharide polymer grafted with (meth)acrylate groups and, on the other hand, of the crosslinking thiol compound.
  • the thiol compound used in the process according to the invention is used according to a thiol compound/grafted-polysaccharide (meth)acrylate group mole ratio ranging from 0.01 to 10, preferably ranging from 0.01 to 5.
  • the thiol compound may be present in composition B used according to the invention in a content ranging from 0.1 % to 100% by weight, relative to the total weight of the composition, and preferably ranging from 1 % to 10% by weight.
  • the crosslinking thiol compound in contact with the polysaccharide grafted with (meth)acrylate groups reacts with the ethylenic unsaturations of the (meth)acrylate groups grafted onto the polysaccharide so as to form thio bonds with the end carbon of the ethylenic unsaturation of the (meth)acrylate group (this reaction is known as the Michael reaction).
  • a catalyst can be used in the presence of the thiol compound. This catalyst makes it possible to obtain good reactivity of the thiol compound on the ethylenic unsaturation of the methacrylate group.
  • the catalyst can be chosen from the catalysts described in the articles Tetrahedron Letters 48 (2007), pages 141 -143, and Tetrahedron Letters 46 (2005), pages 8329-8331 , and also in the articles cited in these two articles.
  • compositions used according to the invention are generally suitable for topical application to the skin and thus generally comprise a physiologically acceptable medium, i.e. a medium that is compatible with the skin and/or skin appendages. It is preferably a cosmetically acceptable medium, i.e. a medium which has a pleasant colour, odour and feel and which does not cause any unacceptable discomfort (stinging, tautness or redness) liable to discourage the consumer from using this composition.
  • a physiologically acceptable medium i.e. a medium that is compatible with the skin and/or skin appendages. It is preferably a cosmetically acceptable medium, i.e. a medium which has a pleasant colour, odour and feel and which does not cause any unacceptable discomfort (stinging, tautness or redness) liable to discourage the consumer from using this composition.
  • compositions according to the invention may be in any galenic form conventionally used for a topical application and especially in the form of dispersions of aqueous gel or lotion type, emulsions of liquid or semi-liquid consistency of the milk type, obtained by dispersing a fatty phase in an aqueous phase (O/W) or vice versa (W/O), or suspensions or emulsions of soft, semi-solid or solid consistency of the cream or gel type, or alternatively multiple emulsions (W/O/W or 0/W/O), microemulsions, vesicular dispersions of ionic and/or non-ionic type, or wax/aqueous phase dispersions.
  • These compositions are prepared according to the usual methods.
  • compositions are in the form of an O/W emulsion or an aqueous gel.
  • compositions used according to the invention comprise water, in particular in a content which can range from 10% to 99% by weight and preferably ranging from 50% to 99% by weight, relative to the total weight of the composition.
  • the compositions used according to the invention may also contain one or more adjuvants commonly used in the cosmetics field, such as emulsifiers, preservatives, sequestering agents, fragrances, thickeners, oils, waxes or film-forming polymers.
  • an extemporaneous mixture of a composition in particular a cosmetic composition, comprising the (meth)acrylate-grafted polysaccharide polymer and of a crosslinking thiol compound, as previously described, is applied to the skin.
  • the extemporaneous mixture is advantageously prepared less than 5 minutes before it is applied to the skin, and preferably less than 3 minutes.
  • the composition, in particular cosmetic composition, comprising the (meth)acrylate-grafted polysaccharide polymer is first applied to the skin, then the crosslinking thiol compound or a cosmetic composition containing same is applied.
  • the application of the crosslinking thiol compound can be carried out after a time of between 5 minutes and one hour after having applied the grafted polysaccharide polymer.
  • the application of the cosmetic composition used according to the invention is carried out according to the usual techniques, for example by application (in particular of creams, gels, sera or lotions) to the skin intended to be treated, in particular facial and/or neck skin, especially the skin of the area around the eyes.
  • the composition may, for example, be a care composition.
  • Synthesis example 1 (polymer 1 ): Hyaluronic acid 60%-functionalized with acrylic anhydride
  • hyaluronic acid Hyacare® 50 from Evonik
  • 5 g of hyaluronic acid Hyacare® 50 from Evonik
  • 14.8 g of acrylic anhydride were added dropwise over the course of approximately 2 min.
  • the pH was adjusted to 7.7 by slowly adding (over the course of approximately one hour) sodium hydroxide at 30% in water (7 M). The mixture was left to react for 24 hours.
  • the mixture obtained was purified by dialysis (polymer in 150 ml of water, 3.3% by weight) on a Spectra/Por® 15 kDa membrane for 5 days in 5 litres of water (water changed 4 times, i.e. 20 litres in total), then the mixture of the purified fraction was lyophilized by freezing with a bath of dry ice + acetone at -80°C, then by placing the frozen mixture in a lyophilization apparatus for 4 days. 2.5 g of a white solid were obtained.
  • the hyaluronic acid obtained is 60%-functionalized with acrylate groups.
  • Synthesis example 2 (polymer 2): Dextran 33%-functionalized with methacrylate groups 10 g of dextran (sold under the reference 406261000 by the company Acros) were suspended in 40 ml of a lithium chloride/dimethylformamide mixture (at 10% by weight of LiCI) and the suspension was heated to 100°C. 20 ml of the lithium chloride/dimethylformamide mixture were added until complete dissolution of the dextran. The mixture was then cooled to 80°C, then 0.56 g of triethanolamine was added, the mixture was stirred for 15 minutes at 80°C, then 8.55 g of methacrylic anhydride were slowly added (10 minutes).
  • the dextran obtained is 33%-functionalized with acrylate groups.
  • Synthesis example 3 (polymer 3): Dextran 50%-functionalized with methacrylate groups
  • the dextran obtained is 50%-functionalized with methacrylate groups.
  • Synthesis example 4 (polymer 4): Carrageenan 15%-functionalized with acrylic anhydride
  • the mixture obtained was purified by dialysis (polymer in 150 ml of water, 3.3% by weight) on a Spectra/Por® 15 kDa membrane for 5 days in 5 litres of water (water changed 4 times, i.e. 20 litres in total), then the mixture of the purified fraction was lyophilized by freezing with a bath of dry ice + acetone at -80°C, then by placing the frozen mixture in a lyophilization apparatus for 4 days.
  • the carrageenan obtained is 10%-functionalized with acrylate groups.
  • Examples 1 to 4 Demonstration of the tensioning effect of mixtures of polymers with a thiol
  • the tensioning effect of the polymers of Example 1 was evaluated by means of an in vitro retraction test. This test consists in comparing, in vitro, the tensioning capacity of the mixture of polymer and thiol to be evaluated relative to a reference tensioning polymer: Hybridur ® 875 polymer dispersion from Air Products (aqueous dispersion at 40% by weight of particles of an interpenetrated network of polyurethane and acrylic polymers).
  • the mixture of polymer and thiol to be evaluated was deposited on a nitrile rubber strip cut from a glove sold under the reference Safeskin Nitrile Critical No. 038846 by the company Anthony Dutscher SA, having a surface area of 3.5 cm 2 , stretched taut beforehand on a support.
  • the mixture of polyol and thiol was deposited on the elastomer strip, by depositing 1 .8 mg (of solids) of polymer.
  • the tensioning effect obtained was measured according to the protocol previously described.
  • the water resistance of the tensioning effect was then evaluated by immersing the rubber strips treated with the polymer to be evaluated in water at ambient temperature (25°C) for 10 minutes.
  • the tensioning effect of the polymer of Example 3 mixed with a thiol was evaluated by means of an in vitro retraction test. This test consists in comparing, in vitro, the tensioning capacity of the mixture of polymer + thiol to be evaluated, relative to a reference tensioning polymer: Hybridur ® 875 polymer dispersion from Air Products (aqueous dispersion at 40% by weight of particles of an interpenetrated network of polyurethane and acrylic polymers).
  • the polymer to be evaluated was deposited on a nitrile rubber strip cut from a glove sold under the reference Safeskin Nitrile Critical No. 038846 by the company Miguel Dutscher SA, having a surface area of 3.5 cm 2 , stretched taut beforehand on a support.
  • An aqueous solution containing 7% AM of Hybridur ® 875 polymer was thus deposited on a nitrile rubber strip so as to thus obtain a reference tensioning strip.
  • a mixture containing the polymer and the thiol according to the amounts described in the table hereinafter is deposited on another strip.
  • the persistence of the tensioning effect (i.e. the retaining of the tensioning effect in the face of perspiration or washing) was evaluated by rinsing the nitrile strips with a 0.9 M aqueous NaCI solution (10 ml of the saline solution are projected onto the strip at a distance of 5 cm using a pipette).
  • the strip was left to dry for 3 hours and the tensioning effect (the curving (retraction) of the strip) was again observed, comparing it with the effect observed before rinsing.
  • the following solutions were prepared and immediately applied (26 ⁇ of the final solution) to the strips.
  • Example 2 The result obtained with the methacrylate-grafted dextran of Example 2 without thiol (Example 2) shows that it exhibits a good tensioning effect, but the latter is not persistent with respect to water.
  • a thiol such as dithiothreitol (Example 2a)
  • the tensioning effect of the polymer after rinsing does not show any change compared with the tensioning effect before rinsing.
  • the treatment with the thiol compound therefore makes it possible to obtain a persistent tensioning effect.
  • aqueous solution of the polymer to be evaluated was deposited on an elastomer strip according to the amount indicated in the table hereinafter. After waiting for 5 minutes, the aqueous solution containing the thiol was then applied.
  • An anti-wrinkle gel having the following composition is prepared:
  • a basecoat gel having the following composition is prepared:
  • the gel obtained is applied to wrinkled facial skin (approximately 20 mg of the composition per cm 2 of skin treated).
  • An aqueous solution (topcoat) containing 0.5% by weight of cysteamine is then applied to the treated area according to the following weight criteria: 26 ⁇ of basecoat gel and either 2.6 ⁇ or 10.6 ⁇ of topcoat solution.
  • An anti-wrinkle gel having the following composition is prepared:
  • aqueous solution containing 5% by weight of dithiothreitol, pH adjusted to 8 with aqueous ammonia.
  • Example 17 An anti-wrinkle basecoat gel having the following composition is prepared:
  • the gel obtained is applied to wrinkled facial skin (approximately 20 mg of the composition per cm 2 of skin treated).
  • An aqueous gel (topcoat) having the following composition is then applied to the treated area:
  • Hydroxyethylcellulose (Natrosol® 250 HHR CS from Ashland) 0.5 g
  • An anti-wrinkle gel having the following composition is prepared:
  • a similar composition is also prepared using the polymer of Example 4. Just before the application to the skin, 10 g of an ethanolic solution containing 10% by weight of pentaerythritol tetra(3-mercaptopropionate) are added to the gel.
  • composition obtained as a mixture with pentaerythritol tetra(3-mercaptopropionate), applied to the face, makes it possible to effectively smooth out the wrinkles.

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Abstract

L'invention concerne un procédé cosmétique pour la peau ridée, comprenant l'application topique sur la peau d'un mélange extemporané d'une composition cosmétique comprenant un polymère de polysaccharide greffé avec des groupes (méth)acrylate et un composé thiol réticulant ayant un ou plusieurs groupes thiol; ou bien comprenant l'application séquentielle sur la peau d'une composition cosmétique comprenant un polymère de polysaccharide greffé avec des groupes (méth)acrylate, suivie par l'application d'un composé thiol réticulant ayant un ou plusieurs groupes thiol, ou d'une composition cosmétique le contenant. L'invention concerne également l'utilisation du mélange dudit polymère de polysaccharide greffé et dudit thiol réticulant en tant qu'agent tenseur de la peau. L'invention concerne également une composition cosmétique obtenue par mélange d'une composition cosmétique comprenant ledit polymère de polysaccharide greffé et ledit thiol réticulant. L'invention concerne un kit comprenant une première composition cosmétique comprenant ledit polymère de polysaccharide greffé, et une seconde composition comprenant ledit thiol réticulant, les première et seconde compositions étant chacune conditionnées dans un ensemble conditionnement distinct.
PCT/EP2015/072465 2014-09-30 2015-09-29 Procédé cosmétique pour atténuer les rides WO2016050788A1 (fr)

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FR1459263A FR3026299B1 (fr) 2014-09-30 2014-09-30 Procede cosmetique pour attenuer les rides

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Cited By (3)

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CN111249472A (zh) * 2020-01-16 2020-06-09 上海交通大学医学院附属第九人民医院 一种可经皮给药的透明质酸纳米凝胶及其制备方法
WO2021098098A1 (fr) * 2019-11-18 2021-05-27 孛朗孚有限公司 Acide hyaluronique modifié par du sulfhydryle, procédé de préparation associé et utilisation correspondante
WO2021098097A1 (fr) * 2019-11-18 2021-05-27 孛朗孚有限公司 Composé polymère modifié par un thiol, procédé de préparation associé et application associée

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FR3131316A1 (fr) * 2021-12-24 2023-06-30 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procédé de fonctionnalisation du dextran par des (méth)acrylates et utilisation du dextran ainsi fonctionnalisé pour préparer un hydrogel

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021098098A1 (fr) * 2019-11-18 2021-05-27 孛朗孚有限公司 Acide hyaluronique modifié par du sulfhydryle, procédé de préparation associé et utilisation correspondante
WO2021098097A1 (fr) * 2019-11-18 2021-05-27 孛朗孚有限公司 Composé polymère modifié par un thiol, procédé de préparation associé et application associée
JP2023502470A (ja) * 2019-11-18 2023-01-24 孛朗孚(杭州)生物科技有限公司 スルフヒドリル変性ヒアルロン酸及びその調製方法並びに用途
JP2023503894A (ja) * 2019-11-18 2023-02-01 孛朗孚(杭州)生物科技有限公司 スルフヒドリル変性高分子化合物及びその調製方法並びに用途
CN111249472A (zh) * 2020-01-16 2020-06-09 上海交通大学医学院附属第九人民医院 一种可经皮给药的透明质酸纳米凝胶及其制备方法
CN111249472B (zh) * 2020-01-16 2024-02-23 上海交通大学医学院附属第九人民医院 一种可经皮给药的透明质酸纳米凝胶及其制备方法

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