Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/04—Dispersions; Emulsions
  • A61K8/046—Aerosols; Foams
• • 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
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8129—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers or esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers, e.g. polyvinylmethylether
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
  • A61Q1/02—Preparations containing skin colorants, e.g. pigments
• • 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
• • 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
  • A61K2800/81—Preparation or application process involves irradiation
• • 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
  • A61K2800/95—Involves in-situ formation or cross-linking of polymers

Definitions

• the present invention relates to a cosmetic process for making up and/or caring for the skin, in particular for treating aesthetic skin defects and imperfections.
• skin imperfections may also result from skin imperfections, for instance acne scars, or from the effects of surgical intervention such as scars.
• wrinkles are manifestly the most representative thereof.
• These wrinkles may be categorized as "deep” wrinkles, which are very visible or which may have a depth of 300 microns or more, “medium” wrinkles, which are visible and have a depth ranging between 150 microns and 300 microns, and “shallow” wrinkles, which are less visible than the previous ones and have a depth of less than 150 microns.
• the object of the present invention is, precisely, to satisfy the abovementioned expectations.
• the present invention relates to a cosmetic process for making up and/or caring for a skin surface, comprising at least the steps consisting in:
• composition (M) comprising, in a physiologically acceptable medium, at least one photo-crosslinkable compound, the said compound comprising at least one activated photo-dimerizable group bearing at least one activated double bond;
• step (ii) exposing all or part of the surface of the said coat formed in step (i) to conditions favourable for crosslinking the said photo-crosslinkable compound.
• physiologically acceptable medium means a medium free of toxicity, which is compatible with application to human keratin materials, in particular the skin.
• the coating formed according to the invention may be more particularly intended for making up and/or caring for a facial skin surface.
• anrated composition means a composition comprising a gaseous phase (for example air) in the form of bubbles. It is also known as a composition "in foam form”.
• patent applications US 2004/126 345, WO 04/060 292 and WO 04/060 334 disclose the application, to the skin, the lips or keratin fibres such as the hair, of a composition which forms a foam after application, which will be stabilized via the film formation of a film-forming polymer.
• the coating formed on the surface of the skin according to the process of the invention may have, after a single application of aerated composition, a thickness of greater than or equal to 10 ⁇ , in particular ranging from 20 ⁇ to 2 mm and more particularly from. 50 ⁇ to 500 ⁇ . Needless to say, the thickness of the coating formed is adjusted with regard to the desired makeup effect.
• the coating thus formed is stable and long-lasting, in particular for at least 4 days and more particularly up to 7 days. It advantageously has good resistance to rubbing.
• the process of the invention may advantageously be performed for hiding relief imperfections and more particularly wrinkles and in particular, as developed hereinbelow, the process of the invention makes it possible to obtain efficient and flexible filling of the skin wrinkles, for example facial wrinkles.
• the process of the invention may also be used for concealing or attenuating skin defects, such as bags and/or shadows in the region around the eyes.
• step (i) of the process of the invention may be formed according to various embodiments.
• it is formed in situ on the said skin surface via the application of a composition with delayed expansion.
• the present invention is thus directed towards such a cosmetic composition with delayed expansion comprising, in a physiologically acceptable medium:
• self-foaming compound is intended to denote a compound that is capable of giving the composition containing it the form of a foam with an acceptable degree of aeration.
• the self-foaming compounds that may be used according to the inventio will be described more precisely in the text hereinbelow.
• the said aerated coat may be formed, simultaneously with its application to the surface of the skin, with the aid of an aerated-composition dispenser, using a non- aerated base composition comprising the said photo-crosslinkable compound.
• the present invention thus relates to a product for forming an aerated cosmetic composition, comprising:
• the present mvention relates to a cosmetic kit, in particular for making up and/or caring for the skin, comprising at least:
• the process of the invention comprises the formation, on the said skin surface, of an aerated coat of a composition, referred to hereinbelow as (M), comprising at least one photo-crosslinkable compound.
• the photo-crosslinkable compounds under consideration according to the invention comprise at least one activated photo-dim erizable group bearing at least one activated double bond.
• the said photo-crosslinkable compound(s) may be present in the composition (M) in a proportion of from 1% to 50% by weight and in particular from 3% to 20% by weight relative to the total weight of the said composition.
• the mean number of activated double bonds per molecule of compound is preferably greater than 1, in particular greater than 2 and better still greater than 3.
• photo-dimerizable group means a chemical group that leads to photo-dimerization reactions under irradiation.
• photo-dimerization means a chemical reaction between two double bonds (of 2+2 type) or two pairs of double bonds (of 4+4 type), and more particularly between two double bonds (of 2+2 type).
• the double bond under consideration accordin to the invention when it is photo-stimulated or, in other words, subjected to a specific radiation, generally UV, proves to be capable of reacting with another double bond by cyclization.
• the double bond under consideration is said to be activated.
• This characterization means that the double bond is spontaneously photo- dimerizable in response to a photo-stimulus, without requiring the mandatory presence of a photoinitiator or of a chemical initiator.
• composition according to the invention is advantageously free of photoinitiator and/or of chemical initiator.
• the activation of the double bond intended to become dimerized is commonly induced by the presence close thereto, generally in the alpha position, of an electron- withdrawing group, for instance an aromatic nucleus such as a phenyl.
• the materials bearing photo-dimerizable groups according to the invention have the advantage of being stable towards oxygen, moisture and heat, and of leading to reversible crosslinking.
• the photo-dimerizable groups according to the invention are highly photosensitive. Consequently, irradiation even of low energy leads to rapid and efficient crosslinking of the material, which, in the case of a cosmetic application, induces irradiation of short duration and of low energy, which does not cause any degradation of the keratin materials .
• the activated photo-dimerizable groups that may be used according to the invention are chosen from:
• R represents a hydrogen atom or a C 1 -C4 alkyl or C1-C4 hydroxyalkyl group, preferably R represents a hydrogen atom, a methyl group, an ethyl group or a hydroxyefhyl group, and preferentially R is a methyl group;
• R' represents a hydrogen atom or a C1-C4 alkyl group and preferably R represents a hydrogen atom
• X " denotes an ion chosen from chloride, bromide, iodide, perchlorate, tetrafiuoroborate, methyl sulfate, phosphate, sulfate, 1 methanesulfonate and p- toluenesulfonate ions, preferably X " is an ion chosen from chloride and methyl sulfate ions, and preferentially X " is a methyl sulfate ion.
• R denotes an alkylene radical (divalent) containing from 2 to 8 carbon atoms, and preferably R" denotes an alkyl ene radical (divalent) containing from 2 to 4 carbon atoms;
• Rj denotes a hydrogen atom or a C 1 -C4 alkyl or C1-C4 hydroxyalkyl group
• - A denotes a sulfur atom, an oxygen atom or a group NR' or C(R')2, R'; with R' representing a hydrogen atom or a C r C 4 alkyl group, R' preferably representing a hydrogen atom; and
• Such chemical groups bear activated double bonds, and as such the photo- dimerization of these double bonds is triggered spontaneously in the UVA range, without requiring a photoinitiator.
• the photo-dimerizable groups that may be used according to the invention bear a stylbazolium function of formula (la):
• - R represents a hydrogen atom or a C r C 4 alkyl or Cs-Cj hydroxyalkyl group
• R' represents a hydrogen atom or a Ci-C 4 alkyl group
• - X denotes an ion chosen from chloride, bromide, iodide, perchlorate, tetrafluoroborate, methyl sulfate, phosphate, sulfate, methanesulfonate and p- toluenesulfonate ions.
• the photo-crosslinkable compound is derived from the functionalization of a natural backbone, which is preferably polymeric, with at least one photo-dimerizable group.
• the compound comprising at least one photo-dimerizable group is a hydrocarbon-based polymer chosen from polyvinyl alcohol, partially or totally hydrolysed polyvinyl acetate and polysaccharides chosen from chondroitin sulfate, keratan, keratan sulfate, heparin, heparin sulfate, xanthan, carrageenan, chitosan, cellulose and derivatives thereof, alginate, starch, dextran, pullulan and galactomannan, and biologically acceptable salts thereof.
• the photo- crosslinkable compound according to the invention may bear one or more functions that can. be cyclized in a 2/2 reaction., which are sensitive to light irradiation, in particular in the absence of photoinitiator and/or of chemical initiator.
• a photo-crosslinkable compound comprises at least one photo- dimerizable unit bearing a photo-dimerizable activated double bond, borne by a polymer of partially or totally hydrolysed polyvinyl acetate type, a polysaccharide or a polyvinyl alcohol.
• the compounds containing photo-dimerizable groups bearing a stylbazolium function are obtained by reacting the polymer under consideration with a chemical species comprising a group of formula (la) or (lb).
• the chemical species comprising a group (la) bears a reactive group W of aldehyde or acetal ty e.
• this chemical species corresponds to the general formula W-A, with A denoting the group (la).
• the quaternary pyridinium salts may be chloride, bromide, iodide, perchlorate, tetrafluoroborate, methosulfate, phosphate, sulfate, methanesulfonate or p-toluenesulfonate salts.
• Such chemical species are described in GB-A-2 030 575.
• species that may be ' mentioned include 4-(4- formylphenylethenyl)-l-methylpyridinium methosulfate, l-(3 ⁇ ethoxycarbonylmethyl)-4- [2-(4-formylphenyl)ethenyl]pyridinium bromide and l-(methoxycarbonylpropyl)-4-[2-(4- formylphenyl)ethenyl]pyridimurn bromide.
• 4-(4- formylphenylethenyl)-l-methylpyridinium methosulfate l-(3 ⁇ ethoxycarbonylmethyl)-4- [2-(4-formylphenyl)ethenyl]pyridinium bromide and l-(methoxycarbonylpropyl)-4-[2-(4- formylphenyl)ethenyl]pyridimurn bromide.
• Such species are described in US 2007/0 1 12 094.
• the chemical species of formula W-A react with a polymer of polyvinyl alcohol or polyvinyl acetal type as described in the documents mentioned previously.
• Polyvinyl alcohol polymers grafted with a styrylpyridinium group are especially described in the publication ichimura K et al., Preparation and characteristics of photo-crosslinkable poly( vinyl alcohol), Journal of Polymer Science, polymer chemistry edition, Vol 20, 1419-1432 (1982).
• the polymers may be obtained by reaction of polyvinyl alcohol or partially hydrolysed polyvinyl acetate with styrylpyridinium salts bearing a formyl or acetal group as described in GB-A-2 030 575, WO 96/29312, US 5 061 603, GB-A-2 076 826 and EP- A-092 901.
• the chemical species bearing a group (la) bears a reactive group which is a chlorine atom.
• the chemical species corresponds to a general formula Cl-A', with A' denoting the group (la).
• the photo-crosslinkable compound comprising the groups (lb) is advantageously obtained by reaction of the species Cl-A 1 with the polysaccharide chosen from those defined previously, in the presence of water.
• the compounds containing photo-dimerizable groups bearing a styrylazolium function are obtained by reaction of the polymer with a chemical species comprising a group of formula (II).
• the chemical species comprising a group (II) bears a reactive group
• the chemical species corresponds to a general formula W-B, with B denoting the group (II).
• these chemical species of formula W-B react with a polymer of polyvinyl alcohol or polyvinyl acetal type as described in the documents mentioned previously.
• a polyvinyl alcohol-grafted polymer comprising units having the following structure is thus obtained:
• Polyvinyl alcohol polymers grafted with a styrylazolium group are especially described in EP-A-313 220.
• these polymers may be obtained by reaction of polyvinyl alcohol or partially hydrolysed polyvinyl acetate with styrylazolium salts bearing an aldehyde or acetal group.
• the polymer bearing photo-dimerizable group(s) is in the form of particles, in particular dispersed particles.
• the polymer particles are very preferentially polyvinyl alcohol particles.
• the photo-crosslinkable compound is a polyvinyl alcohol (PVA) partly functionalized with one or more hydroxyl functions and one or more functions of formula (III):
• PVA polyvinyl alcohol
• the degree of polymerization of the polyvinyl alcohol may be between 100 and 120.
• the polymer has a degree of substitution, as a percentage of functions of formula (la), (lb) or (II) as defined above, which may be between 0.1 and 25.
• the following scheme represents a variant in which the polymer is PVA-SbQ (polymer of polyvinyl alcohol PVA type bearing a few hydrolysed functions and a few functions grafted with stylbazolium species), which is capable of crossiinking under the effect of light, as illustrated below:
• PVA-SbQ poly( vinyl alcohol) with N-methylstyrylpyridinium side groups in the form of the methyl sulfate salt
• MQ2012 poly( vinyl alcohol) with N-methylstyrylpyridinium side groups in the form of the methyl sulfate salt
• Murakami especially in the form of a dispersion at 13.3% by weight in water, for example of CAS No: 107845-59-0.
• the photo-crosslinkable compound is featured by a polysaccharide that is functionalized with photo-dim erizable groups.
• It may especially be a polysaccharide that may be chosen especially from chondroitin sulfate, keratan, keratan sulfate, heparin, heparin sulfate, xanthan, carrageenan, chitosan, cellulose and derivatives thereof, alginate, starch, dextran, puliulan and galactomannan, and biologically acceptable salts thereof.
• the degree of functionalization is obviously adjusted so as to be able to impart the required degree of crosslinking during step (ii) of the process of the invention.
• the degree of functionalization with photo- dimerizable units is at least 0.1%, or even at least 0.5%, or even at least 2%.
• the photo- dimerizable groups are preferably borne by a polymer of polyvinyl acetate type, a polyvinyl alcohol or a polysaccharide.
• the photo-dimerizable groups are borne by a polyvinyl alcohol.
• the photo-crosslinkable compound may be conveyed in a physiologically acceptable medium and in particular an aqueous medium or even pure water.
• the photo-crosslinkable compound may have a number-average molecular weight ranging from 2000 to 100 000 and preferably ranging from 2000 to 20 000.
• the photo-crosslinkable compound may be chosen from polyurethane and/or polyurea polymers or oligomers bearing (meth)acrylate groups, in particular polyurethane (meth)acrylate oligomers.
• Such polyurethanes/polyureas bearing acrylate groups are sold, for example, under the name Ebecryl® by the company Cytec (Ebecryl ⁇ 210: molar mass 1500, 2 acrylate functions per molecule, Ebecryl® 230: molar mass 5000, 2 acrylate functions per molecule, Ebecryl® 270: molar mass 1500, 2 acrylate functions per molecule, Ebecryl® 8402: molar mass 1000, 2 acrylate functions per molecule, Ebecryl® 8804: molar mass 1300, 2 acrylate functions per molecule, Ebecryl® 220: molar mass 1000, 6 acrylate functions per molecule, Ebecryl® 1290: molar mass 1000).
• These compounds are capable of crosslinkmg when they are subjected to radiation comprising at least UV light.
• diurethane methacrylate (INCI: Di- HEMA trimethylhexyl dicarbamate).
• composition may contain a single photo-crosslinkable polymer bearing functions of identical or different nature.
• the reactions may be performed between two photo-dimerizable groups of identical or different chemical nature.
• the activated double bonds may react with another double bond of the same chemical nature or react with another double bond of different chemical nature.
• the photo-crosslinkable compound under consideration according to the invention is chosen from polymers that are capable of photo- crosslinkmg via a 2+2 cycloaddition reaction, in particular polymers bearing stylbazolium functions. Characteristics of the aerated coat
• the said aerated coat formed in step (i) has a degree of aeration of greater than or equal to 10% and preferably less than 1000%.
• the degree of aeration may range, for example, from 10% to 500% and preferably from 20% to 200%.
• the degree of aeration corresponds to the amount of gas incorporated into the composition.
• the degree of aeration is measured according to the following protocol: prior to the measurement, a quantity Q of composition to be characterized is placed in a transparent container bearing graduations indicating the volume, before aeration, and the volume Vb e f ore aeration (in cm ) is measured (in practice, the quantity is such that Vb e f OT e aeration is of the order of 10 cm J ) at a room temperature of 23 °C and at atmospheric pressure. In practice also, provision is made, in order to measure the volume, to tap the quantity Q in the bottom of the container, gently enough so as not to cause appreciable expansion of the product. The quantity Q of composition is then left alone for about 10 minutes in order for it to aerate by itself, naturally. The new volume V foam of the composition in foam form is then measured. If need be, the top of the foam is levelled off somewhat in order to give it a flat surface, in this way, it is easier to evaluate the volume.
• the aeration may result from expansion of the composition with delayed expansion or may be created via an aerated-composition distributor.
• degree of aeration [(V foaro - V bd re aeration)/ V before aeration] x 100
• the composition in foam form is created in situ on the said skin surface, after application of a composition with delayed expansion (E).
• a composition with delayed expansion is a system comprising a "self- foaming" agent which is capable of enabling expansion of the said composition to give it the form of a foam, generally by release or formation of a volatile agent in the composition after it has been applied to the said skin surface.
• the said aerated coat is formed via at least the steps consisting in:
• step (b) exposing all or part of the said coat from step (a) to conditions that are favourable for expanding the said composition.
• the second crosslinking step is delayed until the transformation of the coat with delayed expansion into an aerated coat.
• self-foaming agent means a compound that is capable of imparting to a composition the form of a foam with an acceptable degree of aeration.
• This variant is particularly advantageous in so far as it does not require, unlike compositions conditioned in foam form, the spreading of a foam in order to form the aerated coat, which may often prove to be difficult to form a uniform coating.
• the present invention relates to a cosmetic composition with delayed expansion comprising, in a physiologically acceptable medium:
• composition with delayed expansion used according to the invention before aeration, may be more or less fluid and may have the appearance of a coloured or colourless cream, an ointment, a milk, a lotion, a serum, a paste or a powder. It may also be in solid form, in particular in stick or dish form.
• composition with delayed expansion may be in anhydrous form or in the form of an emulsion or a gel.
• composition with delayed expansion may be applied to the skin via any applicator usually used for the application of a cosmetic composition.
• composition with delayed expansion may be dispensed, for example, on the skin in the form of a cream, in particular formed from an emulsion.
• the said composition may be conditioned in a standard aerosol device, with a separation such as a piston or a flexible bag to separate the self-foaming compound from the propellant required for expelling the composition. It may also be a flexible tube, a pump bottle or a bottle with a deformable wall.
• Examples 1 and 2 describe an example of a dispenser for compositions with delayed expansion in accordance with the invention.
• the dispenser may be equipped, for example, with a dispensing control device specially adapted for the dispensing of a self-foaming product, as described, for example, in patent application EP 0 547 925.
• the said self-foaming compound(s) may be chosen from the agents known to those skilled in the art, provided that they are capable of giving the composition the form of a foam with an acceptable degree of aeration, and of doing so under conditions that are compatible with application to the skin.
• These self- foaming compounds may be chosen, for example, from: - slow-expanding systems
• the self-foaming agent may be chosen, for example, from volatile hydrocarbons and volatile halogenated hydrocarbons with a boiling point low enough to enable them to evaporate and to foam the composition after application to the skin, and a boiling point that is high enough to prevent premature foaming.
• the boiling point of the self- foaming agent preferably ranges from -20 to 40°C.
• the self-foaming agent is preferably chosen from linear or branched C-4-C 6 aliphatic hydrocarbons.
• n-pentane isopentane, . neopentane, n-butane, isobutane and isohexane, and mixtures thereof; and more preferentially isopentane.
• These may be systems that release C0 2 by acidification of a carbonate, as described, for example, in patent application EP 1 133 983; or aqueous hydrogen peroxide solution that has been made unstable by basification or addition of a compound that promotes the dismutation of water.
• thermoplastic particles which are capable of deforming under the action of heat and of conserving their new shape, including after cooling, especially to room temperature.
• the said self-foaming compound is chosen from slow-expanding systems, in particular as described previously.
• it is isopentane, or alternatively an isopentane/isobutane mixture especially in a weight ratio ranging from 1/1 to 3/1 .
• the said composition advantageously has a degree of expansion ranging from 10% to 5000%.
• degree of expansion means the ratio between the volume occupied by the composition measured 15 minutes after its application, divided by the volume occupied by the composition measured immediately after its application.
• a person skilled in the art is capable of using the said self-foaming agent(s) in an adequate amount for obtaining the desired degree of expansion.
• the said self-foaming agent(s) may be present in the composition with delayed expansion in a content ranging from 0.1 % to 40% by weight relative to the total weight of the said composition.
• a person skilled in the art. is capable of using the conditions of exposure of the said coat formed in step (a) to obtain the desired expansion of the said composition.
• the aerated composition may be obtained, for example, after exposure to atmospheric pressure and/or to a shear and/or to a temperature above room temperature.
• step (b) may consist simply in leaving the said coat formed in step (a) to expand in the ambient atmosphere, especially for a time ranging from 10 seconds to 5 minutes.
• the process of the invention also comprises the application, prior to, simultaneously with or subsequent to the application in step (a) of the said composition with delayed expansion (E) and prior to step (b), of at least one conventional cosmetic composition, for example a conventional foundation.
• the said compositions are mixed on the said skin surface itself, so as to create partial or total homogenization.
• Such a variant makes it possible to obtain a volume effect via the expansion of the composition, while at the same time maintaining good smoothing.
• step (a) of applying the composition with delayed expansion to the wrinkles may be followed by a levelling step prior to the expansion step (b), for example using a spatula or a pad of cotton wool.
• a mould may be applied, simultaneously with the expansion (b) of the said composition, the mould being such that it makes it possible to define a specific volume above the said skin surface.
• the mould may be made, for example, of plastic, for instance of polyethylene, polystyrene or of fluorinated material, for example of polytetrafluoroethylene (PTFE).
• plastic for instance of polyethylene, polystyrene or of fluorinated material, for example of polytetrafluoroethylene (PTFE).
• PTFE polytetrafluoroethylene
• the application of a mould advantageously makes it possible to control the expansion of the composition, in particular the volume and shape of the aerated coat that will be fonned on the skin surface, and thus makes it possible to obtain a very smooth coating with very good homogeneity.
• the foam appearance is generated at the time of dispensing the composition onto the skin.
• the said aerated coat of step (i) of the process of the invention may be formed, simultaneously with its application to the said skin surface, from a non-aerated base composition comprising the said photo-crossl kable compound, and using an aerated-composition dispenser that is capable of dispensing the base composition in the form of an aerated composition.
• the invention relates to a product for forming an aerated cosmetic composition, comprising:
• a non-aerated base composition comprising, in a physiologically acceptable medium, at least one photo-crosslinkable compound as defined previously;
• an aerated-composition dispenser for dispensing the said base composition in the form of an aerated composition.
• the aerated composition may be formed from the base composition and air or an inert gas.
• the base composition which serves to obtain the aerated composition has a similar composition to the aerated composition except for its higher density in so far as it is free of air or inert gas.
• Such a dispenser comprises at least:
• a dispensing head for dispensing the aerated composition.
• This dispenser may be an aerosol, comprising, besides the base composition, a propellant gas.
• the propellant gas that may be used may be chosen from carbon dioxide, nitrogen, nitrous oxide, volatile hydrocarbons such as butane, isobutane, propane, ethane, pentane, isododecane or isohexadecane, and mixtures thereof.
• the dispenser may contain no propellant gas.
• the base composition may be in an aerated-composition dispenser comprising a dispensing head for dispensing the aerated composition, a pump and a dip tube for transferring the composition from the container into the head to dispense the aerated composition.
• the aerated composition is formed by forcing the base composition to pass through a material comprising a porous substance such as a sintered material, a plastic or metal filtering grille, or similar structures.
• composition under consideration according to the invention should be cosmetically or dermatologically acceptable, i.e. it should contain a non-toxic physiologically acceptable medium that can be applied to human skin.
• cosmetically acceptable means a composition of pleasant appearance, odour and feel.
• the composition used according to the invention may be in any galenical form normally used in the cosmetics field, and may especially be in the form of an oily solution, which is preferably thick or thickened, an emulsion obtained by dispersing a fatty phase in an aqueous phase (O/W) or conversely (W/O), a triple emulsion (W/O/W or 0/W/O), an aqueous gel, which is preferably thick, a vesicular dispersion of ionic type (liposomes or oieosomes) and/or of nonionic type (niosomes) and/or a dispersion of nanocapsules or nanospheres, which is preferably thick.
• an oily solution which is preferably thick or thickened
• W/O triple emulsion
• aqueous gel which is
• the proportion of the fatty phase in the composition under consideration may range, for example, from 5% to 80% by weight and especially from 5% to 50% by weight relative to the total weight of the composition.
• composition may comprise at least one aqueous phase.
• the aqueous phase may consist essentially of water. However, it may also comprise a mixture of water and of water-miscible organic solvent (mi stability in water of greater than 50% by weight at 25°C), such as lower monoalcohols containing from 1 to 5 carbon atoms such as ethanol and isopropanol, glycols containing from 2 to 8 carbon atoms such as propylene glycol, ethylene glycol, 1 ,3-butylene glycol and dipropylene glycol, C 3 - C 4 ketones and C2-C4 aldehydes.
• water-miscible organic solvent such as lower monoalcohols containing from 1 to 5 carbon atoms such as ethanol and isopropanol, glycols containing from 2 to 8 carbon atoms such as propylene glycol, ethylene glycol, 1 ,3-butylene glycol and dipropylene glycol, C 3 - C 4 ketones and C2-C4 aldehydes.
• This aqueous phase (water and optionally the water-miscible organic solvent) may be present in the composition in a content ranging from 1% to 95% by weight, especially ranging from 3% to 80% by weight and in particular ranging from 5% to 60% by weight relative to the total weight of the composition,
• composition may also comprise a fatty phase.
• the fatty phase of the composition may comprise at least one oil chosen especially from:
• hydrocarbon-based oils of animal origin such as perhydrosqual ene
• oils of plant origin such as liquid triglycerides of fatty acids containing from 4 to 10 carbon atoms, and the liquid fraction of shea butter;
• esters and ethers especially of fatty acids, for instance the oils of formulae R' COOR 2 and R OR 2 in which R 1 represents a fatty acid residue containing from 8 to 29 carbon atoms and R 2 represents a branched or unbranched hydrocarbon-based chain containing from 3 to 30 carbon atoms, for instance purcellin oil, isononyl isononanoate, isopropyl myristate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2 -octyldodecyl erucate or isostearyl isostearate; hydroxylated esters, for instance isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, and fatty alcohol heptanoates, octanoates and decan
• hydrocarbons of mineral or synthetic origin such as volatile or non-volatile liquid paraffins and derivatives thereof, petroleum jelly, polydecenes, and hydrogenated polyisobutene such as sesam oil;
• - fatty alcohols containing from 8 to 26 carbon atoms for instance cetyl alcohol, stearyl alcohol and the mixture thereof (cetyl stearyl alcohol), octyl dodecanol, 2- butyloctanol, 2-h.exyldecanol, 2-undecylpentadecanol, oleyl alcohol or linoleyl alcohol;
• silicone oils for instance volatile or non-volatile polymethylsiloxanes (PDMS) containing a linear or cyclic silicone chain, which are liquid or pasty at room temperature, especially cyclopolydimethylsiloxanes (cyclomethicones) such as cyclohexasiloxane; polydimethylsiloxanes comprisin alkyl, alkoxy or phenyl groups, which are pendent or at the end of a silicone chain, these groups containing from 2 to 24 carbon atoms; phenyl silicones, for instance phenyl trimethi cones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyl- trisiloxanes, 2-pheny ethyltrimethyl siloxysilicates and polymethylphenylsiloxanes; and
• PDMS volatile or non-volatile polymethylsilox
• composition may also comprise at least one wax, at least one gum and/or at least one pasty fatty substance, of silicone or non-silicone plant, animal, mineral or synthetic origin.
• the waxes may be hydrocarbon-based, silicone and/or fluoro waxes, optionally comprising ester or hydroxy! functions. They are especially of natural origin.
• the wax may represent from 0.01% to 10% by weight and especially from
• the composition may be free of waxes.
• composition may also comprise at least one film-forming polymer.
• film-forming polymer means a polymer that is capable of fomiing, by itself or in the presence of an auxiliary film-forming agent, a continuous film that adheres to the skin.
• a film-forming polymer capable of forming a hydrophobic film i.e. a polymer whose film has a solubility in water at 25°C of less than 1% by weight, is advantageously used.
• the film-forming polymer may especially be at least one polymer chosen from the group comprising:
• composition of foundation type should comprise an aqueous phase
• non-aqueous dispersions of polymer particles preferably dispersions of polymeric particles, where appropriate surface-stabilized with at least one stabilizer, in one or more silicone and/or hydro carbon -based oils; these non-aqueous dispersions are also known as "NADs", and
• Aqueous dispersions of film-forming polymer that may be used according to the invention include the acrylic dispersions sold under the names Neocryl XK-90 ® , Neocryl A-1070 ® , Neocryl A-1090 ® , Neocryl BT-62 ® , Neocryl A-1079 ® , Neocryl A-523 ® by the company Avecia-Neoresins. Dow Latex.
• Neorez R-981 ® by the company Dow Chemical
• Neorez R-974 ® by the company Avecia-Neoresins
• Avalure UR-405 ® Avalure UR-410 ®
• Avalure UR-425 ® Avalure UR-450 ®
• Sancure 875 ® Sancure 861 ®
• Sancure 878 ® Sancure 2060 ® by the company Goodrich
• Impranil 85 ® by the company Bayer and Aquamere H-l 51 1 ® by the company Hydromer.
• Aqueous dispersions of film-forming polymer that may also be mentioned include the polymer dispersions resulting from the free-radical polymerization of one or more free-radical monomers inside and/or partially at the surface of pre-existing particles of at least one polymer chosen from the group consisting of polyurethanes, polyureas, polyesters, polyesteramides and/or alkyd polymers. These polymers are generally referred to as hybrid polymers.
• water-soluble film-forming polymers that may be used according to the invention, mention may be made of proteins, for instance proteins of plant origin, anionic, cationic, amphoteric or nonionic chitin or chitosan polymers, cellulose polymers, acrylic polymers or copolymers, vinyl polymers and polymers of natural origin, which are optional! ⁇ modified, and mixtures thereof.
• Dispersions of film-forming polymer in the liquid fatty phase, in the presence of stabilizers are described especially in documents EP-A-749 746, EP-A-923 928 and EP-A-930 060, the content of which is incorporated into the present patent application by way of reference.
• liposoluble polymers which may be mentioned are copolymers of vinyl ester (the vinyl group being directly linked to the oxygen atom of the ester group and the vinyl ester containing a saturated, linear or branched hydrocarbon-based radical of 1 to 19 carbon atoms, linked to the carbonyl of the ester group) and of at least one other monomer which may be a vinyl ester (other than the vinyl ester already present), an ⁇ -olefin (containing from 8 to 28 carbon atoms), an alkyl vinyl ether (in which the alkyl group comprises from 2 to 18 carbon atoms) or an allylic or methallylic ester (containing a saturated, linear or branched hydrocarbon-based radical of 1 to 19 carbon atoms, linked to the carbonyl of the ester group).
• vinyl ester the vinyl group being directly linked to the oxygen atom of the ester group and the vinyl ester containing a saturated, linear or branched hydrocarbon-based radical of 1 to 19 carbon atoms, linked to the carbonyl of
• the film-forming polymer may be present in the composition in a solids content ranging from 0.01% to 20% by weight and especially from 0.5% to 10% by weight relative to the total weight of the composition.
• composition may also contain adjuvants that are common in cosmetics, such as emulsifiers, hydrophilic or lipophilic gelling agents, dyestuffs, hydrophilic or lipophilic active agents, preserving agents, antioxidants, solvents, fragrances, fillers, sebum-absorbing compounds, physical sunblocks and chemical sunscreens, odour absorbers and pH regulators.
• adjuvants that are common in cosmetics, such as emulsifiers, hydrophilic or lipophilic gelling agents, dyestuffs, hydrophilic or lipophilic active agents, preserving agents, antioxidants, solvents, fragrances, fillers, sebum-absorbing compounds, physical sunblocks and chemical sunscreens, odour absorbers and pH regulators.
• these various adjuvants are those conventionally used in the field under consideration, for example from 0.01% to 20% of the total weight of the composition. Depending on their nature, these adjuvants may be introduced into the fatty phase or into the aqueous phase.
• these adjuvants, and the proportions thereof, will be chosen so as not to harm the desired properties according to the invention.
• composition may also comprise at least one surfactant.
• surfactants may be chosen from anionic and nonionic surfactants.
• fatty acids fatty alcohols, polyethoxylated or poiyglycerolated fatty alcohols such as polyethoxylated stearyl or cetyistearyl alcohols, fatty acid esters of sucrose, alkylglucose esters, in particular polyoxyethylenated Cj-C 6 alkyl glucose fatty esters, and mixtures thereof,
• anionic surfactants C16-C30 fatty acids neutralized with amines, aqueous ammonia or alkaline salts, and mixtures thereof.
• O/W emulsifiers such as fatty acid esters of polyethylene glycol, especially PEG-100 stearate, and fatty acid esters of glycerol, such as glyceryl stearate, and also W/O emulsifiers available, for example, under the trade names Abil WE09, Abil EM 90 and Abil EM97 from the company Degussa Goldschmidt, or the mixture of acetyl ethylene glycol stearate and of glyceryl tristearate sold by the company Guardian under the trade name Unitwix.
• O/W emulsifiers such as fatty acid esters of polyethylene glycol, especially PEG-100 stearate, and fatty acid esters of glycerol, such as glyceryl stearate
• W/O emulsifiers available, for example, under the trade names Abil WE09, Abil EM 90 and Abil EM97 from the company Degussa Goldschmidt, or
• hydrophilic gelling agents that may be used, mention may be made in particular of carboxy vinyl polymers (carbomer), acrylic copolymers such as acrylate/alkylacrylate copolymers, polyacrylamides, polysaccharides, natural gums and clays, and lipophilic gelling agents that may be mentioned include modified clays, for instance bentones, metal salts of fatty acids, hydrophobic silica and polyefhylenes.
• dyestuffs that may be used in particular in the composition, mention may be made of lipophilic dyes, hydrophilic dyes, pigments and nacres usually used in cosmetic or dermatological compositions, and mixtures thereof.
• the liposoluble dyes are, for example, Sudan Red, DC Red 17, DC Green 6, ⁇ -carotene, soybean oil, Sudan Brown, DC Yellow 11, DC Violet 2, DC Orange 5 and quinoline yellow.
• the pigments may be white or coloured, mineral and/or organic, and coated or uncoated.
• mineral pigments that may be mentioned are titanium dioxide, optionally surface-treated, zirconium, oxide or cerium oxide, and also iron oxide or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and feme blue.
• organic pigments that may be mentioned are carbon black, pigments of D&C type and lakes based on cochineal carmine or on barium, strontium, calcium or aluminium.
• the nacreous pigments may be chosen from white nacreous pigments such as mica coated with titanium or with bismuth oxychloride, coloured nacreous pigments such as titanium mica with iron oxides, titanium mica with, in particular, ferric blue or chromium oxide, titanium mica with an organic pigment of the abovementioned type, and nacreous pigments based on bismuth oxychloride.
• the pigments may have undergone a surface treatment.
• fillers that may be used in the composition, mention may be made, besides the fillers described above in relation to the soft-focus composition, of pigments, starch crosslinked with octenylsuccinic anhydride sold by the company National Starch under the name Dry Flo Plus (28-1 160); polyamide particles and especially those sold under the name Orgasol by the company Atochem; microspheres based on acrylic copolymers, such as those made of ethylene glycol dimethacrylate/lauryl methacrylate copolymer sold by the company Dow Coming under the name Polytrap; expanded powders such as hollow microspheres and especially the microspheres sold under the name Expancel by the company Kemanord Plast or under the name Micropearl F 80 ED by the company Matsumoto; polymethacrylate-type powders (PMMA), silicone elastomers and silica powders of the Sunsphere type, silicone resin microbeads such as those sold under the name Tospearl by the company Toshiba Silicone; and mixtures
• fillers may be present in amounts ranging from 0.01% to 20% by weight and preferably from 1 % to 10% by weight relative to the total weight of the composition.
• Fillers that are advantageous for use in the present invention are silica, mica and titanium dioxide.
• composition used according to the invention may comprise at least one compound for absorbing water and/or an oil or a liquid fatty substance, for instance sebum.
• water-absorbing compounds also known as hydro-absorbing compounds
• superabsorbent crosslinked polyacrylates such as those sold by the company Norsolor under the name Aquakeep*, polyvinyl alcohol, carboxyvinyl polymers such as those sold by the company Goodrich under the name Carbopol ® , semi -synthetic cellulose derivatives such as carboxymethylcellulose, starches, biogums such as xanthan gum, guar gum, gum. arabic, gum tragacanth, biosaccharides, scleroglucans, casein, phytocolloids such as alginates, carrageenates, agar-agar, gelatin and cotton fibres.
• oil-uptake fillers which may be of organic or mineral nature.
• the filler may be chosen more particularly from silicas, silica silylates, polyamide powders (in particular Nylon-6), acrylic polymer powders, especially of polymethyl methacrylate, of polymethyl methacrylate/ethylene glycol dimethacrylate, of polyallyl methacrylate/ethylene glycol dimethacrylate or of ethylene glycol dimethacrylate/lauryl methacrylate copolymer; perlites; magnesium carbonate, and mixtures thereof.
• the oil-absorbing powder may be a powder coated with a hydrophobic- treating agent.
• the hydrophobic-treating agent may be chosen especially from fatty acids such as stearic acid; metal soaps such as aluminium dirayristate or the aluminium salt of hydrogenated tallow glutamate; amino acids; N-acylamino acids or salts thereof; lecithin, isopropyl triisostearyl titanate, and mineral waxes, and mixtures thereof.
• Silica powders that may be mentioned include:
• silica particles especially those sold under the name Silica Shells by the company obo (oil uptake equal to 5.50 ml/g),
• precipitated silica powders surface-treated with a mineral wax such as precipitated silica treated with a polyethylene wax, and especially those sold under the name Acematt OR 412 by the company Evonik-Degussa (oil uptake equal to 3.98 ml/g).
• Acrylic polymer powders that may be mentioned include:
• Microsponge 5640 porous polymethyl methacrylate/ ethylene glycol dimethacrylate spheres sold under the name Microsponge 5640 by the company Cardinal Health Technologies (oil uptake equal to 1.55 ml/g),
• Polyamide powders that may be mentioned include:
• a perlite powder that may especially be mentioned is the product sold under the name Optimat 1430 OR by the company World Minerals (oil uptake equal to 2.4 ml/g).
• a magnesium carbonate powder that may especially be mentioned is the product sold under the name Tipo Carbomagel by the company Buschle & Lepper (oil uptake equal to 2.14 ml/g) .
• active agents that are common in cosmetics or dermatology, which may be used in the composition, mention may in particular be made of any active agent known for its activity on the ageing of the skin, for instance keratolytic or pro -desquamating agents, for example a-hydroxy acids, ⁇ -hydroxy acids, a-keto acids and ⁇ -keto acids, retinoids and esters thereof, retinal and retinoic acid and derivatives thereof.
• keratolytic or pro -desquamating agents for example a-hydroxy acids, ⁇ -hydroxy acids, a-keto acids and ⁇ -keto acids, retinoids and esters thereof, retinal and retinoic acid and derivatives thereof.
• extracts of veinotonic plants such as extracts of ruscus and/or of common horse chestnut
• xanthine bases such as caffeine
• vitamins for instance vitamins A, B3, PP, B5, E, l and/or C and derivatives of these vitamins and especially esters thereof
• the composition may contain at least one active agent chosen from: vitamins B3 and B5; zinc salts, and in particular zinc oxide and zinc gluconate; salicylic acid and derivatives thereof such as 5-n-octanoylsalicylic acid; triclosan; capryloylglycine; an extract of clove; octopirox; hexamidine; and azeleic acid and derivatives thereof.
• active agent chosen from: vitamins B3 and B5; zinc salts, and in particular zinc oxide and zinc gluconate; salicylic acid and derivatives thereof such as 5-n-octanoylsalicylic acid; triclosan; capryloylglycine; an extract of clove; octopirox; hexamidine; and azeleic acid and derivatives thereof.
• UVA and/or UVB screening agents chosen from organic screening agents and mineral screening agents optionally coated to make them hydrophobic may also be introduced into the composition.
• the composition used according to the invention comprises one or more additional compounds chosen from preserving agents, fragrances and absorbent compounds.
• the composition under consideration according to the invention is free of photoinitiator and/or of chemical initiator.
• photoinitiator means a compound which initiates the photo-dimerization reaction and releases a radical under irradiation, especially i the UV range.
• step (ii) may be preceded by a step of smoothing the said coat of composition (M).
• This step may be performed, for example, using a mould to be applied onto the surface of the coat so as to give it a shape, or alternatively via a system for levelling or for removing the surplus foam, by scraping.
• Such a step advantageously makes it possible to improve the smooth and uniform appearance of the coating formed.
• the process of the invention comprises at least one step (ii) of exposing all or part of the surface of the said aerated coat formed in step (i) to conditions suitable for crosslinking the said photo-crosslinkable compound.
• Step (ii) may consist in illuminating the surface of the said coat with ambient light or with a source of artificial light.
• the ambient or artificial light may emit radiation in the visible and/or UV range. Preferably, it emits at least a proportion of radiation in the UV range, for example a proportion of UV of at least 2% of the total light energy of the ambient light.
• step (ii) comprises, or even consists in. illuminating the surface of the said coat with ambient light, in particular for a time of at least 1 minute.
• the time of exposure to the ambient light may more particularly range from 10 seconds to 15 minutes and especially from 5 to 10 minutes.
• step (ii) comprises, or even consists in, illuminating the surface of the said coat with a source of artificial light.
• the time of exposure to the said artificial light may range from 10 seconds to 10 minutes and in particular from 30 seconds to 5 minutes.
• the lighting system for providing artificial light may consist, for example, of lighting with a lamp, a torch, a laser or LEDs, for example in the form of an LED array.
• the artificial light source may emit radiation in the visible range and/or radiation in the UV range.
• the emitted light may or may not be monochromatic.
• the wavelength of the emitted light is preferably centred on 365 nm, in particular between 400 nm and 700 nm and better still between 365 nm and 550 nm.
• the crosslinking may be initiated by illumination without the need for a photoinitiator.
• it will be a source of artificial light emitting energy of at least 0.2 mW/cm' and in particular from 0.5 to 20 mW/cm .
• the crosslinking may take place with a reduced light intensity, and the lighting system may, for example, produce a light intensity of less than 50 mJ/cm 2 or even l O J/cm 2 .
• the light energy in the UV range is preferably less than 10 J/cm .
• the twofold characteristic of the absence of photoinitiator and of relatively weak light intensity is particularly advantageous since it makes it possible to limit the harmful effects of aggressive initiators or of prolonged exposure to intense light, in particular in UV wavelengths.
• a person skilled in the art will be capable of adapting the illumination characteristics, especially in terms of duration of exposure and of radiation wavelengths, wi th regard to the nature of the photo-crosslinkable compound used.
• the photo-crosslinking of polyurefhanes bearing (meth)acrylate groups will require light emitting at least radiation in the UV range, whereas the photo- crosslinking of polymers of PVA-SbQ type may be performed with radiation in the visible range.
• step (ii) may be performed, on all or part of the surface of the said coat, before the full expansion of the composition with delayed expansion (E).
• This embodiment variant may prove to be particularly advantageous in the case of performing the process of the invention for the treatment of wrinkles.
• the degree of expansion of the composition (E) it is possible to adjust the volume of expanded composition obtained to the volume required to fill the wrinkle, without creating a visible ridge on the surface of the skin.
• - Figure la represents a coat (2) of composition with delayed expansion (E) applied to a wrinkle (1), before expansion
• - Figure lb represents the aerated composition (2), in the case where it has reached its maximum degree of expansion
• FIG. 1 c represents the coat of aerated composition (2), in the case where the • expansion of the composition has been stopped by illumination, when the thickness of the coat is sufficient to fill the wrinkle (1).
• the process of the invention may comprise at least one step of illumination, as described previously, of one or more localized zones of the surface of the said coat of composition with delayed expansion (E), before the complete expansion of the said composition (E), or even immediately after its application (a) and prior to its expansion (b).
• the said zones may be defined, for example, by means of a cache that is capable of permitting the illumination of only the said zone(s).
• the process may comprise at least two illumination steps performed for different localized zones of the surface of the said coat of composition with delayed expansion (E), and when the said composition has reached different degrees of aeration.
• the process of the invention may also comprise one or more subsequent steps of superposition, onto the coating formed after step (ii), of one or more additional coats of conventional cosmetic compositions, such as standard foundation compositions.
• the said additional composition(s) are applied to the surface of the coating obtained after the process of the invention, by spraying, for example with a device of aerosol type.
• a lacquer for instance comprising a mixture of acrylic resin, ethanol and dimethyl ether, may be applied to the surface of the coatmg.
• the formulation below is prepared in the absence of light, comprising the gradients given in Table 1 below.
• a rigid pressurizable bottle made of tin, of about 200 ml, from the company Impress Vendel is used (commercial reference 190-Impress Vendel).
• a valve from the company Coster (commercial reference C 30605) is attached to a bag. This bag is crimped onto the drum. The bag is then filled with 60 g of formulation.
• the push button is pressed.
• the product exits via the push button it is spread gently on the skin, at a rate of 0.5 g for the area of a cheek.
• the coating is exposed to the ambient light.
• a thick coating about 0.12 mm thick is then obtained.
• the coating is not regular at the surface, thus imitating the natural irregularities of the skin.
• the operation may optionally be terminated by spreading another foundation or a powder applied with a puff.
• a rigid pressurizable bottle made of tin, of about 200 ml, from the company Impress Vendel is used (commercial reference 190-Impress Vendel).
• a valve from the company Coster (commercial reference C 30605) is attached to a bag. This bag is crimped onto the drum. The bag is then filled with 60 g of formulation.
• the push button is pressed.
• the product exits via the push button it is spread gently on the skin, at a rate of 0.5 g for the area of a cheek.
• the coating is exposed to the ambient light.
• a thick coating about 0.08 mm thick is then obtained.
• the operation may optionally be terminated by spreading another foundation or a powder applied with a puff.

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