Cosmetic composition containing photoluminescent particles The present invention relates to a cosmetic composition for caring for and/or making up the skin, especially of the body, the hands, the neck and the face, the lips and/or keratin fibers. More particularly, the compositions under consideration according to the invention may constitute a makeup product for the skin, and especially of the face, with covering and/or lightening properties.
People with colored or even dark skin may wish to lighten their skin. Moreover, people with dyschromia, for example pigmentation marks, shadows under the eyes or red blotches, may wish to efface these skin defects.
To this end, they may especially use cosmetic or dermatological compositions containing one or more lightening agents or bleaching agents. However, to obtain an appreciable lightening effect, these compositions firstly must contain large amounts of lightening agents, and secondly must be used for a long time. Specifically, in the majority of cases, a lightening effect is not observed immediately after applying compositions comprising said lightening agents.
To obtain visible lightening of the skin, it is also known practice to use compositions comprising optical brighteners.
Among the lightening cosmetic compositions comprising optical brighteners that may in particular be mentioned are those described in patent application EP 0 962 224. They use optical brighteners such as stilbene derivatives, coumarin derivatives, oxazole and benzoxazole derivatives and imidazole derivatives as optical skin-bleaching agents. Such compounds are available, for example, under the trade names Tinopal SOP® and Uvitex OB® from the company Ciba Geigy. Reference may also be made to document WO 01/43714A1 from Ciba
Specialty Chemicals, which deals with polymeric vectors, in particular of starch and of cellulose, treated with fluorescent agents.
It is also known practice to bind optical brighteners to a mineral particulate support. For example, document FR 2 810 881 from LCW describes microparticles covered with optical agents, among which are mentioned optical brighteners.
However, a certain number of optical brighteners have toxicological profiles that limit or even oppose their use in the context of cosmetic products.
Document WO 2004/050046 concerns makeup compositions comprising alloy- based composite fluorescent semiconductor nanoparticles as pigments. Document DE 10 225 819 describes cosmetic compositions comprising fluorescent mineral particles with a ceramic core and a polymeric or ceramic shell. These particles are about one micrometer in size and are thus large.
In point of fact, there is still a need for cosmetic compositions for obtaining a skin defect effacing effect and/or a skin-lightening effect, while at the same time not having the abovementioned drawbacks.
The inventors have discovered, surprisingly, that it is possible to obtain a skin defect effacing effect, and especially a skin-bleaching effect, by introducing specific mineral particles into a cosmetic composition.
Thus, according to a first of its aspects, the present invention relates to a cosmetic composition for making up and/or caring for the skin, especially of the face, the lips and/or keratin fibers, comprising, in a physiologically acceptable medium, at least photoluminescent and especially noncomposite mineral nanoparticles.
According to another of its aspects, the present invention also relates to the use of photoluminescent and especially noncomposite mineral nanoparticles as lightening agents for the skin, the lips and/or keratin fibers in a cosmetic composition.
According to another of its aspects, the present invention also relates to the use of photoluminescent and especially noncomposite mineral nanoparticles as agents for effacing skin and/or lip defects in a cosmetic composition.
According to another of its aspects, the invention also relates to the use of photoluminescent and especially noncomposite mineral nanoparticles as sunscreens, and especially as UV-screening agents, in a cosmetic composition. According to another of its aspects, the present invention also relates to a nontherapeutic makeup and/or care process, especially for the skin, the lips and/or keratin fibers, comprising at least one step of applying a composition according to the invention to the skin, the lips and/or the keratin fibers.
Finally, according to another of its aspects, the present invention also relates to a cosmetic process for lightening the skin, especially of the face and/or the neck, the lips and/or keratin fibers, comprising at least one step of applying a composition according to the invention to the skin, the lips and/or the keratin fibers.
Photoluminescent mineral nanoparticles
The term "photoluminescent nanoparticles" means that the nanoparticles have the property of absorbing light and of re-emitting energy at a wavelength ranging from 380 nm to 830 nm.
This photoluminescence may be measured using a spectrofluorimeter.
Depending on their size, the photoluminescent mineral nanoparticles may especially absorbe light in the ultraviolet range, and in particular may have a maximum absorption at a wavelength of less than 400 nm. As regards the re-emission wavelength, which corresponds to the peak of maximum intensity, also referred to hereinbelow as the photoluminescence wavelength, it is generally emitted in the visible range.
Advantageously, the mineral nanoparticles have a photoluminescence wavelength in the range from about 400 nm to about 480 nm, i.e. an emission in the blue region of the visible range. When this emission takes place on the skin, it contributes toward visually bleaching the skin. More particularly, the mineral nanoparticles have a photoluminescence wavelength of about 400 nm.
According to another variant of the invention, the mineral nanoparticles have a photoluminescence wavelength in the range from about 490 nm to about 550 nm, i.e. an emission in the green region of the visible range. This may especially make it possible to efface red-colored skin defects, for instance red blotches. More particularly, the mineral nanoparticles have a photoluminescence wavelength of about 540 nm.
According to yet another variant of the invention, the mineral nanoparticles have a photoluminescence wavelength in the range from about 560 nm to about 600 nm, i.e. an emission in the yellow region of the visible range. More particularly, the mineral nanoparticles have a photoluminescence wavelength of about 570 nm.
According to yet another variant of the invention, the mineral nanoparticles have a photoluminescence wavelength in the range from about 610 nm to about 660 nm, i.e. an emission in the red-orange region of the visible range. This may contribute toward making the complexion look radiant, for example giving it a healthy appearance. More particularly, the mineral nanoparticles have a photoluminescence wavelength of about 620 nm.
The term "nanoparticles" means particles with a numerical mean size of less than 10 run. The term "numerical mean size" denotes the size given by the statistical particle size distribution to half of the population, known as the D50. In the present case, this size may be measured by electron microscopy. hi general, the small size of these nanoparticles is a determining factor for the manifestation of photoluminescence and is liable to change according to the chemical nature of the particle.
The term "noncomposite" means that the photoluminescent nanoparticles consist of only one material, which is generally of inorganic nature and especially silicon- based. In this respect, the photoluminescent nanoparticles according to the invention differ from nanoparticles consisting of an alloy, i.e. a mixture of at least two different materials. Similarly, the noncomposite mineral nanoparticles do not have a core/shell architecture obtained from at least two different materials.
The photoluminescent nanoparticles according to the invention consist essentially, or even exclusively, of silicon, oxygen and hydrogen atoms, or even exclusively of silicon and hydrogen atoms. Also included in the context of the present invention are silicon-based nanoparticles that have undergone a surface treatment, for example of oxidation type.
Silicon nanoparticles, also known as nanocrystals or quantum dots, correspond to a novel form of elemental silicon comprising intrinsically highly radiative silicon-silicon bonds.
Advantageously, the silicon nanoparticles have a numerical mean size of less than or equal to 8 nm, especially less than or equal to 6 nm and in particular less than or equal to 4 nm. Such photoluminescent nanoparticles are illustrated in the following table:
These silicon nanoparticles may especially be obtained via the processes described in documents WO 01/38222 and US 2002/0070121. These photoluminescent silicon nanoparticles are essentially proposed therein for applications in the fields of optoelectronics, nonlinear optics and medical diagnostics (WO 01/31374, WO 01/88552, WO 01/57927 and US 6 410 934).
More specifically, the processes described in documents WO 01/38222 and US
2002/0070121 involve a controlled electrochemical attack of a silicon surface used as anode. This anode is placed in contact slowly and gradually with a chemical attack solution, especially based on hydrofluoric acid (HF), optionally comprising aqueous hydrogen peroxide solution (H2O2), in a solvent, for instance methanol. According to the chemical attack current density, it is possible to modify the size distribution of the nanoparticles. The nanoparticles thus obtained generally consist of a silicon core coated with hydrogen atoms, hi particular, the silicon atoms may be concentrated at the center of the structural organization and the hydrogen atoms may be arranged at the periphery of this core based on silicon atoms.
The silicon nanoparticles that are most particularly suitable for the invention contain Si-Si and Si-H bonds. They will also be referred to hereinbelow as Si-H nanoparticles.
However, silicon nanoparticles in which the Si-H bonds are totally or partially substituted with Si-O bonds are also included in the field of the invention. According to this variant, the nanoparticles have a coating of the oxide type that does not harm the optical properties, in particular as regards the efficacy of the blue re-emission. They may especially be obtained by oxidation of the silicon nanoparticles described above.
According to one particular embodiment, the photoluminescent silicon nanoparticles are chosen from the group consisting of Si-H nanoparticles and more particularly nanoparticles with a numerical mean size of 1 run, 1.67 nm, 2.15 nm or 2.90 nm, and mixtures thereof.
The Si-H silicon nanoparticles with a numerical mean size of 1 nm have, when exposed to UV irradiation with a wavelength of 355 nm, a re-emission spectrum ranging from 390 to 920 nm. This spectrum has a dark blue band of very strong intensity centered at 390 nm, a weak orange/red end (490-640 nm) and a weak infrared band centered at
760 nm.
Illustrations of photoluminescent silicon nanoparticles of this type that may be mentioned most particularly are those proposed by the company NanoSI.
For obvious reasons, the amount of photoluminescent mineral nanoparticles in the composition of the invention depends on the desired effect. They are generally present in an amount ranging from 0.001% to 10% by weight, especially from 0.05% to 5% by weight and in particular from 0.1% to 1% by weight relative to the total weight of the composition.
The photoluminescent mineral nanoparticles may be incorporated into the compositions according to the invention in the form of a suspension in water, ethanol or any other solvent or a mixture of common solvents.
The compositions according to the invention may comprise only one type of photoluminescent nanoparticles or a mixture of these photoluminescent nanoparticles, which differ in their nature and/or their size.
In general, the compositions according to the invention make it possible to immediately give the skin onto which they are applied, and in particular to the complexion, improved qualities in terms of uniformity, homogeneity, transparency and whiteness. These compositions also have concealing properties.
They also make it possible to attenuate the perception of the skin surface defects and in particular to mask wrinkles and pores and/or to cover color defects of the skin, namely redness or marks.
The abovementioned properties are particularly appreciable in the case of photoluminescent mineral nanoparticles, and especially photoluminescent silicon nanoparticles, with a re-emission wavelength in the visible blue range.
Similarly, the compositions according to the invention may be provided with very advantageous UV-radiation screening properties, in particular between 370 and 400 nm. Such wavelengths correspond to UVA, the action of which must be combated in the context of daily photoprotection in order to reduce its harmful effects on the skin.
In the context of this photoprotection, the compositions may advantageously comprise a mixture of photoluminescent mineral nanoparticles, especially so as to obtain a UV absorption spectrum suitable for adequate protection.
According to one particular embodiment, the compositions according to the invention combine at least one dyestuff with said noncomposite photoluminescent mineral nanoparticles.
For the purposes of the invention, the term "dyestuff' is intended to denote any organic or inorganic substance capable of affording a colored effect.
By means of the choice of the combined dyestuff, it is found to be possible to modify the effect provided by said photoluminescent mineral nanoparticles.
For example, the compositions according to the invention combining with the photoluminescent mineral nanoparticles at least one dyestuff whose color corresponds to a wavelength close to the re-emission wavelength of said photoluminescent mineral nanoparticles may prove to be particularly advantageous for reinforcing the radiance and the depth of makeup obtained by application of a composition according to the invention.
Among these combinations, mention may be made especially of the following:
- photoluminescent mineral nanoparticles with a re-emission wavelength in the red region combined with at least one red dyestuff,
- photoluminescent mineral nanoparticles with a re-emission wavelength in the yellow region, with at least one yellow dyestuff, and
- photoluminescent mineral nanoparticles with a re-emission wavelength in the green region, with at least one green dyestuff. This dyestuff is generally present in a proportion of from 0.01% to 10% by weight, especially from 0.05% to 7% by weight, in particular from 0.1% to 7% by weight and more particularly from 0.1% to 5% by weight relative to the total weight of the composition.
Illustrations of these dyestuffs that may especially be mentioned include the liposoluble dyes, water-soluble 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, β- carotene, soybean oil, Sudan brown, DC Yellow 11, DC Violet 2, DC Orange 5 and quinoline yellow. The pigments may be white or colored, mineral and/or organic, and coated or uncoated. Among the 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 ferric blue. Among the 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 aluminum.
The nacreous pigments may be chosen from white nacreous pigments such as mica coated with titanium or with bismuth oxychloride, colored nacreous pigments such as titanium mica with iron oxides, titanium mica with, especially, ferric blue or chromium oxide, titanium mica with an organic pigment of the abovementioned type, and also nacreous pigments based on bismuth oxychloride.
The pigments may have undergone a surface treatment.
Physiologically acceptable medium
The composition according to the invention comprises at least one physiologically acceptable medium.
The term "physiologically acceptable medium" denotes a nontoxic medium that may be applied to human skin, lips or keratin materials. The physiologically acceptable medium is generally adapted to the nature of the support onto which the composition is to be applied, and also to the aspect in which the composition is intended to be packaged.
The composition of the invention may especially comprise a fatty phase, especially in a proportion of from 5% to 80% by weight and in particular from 5% to 50% by weight relative to the total weight of the composition.
The oils that may be used in the composition may be chosen from those conventionally used in the field under consideration.
In particular, the composition of the invention may comprise an oil chosen especially from:
- hydrocarbon-based oils of animal origin, such as perhydrosqualene;
- hydrocarbon-based 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;
- synthetic esters and ethers, especially of fatty acids, for instance the oils of formulae R1COOR2 and R1OR2 in which R1 represents a fatty acid residue or a fatty alcohol residue containing from 8 to 29 carbon atoms and R2 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, isostearyl isostearate; hydroxylated esters, for instance isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, and fatty alcohol heptanoates, octanoates and decanoates; polyol esters, for instance propylene glycol dioctanoate, neopentyl glycol diheptanoate and diethylene glycol diisononanoate; and pentaerythritol esters, for instance pentaerythrityl tetraisostearate;
- linear or branched hydrocarbons of mineral or synthetic origin, such as volatile or nonvolatile liquid paraffins and derivatives thereof, petroleum jelly, polydecenes, and hydrogenated polyisobutene such as parleam oil;
- fatty alcohols containing from 8 to 26 carbon atoms, for instance cetyl alcohol, stearyl alcohol and the mixture thereof (cetylstearyl alcohol), octyldodecanol, 2- butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol or linoleyl alcohol;
- partially hydrocarbonated and/or siliconated fluorin-based oils, for instance those described in document JP-A-2-295 912;
- silicone oils, for instance volatile or nonvolatile polymethylsiloxanes (PDMS) containing a linear or cyclic silicone chain, which are liquid or pasty at room temperature, especially cyclopolydimethylsiloxanes (cyclomethicones) such as cyclohexasiloxane; polydimethylsiloxanes comprising 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 trimethicones, phenyl dimethicones, phenyltrimethylsiloxy- diphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes, 2-phenyl- ethyltrimethyl siloxysilicates and polymethylphenylsiloxanes; and
- mixtures thereof. When the composition is in the form of an emulsion containing a fatty phase, it may also comprise an emulsifier, and optionally a co-emulsifier.
As emulsifϊers and co-emulsifiers that may be used in the invention, examples that may be mentioned include 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 such as the oxyethylenated poly(methylcetyl)-
(dimethyl)methylsiloxane available under the trade name Abil WE 09 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.
The emulsifier and optionally the co-emulsifier are generally present in the composition in a proportion ranging from 0.3% to 30% by weight and in particular from 0.5% to 20% by weight relative to the total weight of the composition.
The composition according to the invention may also comprise at least one wax, at least one gum and/or at least one pasty fatty substance, which may or may not be silicone-based, of plant, animal, mineral or synthetic origin.
For the purposes of the present invention, the waxes may be hydrocarbon- based, silicone and/or fluoro waxes, optionally composed of ester or hydroxyl functions. They may especially be of natural origin.
The wax may represent from 0.01% to 10% by weight and especially from 0.1% to 5% by weight relative to the total weight of the composition. According to one embodiment, the composition may be wax-free. The compositions according to the invention may also comprise at least one common matting agent such as mineral fillers (zinc oxide, zirconium oxide, silica, alumina, boron nitride, talc, sericite, mica, etc.), which may be coated or uncoated, clays, starch and its derivatives, aqueous dispersions of acrylic styrene, melamine-formaldehyde or urea- formaldehyde resin particles, aqueous dispersions of polytetrafluoroethylene, wax microdispersions, vinylpyrrolidone/1-triacontene copolymers, water-dispersible polymers containing units with an LCST, silicone waxes and resins, expanded terpolymer microspheres of vinylidene chloride, of acrylonitrile and of methacrylate, nylon particulates, cellulose microbeads and fibers.
The matting agent may be present in a content ranging from 0.1% to 10% by weight relative to the total weight of the composition.
It is clearly understood that the choice of this matting agent, and also that of the amount used, will be made by a person skilled in the art so as not to harm the desired properties.
In a known manner, the composition according to the invention may also contain at least one adjuvant that is common in cosmetics, such as fillers, hydrophilic or lipophilic gelling agents, water-soluble or Hposoluble active agents, preserving agents, moisturizers, such as polyols and especially glycerol, sequestering agents, antioxidants,
solvents, fragrances, physical sunblocks and chemical sunscreens, especially acting against UVA and/or UVB, odor absorbers and pH regulators (acids or bases), and mixtures thereof.
The amounts of 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.
In any case, these adjuvants, and also the proportions thereof, will be chosen so as not to harm the desired properties according to the invention.
The composition according to the invention may also comprise at least one filler.
Illustrations of fillers that may especially be mentioned include talc; starch crosslinked with octenylsuccinic anhydride, sold by the company National Starch under the name Dry Flo Plus (28-1160); polyamides particles and especially those sold under the name Orgasol by the company Atochem; polyethylene powders; microspheres based on acrylic copolymers, such as those made of ethylene glycol dimethacrylate/lauryl methacrylate copolymer sold by the company Dow Corning under the name Polytrap; 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; silicone resin microbeads such as those sold under the name Tospearl by the company Toshiba Silicone; and mixtures thereof.
These fillers may be present in amounts ranging from 0 to 20% by weight and especially from 1% to 10% by weight relative to the total weight of the composition.
Active agents that may be mentioned in particular include:
- active agents known for their activity on the ageing of the skin, for instance keratolytic agents or prodesquamating agents, for example α-hydroxy acids, β-hydroxy acids, α-keto acids, β-keto acids, retinoids and esters thereof, retinal, and retinoic acid and derivatives thereof;
- vitamins, for example vitamin A, B3, PP, B5, E, Kl and/or C, and derivatives of these vitamins and especially esters thereof; - free-radical scavengers;
- sunscreens;
- moisturizers, for instance polyols;
- ceramides;
- DHEA and derivatives thereof;
- coenzyme QlO;
- additional biologically-acting bleaching agents and depigmenting agents, for instance kojic acid, extracts of skullcap, of mulberry, of licorice and/or of camomile, para- aminophenol derivatives and arbutin and derivatives thereof, and mixtures thereof;
- active agents that are useful for greasy or combination skin, such as zinc salts and in particular zinc oxide and zinc gluconate;
- antibacterial agents, for instance salicylic acid and derivatives thereof such as 5-n-octanoylsalicylic acid, triclosan, lipacid, capryloylglycine, extract of clove, octopirox, hexamidine, and azeleic acid and derivatives thereof;
- antiacne active agents, or alternatively
- venotonic plant extracts such as extracts of butcher's broom and/or of common horse chestnut; xanthine bases such as caffeine. The composition according to the invention may be in any galenical form normally used in cosmetics, normally used for topical application: direct, inverse or multiple emulsions, gels, creams, solutions, suspensions, lotions, loose or compact powders, and sticks.
They may more specifically be in the form of an optionally gelled oily solution, an emulsion of liquid or semiliquid consistency of the milk type, obtained by dispersing a fatty phase in an aqueous phase (OAV) or, conversely, (W/O), a triple emulsion (W/O/W or
0/W/O), or a suspension or emulsion of soft, semisolid or solid consistency of the cream or gel type, or alternatively microemulsions, microcapsules, microparticles or a vesicular dispersion of ionic type (liposomes or oleosomes) and/or of nonionic type (niosomes) and/or a dispersion of nanocapsules or nanospheres.
The cosmetic composition according to the invention may especially be in the form of a care, makeup and/or antisun composition.
More particularly, the composition according to the invention is in the form of a facial makeup product, especially for the skin and/or the lips, especially in the form of a foundation or a lipstick.
The composition according to the invention may also be in the form of a care and/or makeup composition for the skin, the lips and/or keratin fibers.
According to one variant of the invention, the composition is in the form of a concealer gel or a photoprotective and especially an anti-UV care cream or lotion.
The examples given below are presented as nonlimiting illustrations of the invention.
Example 1
* as described in documents WO 01/38222 and US 2002/0070121
Example 2
* as described in WO 01/38222 and US 2002/0070121
Procedure:
The emulsion is prepared by adding, with stirring, the oily phase heated to 650C to the hot aqueous phase.
Example 3
*as described in WO 01/38222 and US 2002/0070121
Procedure:
The emulsion is prepared by adding, with vigorous stirring using a stator rotor, the oily phase, heated to 65°C, to the hot aqueous phase until a fine emulsion is obtained. After cooling, the silicon nanoparticles are added and dispersed.
An emulsion that is perfectly suitable for photoprotecting the skin and that covers the whole UV spectrum is obtained.