# Patent

## Title
Application of dehydroascorbic acid or derivatives/isomers thereof for artificially coloring the skin

## Abstract

Dehydroascorbic acid and polymeric/monomeric derivatives and isomers thereof are useful for artificially coloring the skin and more particularly as a skin self-tanning agent; the dehydroascorbic acid may be formed “in situ” from ascorbic acid or a derivative or salt thereof via chemical oxidation and/or via enzymatic oxidation, and a two-component agent thereof includes

    
    
        a) a first component (B) containing, in a physiologically acceptable medium, at least ascorbic acid or a derivative or salt thereof;
        b) a second component (C) containing, in a physiologically acceptable medium, at least one chemical oxidizing agent and/or one enzymatic oxidizing agent; components (B) and (C) being stored separately.

## Background
CROSS-REFERENCE TO PRIORITY/PROVISIONAL APPLICATIONS
This application claims priority under 35 U.S.C. §119 of FR 0756353, filed Jul. 9, 2007, and of U.S. Provisional Application No. 60/929,965, Jul. 19, 2007, each hereby expressly incorporated by reference and each assigned to the assignee hereof.


BACKGROUND OF THE INVENTION
Technical Field of the Invention
The present invention relates to the cosmetic topical application of dehydroascorbic acid and monomeric derivatives, polymeric derivatives or isomers thereof, formulated into a composition comprising a physiologically acceptable medium, as an agent for artificially coloring the skin and, more particularly, as a skin self-tanning agent.
Description of Background and/or Related and/or Prior Art
Today, it is important to look healthy and a tanned skin is always a sign of good health. However, a natural tan is not always desirable since it requires long exposure to UV radiation, in particular to UV-A radiation that causes tanning of the skin but, however, is liable to induce an adverse change therein, in particular in the case of sensitive skin or of skin that is continually exposed to solar radiation. It is thus desirable to find an alternative to a natural tan that is compatible with the requirements of such skin types.
Most of the cosmetic products intended for artificially tanning the skin are based on carbonyl derivatives which, by interacting with the free amine functions of the skin, in particular the amino acids, peptides or proteins of the skin, allow the formation of colored species.
To this end, it is known that dihydroxyacetone, or DHA, is a particularly advantageous compound which is commonly employed in cosmetics as an agent for artificially tanning the skin; when applied to the skin, in particular to the face, it gives a tanning or bronzing effect which is similar in appearance to that which may result from prolonged exposure to sunlight (a natural tan) or under a UV lamp.
One drawback of DHA is the length of time the coloration takes to develop: specifically, several hours (3 to 5 hours in general) are required for the coloration to be revealed. Another drawback of DHA is its tendency to produce yellow shades that harm the production of a natural skin tone. There is thus increasing demand for self-tanning products that act quickly and provide a coloration closer to that of a natural tan.
Thus, need continues for novel compounds and novel compositions that can give the skin an artificial coloration close to that of a natural tan in a simple, effective and fast manner.
WO 2005/039 510 discloses the use of dehydroascorbic acid or a salt thereof produced in situ via enzymatic oxidation, as a fixing agent in the permanent waving of hair. DE-197,45,354 also discloses the use of dehydroascorbic acid in combination with particular compounds with primary or secondary amine groups or hydroxyl groups, for coloring the hair.
SUMMARY OF THE INVENTION
After extensive studies conducted in the field of artificial coloring of the skin, it has now been discovered that dehydroascorbic acid or a monomer derivative, polymer derivative or isomer thereof can impart, after application of the product onto the skin, an artificial coloration similar to a natural tan, which develops more quickly than standard self-tanning agents such as DHA (visible within 30 minutes) and provides stronger colors whose red component is more pronounced, and affords, depending on the amount used, a range of shades that are closer to natural pigmentation, unlike standard self-tanning agents such as DHA. The formulations containing dehydroascorbic acid or a polymer thereof also have the advantage of being slightly colored on application to the skin and thus of being able to be dosed and to visualize the zone of application of the product.
The present invention thus features the cosmetic formulation of dehydroascorbic acid or a monomeric derivative, a polymeric derivative or an isomer thereof into a composition comprising a physiologically acceptable medium, as an agent for artificially coloring the skin and, more particularly, as a skin self-tanning agent.
The present invention also features a process for artificially coloring the skin and more particularly a process, whether regime or regimen for artificially tanning the skin, comprising applying to the skin an effective amount of a cosmetic composition which comprises, formulated into a physiologically acceptable medium, at least dehydroascorbic acid and/or a monomeric derivative thereof corresponding to formula (I) defined below and/or an isomer thereof corresponding to formula (I′) defined below and/or polymeric derivatives thereof, in particular those of formula (II).
For the purposes of the present invention, the expression “artificial coloration of the skin” means a long-lasting, non-covering coloration (i.e., a coloration that does not have a tendency to opacify the skin), which is not removed either with water or using a solvent, and which is resistant both to rubbing and to washing with a solution containing surfactants. Such a long-lasting coloration is thus distinguished from the superficial and temporary coloration provided, for example, by a makeup product.
For the purposes of the present invention, the term “polymer” means any molecule having in its structure at least two repeating structural units.
For the purposes of the present invention, the expression “physiologically acceptable medium” means a support that is compatible with the skin, the nails, the lips which has a pleasant color, odor and feel and which does not give rise to any unacceptable discomfort (stinging, tautness or redness) liable to put the consumer off using this composition comprising such a support.
For the purposes of the present invention, the expression “skin self-tanning agent” means a compound that is capable of producing, on contact with the skin, a colored reaction with the free amine functions present in the skin, such as amino acids, peptides or proteins.
Other characteristics, aspects and advantages of the present invention will become apparent from the detailed description that follows.


DETAILED DESCRIPTION OF BEST MODE AND SPECIFIC/PREFERRED EMBODIMENTS OF THE INVENTION
Dehydroascorbic acid and the monomeric derivatives in accordance with the invention correspond to formula (I) below or to their isomeric forms of formula (I′) below:




in which OR1 and OR2, which may be identical or different, are each OH; a linear or branched, saturated or unsaturated C1-C30 and more preferentially C1-C18 alkoxy radical; a glycoside and more preferentially glucose; a linear or branched, saturated or unsaturated C1-C30 (preferably C1-C18) aliphatic carboxylic acid ester, which may be substituted with an aryl group or a heterocycle; an aryl or heterocyclic carboxylic acid ester which may be substituted with at least one linear or branched, saturated or unsaturated C1-C30 (more preferentially C1-C18) alkyl radical; a phosphate group; a sulfate group.

Preferentially, R2 will denote a linear or branched, saturated or unsaturated C1-C30 (preferably C1-C18) aliphatic carboxylic acid ester, which may be substituted with an aryl group or a heterocycle; an aryl or heterocyclic carboxylic acid ester which may be substituted with at least one linear or branched, saturated or unsaturated C1-C30 (more preferentially C1-C18) alkyl radical.
Dehydroascorbic acid of formula (I) is also known as threo-2,3-hexodiulosono-1,4-lactone, 9CI (CAS #490-83-5) and has the structure:




Its isomeric form of formula (I′) also known as 3a,6-dihydroxy-tetrahydro-furo[3,2-b]furan-2,3-dione has the structure:




Among the monomeric derivatives of dehydroascorbic acid of formula (I) that are exemplary are the following particular compounds:
L-threo-2,3-hexodiulosonic acid, γ-lactone, 5,6-bis(3-phenyl-2-propenoate)
(CAS #106406-96-6) with OR1═OR2=3-phenyl-2-propenoate
L-threo-2,3-hexodiulosonic acid, γ-lactone, 6-acetate
(CAS #106227-02-5) with OR2=acetate and R1═H
L-threo-2,3-hexodiulosonic acid, γ-lactone, 5,6-diacetate
(CAS #59681-41-3) with OR1═OR2=acetate
L-threo-2,3-hexodiulosonic acid, γ-lactone, 6-hexadecanoate
(CAS #63247-05-2) with OR2=hexadecanoate and OR1═H
L-threo-2,3-hexodiulosonic acid, γ-lactone, 6-octadecanoate (9CI)
(CAS #59681-40-2) with OR2=octadecanoate and OR1═OH
L-threo-2,3-hexodiulosonic acid, γ-lactone, 6-benzoate
(CAS #63247-04-1) with OR2=benzoate and OR1═OH.
Among the polymeric derivatives that are exemplary are the dimeric compounds of formula (II) below:




in which OR1, OR2, OR3 and OR4, which may be identical or different, denote OH; a linear or branched, saturated or unsaturated C1-C30 and more preferentially C1-C18 alkoxy radical; a glycoside and more preferentially glucose; a linear or branched, saturated or unsaturated C1-C30 (preferably C1-C18) aliphatic carboxylic acid ester, which may be substituted with an aryl group or a heterocycle; an aryl or heterocyclic carboxylic acid ester which may be substituted with at least one linear or branched, saturated or unsaturated C1-C30 (more preferentially C1-C18) alkyl radical; a phosphate group; a sulfate group.

Preferentially, R1 and/or R2 will denote a linear or branched, saturated or unsaturated C1-C30 (preferably C1-C18) aliphatic carboxylic acid ester, which may be substituted with an aryl group or a heterocycle; an aryl or heterocyclic carboxylic acid ester which may be substituted with at least one linear or branched, saturated or unsaturated C1-C30 (more preferentially C1-C18) alkyl radical.
Among the dehydroascorbic acid-based dimers of formula (II), particularly exemplary are the following particular compounds:

    2H,8H-bisfuro[3′,2′:2,3]furo[3,4-b:3′,4′-e][1,4]dioxin-5,11(5aH,11aH)-dione, 3,5a,9,11a-tetrakis(benzoyloxy)tetrahydro-[3S-(3α,3aα,5aβ,6aS*,9aα,11aβ,12aS*)] (CAS #103559-39-3) with OR1═OR2═OR3═OR4=benzoate
    1,6,9,13-tetraoxadispiro[4.2.4.2]tetradecane-7,14-dicarboxylic acid, 4,12-dihydroxy-3,7,11,14-tetramethoxy-, di-γ-lactone (CAS #94329-25-6) with R1═R2═R3═R4=methyl
    2H,8H-bisfuro[3′,2′:2,3]furo[3,4-b:3′,4′-e][1,4]dioxin-5,11(5aH,11aH)-dione, 3,5a,9,11a-tetrakis(acetyloxy)tetrahydro-[3S-(3α,3aα,5aβ,6aS*,9α,9aα,11aβ,12aS*)] (CAS #25726-18-5) with OR1═OR2═OR3═OR4=acetate
    2H,8H-bisfuro[3′,2′:2,3]furo[3,4-b:3′,4′-e][1,4]dioxin-5,11(5aH,11aH)-dione, 3,5a,9,11a-tetrakis(3′′-phenyl-2′′-propenoxy)tetrahydro-[3S-(3α,3aα,5aβ,6aS*,9α,9aα,11aβ,12aS*)] (CAS #106406-97-7) with OR1═OR2═OR3═OR4=3-phenyl-2-propenoate.


Particularly exemplary is the dimeric compound (CAS #72691-25-29) with R1═R2═H, having the following structure:




According to one particular embodiment of the invention, the dehydroascorbic acid or one of its momeric, polymeric derivatives or isomers may be formed “in situ” from ascorbic acid or a derivative thereof or a salt thereof via chemical oxidation and/or via enzymatic oxidation according to the following reaction scheme:




The oxidation reaction may in particular be efficiently catalyzed by many types of enzymes, for instance the ascorbate oxidases produced by the majority of plants and also certain bacteria, yeasts or animals (E.C [1.10.3.3] Lee, M. H.; Dawson, C.R. Methods Enzymol., 1979, 62, 30-39).
This invention also features the cosmetic use of a two-component agent comprising:
a) a first component (B) containing, in a physiologically acceptable medium, at least ascorbic acid or a derivative or salt thereof;
b) a second component (C) containing, in a physiologically acceptable medium, at least one chemical oxidizing agent and/or one enzymatic oxidizing agent; components (B) and (C) being stored separately, for the artificial coloring of the skin, in particular as a skin self-tanning agent.
The present invention also features a process for artificially coloring the skin, and more particularly for artificially tanning the skin, comprising applying to the skin:
a) a first component (B) containing, in a physiologically acceptable medium, at least ascorbic acid or a derivative or salt thereof;
b) a second component (C) containing, in a physiologically acceptable medium, at least one chemical oxidizing agent and/or one enzymatic oxidizing agent; components (B) and (C) being mixed together at the time of use and applied simultaneously to the skin, or, alternatively, applied to the skin one after the other.
The chemical oxidizing agents conventionally employed for the oxidation of ascorbic acid or derivatives or salts thereof are, for example, hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, and peracids, or mixtures thereof.
The enzymatic oxidizing systems used are conventionally oxidize enzymes using either atmospheric oxygen or a substrate to form hydrogen peroxide, among which representative are 2-electron oxidoreductases such as uricases, ascorbate oxidases, etc.
The enzymes in accordance with the present invention are preferably selected from among the ascorbate oxidases using atmospheric oxygen. More preferentially, the enzymes are selected from among those belonging to the Enzyme Commission classification [1.10.3.3].
The ascorbate oxidize enzyme may be derived, for example, from the following botanical types: Arabidopsis, Brassica, Cucumis, Curcubita, Myrothecium, Nicotiana, Oryza, Triticum. It is more preferentially selected from among those derived from Curbita pepo mudullosa (aubergine). It is also possible to use an ascorbate oxidize enzyme obtained from numerous other plants, including cabbage (Brassica oleracea), cucumber (Cucumis savitus), pumpkin (Curcubita cv. Ebisu Nankin), tobacco (Nicotiana tabacum), mustard (Sinapsis alba), rice (Oryza sativa) and wheat (Triticum aestivum). Other sources include mushrooms (Myrotectium verrucaria) and thermophilic bacteria (Acremonium sp. HI-25).
The enzyme may be present as a solution or in powder form and may preferably be stabilized with buffers, glycerol, sugars or other polyhydroxylated compounds, metal-chelating agents such as EDTA, thiols such as thioglycerol, mercaptoethanol or dithiothreitol, polyethylene glycol, unreactive proteins or other enzyme-preservatives. The enzymes may also be stabilized via covalent modification according to standard techniques. The enzyme may also be immobilize by covalent bonding onto a solid support such as surface-modified silica, alumina, glass, oxirane-modified polymethacrylate, carboxyalkylcellulose, aminoalkyl silica, aminoalkyl glass or aminoalkylcellulose microparticles. The enzymes may also be adsorbed onto the surfaces of hydrophobically or ionically modified particles such as carboxyalkylcelluloses or dialkylaminocelluloses. Another possibility entails covalently bonding the enzyme with a synthetic or biosynthetic water-soluble polymer, such as polyethylene glycols, poly(acrylic acids), poly(vinyl alcohols), polyethyleneimines, dextran and proteins such as gelatin or uricase.
The said enzyme is preferably present in the composition resulting from the mixing of components (B) and (C) in contents ranging from 1 to 10,000 ppm and preferably 100 to 1,000 ppm.
The present invention also features a multi-compartment device, also known as a “kit” or “skin-coloring equipment”, comprising:
a first compartment comprising component (B) as defined above;
a second compartment comprising component (C) as defined above.
According to a first embodiment of the device in accordance with the invention, components (B) and (C) may be conditioned independently each in a container delimiting at least one compartment, the said container being closed by means of a closing member.
The container may be in any adequate form. It may especially be in the form of a bottle, a tube, a jar, a case, a box, a sachet or a carton.
The closing member may be in the form of a removable stopper, a lid, a cap, a tear-off strip or a capsule, especially of the type comprising a body attached to the container and a cover cap articulated on the body. It may also be in the form of a member for selectively closing the container, especially a pump, a valve or a flap valve.
The product may be contained directly in the container, or indirectly. By way of example, the product may be arranged on an impregnated support, especially in the form of a wipe or a pad, and arranged (individually or in plurality) in a box or in a sachet. Such a support incorporating the product is described, for example, in WO 01/03538.
The closing member may be coupled to the container by screwing. Alternatively, the coupling from the closing member and the container is done other than by screwing, especially via a bayonet mechanism, by click-fastening, gripping, welding, bonding or by magnetic attraction. The term “click-fastening” in particular means any system involving the crossing of a bead or cord of material by elastic deformation of a portion, especially of the closing member, followed by return to the elastically unconstrained position of the said portion after the crossing of the bead or cord.
The container may be at least partially made of thermoplastic material. Examples of thermoplastic materials that are exemplary include polypropylene or polyethylene.
Alternatively, the container is made of non-thermoplastic material, especially glass or metal (or alloy).
The container may have rigid walls or deformable walls, especially in the form of a tube or a tubular bottle.
The container may comprise means for distributing or facilitating the distribution of the composition. By way of example, the container may have deformable walls so as to cause the composition to exit in response to a positive pressure inside the container, this positive pressure being caused by elastic (or non-elastic) squeezing of the walls of the container.
According to another embodiment, the respective components (B) and (C) are conditioned in two containers that are joined together so as to be securely fastened to each other.
For example, they are contained in two containers held together via an outer packaging. In particular, each container is equipped with a dispensing member, for example a pump or a valve. Preferably, this dispensing member is manually actuated. The pump may also be without an air inlet, in the case where the composition is to be protected from any contact with the exterior, during its storage time.
According to a first embodiment, the actuation of these dispensing members leads the compositions into an assembly mixing chamber, so as to ensure mixing prior to them being dispensed from this assembly formed by these two joined containers.
Alternatively, according to a second embodiment, the actuation of these dispensing members leads to expulsion of the compositions without premixing.
One particular embodiment of the invention is a device as described in EP-1-270,444. It is a device for the simultaneous dispensing of the two components (B) and (C), conditioned separately in first and second flexible-wall sachets, the said device comprising:
i) means for solidly holding the two sachets in a superposed position such that respective outlet orifices of the said sachets are aligned in the region of each other; and
ii) means, which are movable relative to the fixing means, and capable of pressurizing the two sachets so as to force the expulsion of their contents through their respective outlet orifices in a predetermined ratio.
Another particular embodiment of the invention is a device as described in EP-1-300,344. It is a device for the combined dispensing of the two components (B) and (C) conditioned separately, comprising:
a) a first flexible-wall container containing component (B);
b) a second flexible-wall container, outside the first, containing component (C);
c) a stage on which the first and second containers are mounted;
d) a dispensing member, which is movable relative to the stage, and capable of making the device pass, irreversibly, from a first configuration in which the first and second containers are isolated from at least one dispensing orifice formed by the said dispensing member, to a second configuration in which the first and second containers are in communication with the said dispensing orifice(s).
Thus, in the second configuration of the device, in response to a pressure exerted on the flexible walls of the first and second containers, which are arranged adjacent to each other, the first and second products may be dispensed together.
The combined expulsion of the two products in order to prepare a composition, especially a cosmetic composition, may take place via a single dispensing orifice, upstream of which may be located a mixing zone in which the two products are placed in contact before being dispensed in mixed form.
Another particular embodiment of a device of the invention is a twin pump comprising:
a) two reservoirs, which are preferably housed in the same outer housing comprising, respectively, component (B) or component (C), preferably housed in the same outer housing;
b) two pumps, each mounted on a reservoir,
c) a single push-button, which is axially movable along a main elongation axis of the outer housing, and which allows the simultaneous opening of the two pumps to be actuated; these two pumps each moreover being connected via an outlet channel emerging at least one dispensing orifice.
The said dispensing orifice may be unique and common to the two reservoirs. In this case, the products exit in mixed form.
According to another embodiment, each outlet channel is associated with its own dispensing orifice. The products contained in these reservoirs are thus dispensed from the device without ever having come into contact beforehand inside the device. This type of variant is especially described in FR-2-789,371; U.S. Pat. No. 5,224,627; WO 97/05040.
Another particular embodiment of a device of the invention is a double aerosol comprising:
a) two reservoirs, preferably housed in the same outer housing comprising at least one propellant and, respectively, component (B) or component (c),
b) two aerosol valves, each mounted on a reservoir,
c) a single push-button, which is axially movable along a main elongation axis of the outer housing, and allowing the simultaneous opening of the two pumps to be actuated; these two valves each moreover being connected via an outlet channel emerging at least one dispensing orifice.
The said dispensing orifice may be unique and common to the two reservoirs. In this case, the products exit in mixed form.
According to another embodiment, each outlet channel is associated with its own dispensing orifice. The products contained in these reservoirs are then dispensed from the device, without ever having come into contact beforehand inside the device.
Needless to say, depending on the device used, one skilled in the art will take care, for each of components (B) and (C), to select the viscosity and rheological properties that are suitable for allowing good expulsion of the products from the said device.
According to one particular embodiment of the invention, in order to increase the remanence of the color and/or the color uniformity obtained after applying dehydroascorbic acid or a monomeric derivative, a polymer derivative, an isomer thereof to the skin, this product is combined with ascorbic acid or a derivative or salt thereof.
This invention thus features the cosmetic use, as an agent for artificially coloring the skin, and more particularly as a skin self-tanning agent, of a three-component product comprising:
a) a first component (A) containing, in a physiologically acceptable medium, at least dehydroascorbic acid or a monomeric derivative, a polymer derivative, an isomer thereof;
b) a second component (B) containing, in a physiologically acceptable medium, at least ascorbic acid or a derivative or salt thereof;
c) a third component (C) containing, in a physiologically acceptable medium, at least one chemical oxidizing agent and/or one enzymatic oxidizing agent; components (A) and (B) possibly being in the same composition or stored separately and component (C) being stored separately from (A) and from (B).
This invention also features a process for artificially coloring the skin and more particularly for artificially tanning the skin, which comprises applying to the skin:
a) a first component (A) containing, in a physiologically acceptable medium, at least dehydroascorbic acid or a monomeric derivative, a polymer derivative, an isomer thereof;
b) a second component (B) containing, in a physiologically acceptable medium, at least ascorbic acid or a derivative or salt thereof;
c) a third component (C) containing, in a physiologically acceptable medium, at least one chemical oxidizing agent and/or one enzymatic oxidizing agent; components (A), (B) and (C) being mixed together at the time of use and applied to the skin, or else applied to the skin one after the other.
The present invention also features a multi-compartment device, also known as a “kit” or “skin-coloring equipment”, selected from among:
(i) a two-compartment device comprising:
a first compartment comprising component (B) and optionally component (A) as defined above; and
a second compartment comprising component (C) as defined above.
(ii) a three-compartment device, comprising:
a first compartment comprising component (A) as defined above;
a second compartment comprising component (B) as defined above;
a third compartment comprising component (C) as defined above.
The multi-compartment devices that may be used may be selected from among those described previously.
Dehydroascorbic acid or a monomeric derivative, a polymer derivative, an isomer thereof is preferably used in contents ranging from 0.1% to 50% by weight and more preferentially from 1% to 10% by weight relative to the total weight of the composition containing it.
Ascorbic acid or a derivative or salt thereof is preferably employed in contents ranging from 0.1% to 50% by weight and more preferentially from 1% to 15% by weight relative to the total weight of the composition containing it.
The compositions of the invention may be in any form that is suitable for topical application, especially in the form of aqueous gels, in the form of emulsions obtained by dispersing a fatty phase (also known as an oily phase) in an aqueous phase (O/W) or, conversely, (W/O) or multiple emulsions (for example W/O/W, O/W/O or O/O/W). They may be more or less fluid and may have the appearance of a white or colored cream, a pomade, a milk, a lotion, a serum, a paste, a powder or a solid tube, and they may optionally be packaged as an aerosol and be in the form of a mousse or spray. These compositions are prepared according to the usual methods.
According to one particular embodiment of the invention, the compositions of the invention may be in the form of an emulsion and in this case may comprise at least one oily phase. The proportion of the oily phase of the emulsion may range from 1% to 80% by weight, preferably from 2% to 50% by weight and better still from 2% to 40% by weight relative to the total weight of the composition. The fatty substances of the oily phase, especially the oils, and the emulsifiers and coemulsifiers that may be present, used in the composition in emulsion form are selected from among those conventionally used in cosmetics or dermatology. The emulsifier and the coemulsifier, when they are present, are generally in a proportion ranging from 0.1% to 30% by weight, preferably from 0.3% to 20% by weight and better still from 0.5% to 15% by weight relative to the total weight of the composition. The emulsion may also contain lipid vesicles in addition to or instead of the emulsifiers and/or coemulsifiers.
The emulsions generally contain at least one emulsifier selected from among amphoteric, anionic, cationic and nonionic emulsifiers, used alone or as a mixture. The emulsifiers are selected in an appropriate manner according to the continuous phase of the emulsion to be obtained (W/O or O/W). When the emulsion is multiple, it generally comprises an emulsifier in the primary emulsion and an emulsifier in the outer phase into which the primary emulsion is introduced.
As emulsifiers that may be used for the preparation of the W/O emulsions, examples thereof include alkyl esters or ethers of sorbitan, of glycerol or of sugars; silicone surfactants, for instance dimethicone copolyols such as the mixture of cyclomethicone and of dimethicone copolyol, marketed under the trademarks DC 5225 C and DC 3225 C by Dow Corning, and alkyldimethicone copolyols such as laurylmethicone copolyol marketed under the trademark “Dow Corning 5200 Formulation Aid” by Dow Corning, cetyl dimethicone copolyol marketed under the trademark Abil EM 90® by Goldschmidt, and the mixture of polyglyceryl-4 isostearate/cetyl dimethicone copolyol/hexyl laurate marketed under the trademark Abil WE 09® by Goldschmidt. One or more co-emulsifiers may also be added thereto, which may be selected, advantageously, from the group comprising branched-chain fatty acid esters of polyol, and especially branched-chain fatty acid esters of glycerol and/or of sorbitan, for example polyglyceryl isostearate, such as the product marketed under the trademark Isolan GI 34 by Goldschmidt, sorbitan isostearate, such as the product marketed under the trademark Arlacel 987 by ICI, sorbitan glyceryl isostearate, such as the product marketed under the trademark Arlacel 986 by ICI, and mixtures thereof.
As emulsifiers that may be employed for the preparation of the O/W emulsions, examples thereof include nonionic emulsifiers such as fatty acid esters of oxyalkylenated (more particularly polyoxyethylenated) polyols, for example polyethylene glycol stearates, for instance PEG-100 stearate, PEG-50 stearate and PEG-40 stearate; fatty acid esters of oxyalkylenated sorbitan comprising, for example, from 20 to 100 EO, for example those marketed under the trademarks Tween 20 or Tween 60 by Uniqema; oxyalkylenated (oxyethylenated and/or oxypropylenated) fatty alkyl ethers; alkoxylated or non-alkoxylated sugar esters, for instance sucrose stearate such as PEG-20 methylglucose sesquistearate; sorbitan esters such as the sorbitan palmitate marketed under the trademark Span 40 by Uniqema; diacid esters of fatty alcohols, for instance dimyristyl tartrate; mixtures of these emulsifiers, for instance the mixture of glyceryl stearate and of PEG-100 stearate (CTFA name: Glyceryl Stearate/PEG-100 Stearate) marketed under the trademark Arlacel 165 by Uniqema and under the trademark Simulsol 165 by SEPPIC; or the mixture of dimyristyl tartrate, cetearyl alcohol, Pareth-7 and PEG-25 laureth-25, marketed under the trademark Cosmacol PSE by Sasol (CTFA name: Dimyristyl tartrate/cetearyl alcohol/12-15 Pareth 7/PPG 25 laureth 25).
Coemulsifiers such as, for example, fatty alcohols having from 8 to 26 carbon atoms, for instance cetyl alcohol, stearyl alcohol and the mixture thereof (cetearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol or oleyl alcohol, or fatty acids, may be added to these emulsifiers.
It is also possible to prepare emulsions without emulsifying surfactants or containing less than 0.5% of them relative to the total weight of composition (A) or (B), by using suitable compounds, for stabilizing the said emulsions, for example amphiphilic polymers or electrolytes.
When the composition of the invention is in emulsion form, it comprises at least one oily phase that contains at least one oil, especially a cosmetic oil. The term “oil” means a fatty substance that is liquid at room temperature (25° C.).
As oils that may be included in the compositions of the invention, exemplary are hydrocarbon-based oils of animal origin, such as perhydrosqualene (or squalane); hydrocarbon-based oils of plant origin, such as caprylic/capric acid triglycerides, for instance those marketed by Stearineries Dubois or those marketed under the trademarks Miglyol 810, 812 and 818 by Dynamit Nobel, or, alternatively, oils of plant origin, for instance sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, coriander oil, castor oil, avocado oil, jojoba oil and shea butter oil; synthetic oils; silicone oils, for instance volatile or non-volatile polymethylsiloxanes (PDMSs) containing a linear or cyclic silicone chain, which are liquid or pasty at room temperature; fluoro oils, such as partially hydrocarbon-based and/or silicone-based fluoro oils, for instance those described in JP-A-2 295 912; ethers, such as dicaprylyl ether (CTFA name: Dicaprylyl ether); C12-C15 fatty alkyl benzoates (Finsolv TN from Finetex); arylalkyl benzoate derivatives, for instance 2-phenylethyl benzoate (X-Tend 226 from ISP); and amido oils, for instance isopropyl N-lauroylsarcosinate (Eldew SL-205 from Ajinomoto); and mixtures thereof.
The compositions of the invention may also contain one or more organic solvents that may be selected from among the group consisting of hydrophilic organic solvents, lipophilic organic solvents and amphiphilic solvents, or mixtures thereof.
Examples of hydrophilic organic solvents include linear or branched monohydric alcohols having from 1 to 8 carbon atoms, for instance ethanol, propanol, butanol, isopropanol or isobutanol; polyethylene glycols having from 6 to 80 ethylene oxides; polyols such as propylene glycol, isoprene glycol, butylene glycol, glycerol or sorbitol; monoalkyl or dialkyl isosorbides in which the alkyl groups contain from 1 to 5 carbon atoms, for instance dimethyl isosorbide; glycol ethers, for instance diethylene glycol monomethyl ether or monoethyl ether and propylene glycol ethers, for instance dipropylene glycol methyl ether.
Amphiphilic organic solvents that are exemplary include polypropylene glycol (PPG) derivatives such as fatty acid esters of polypropylene glycol, and derivatives of PPG and of fatty alcohols, for instance PPG-23 oleyl ether, and PPG-36 oleate.
Examples of lipophilic organic solvents that include fatty esters such as diisopropyl adipate, dioctyl adipate or alkyl benzoates.
The compositions in accordance with the present invention may also comprise standard cosmetic adjuvants selected from among softeners, humectants, opacifiers, stabilizers, emollients, silicones, anti-foams, fragrances, preservatives, anionic, cationic, nonionic, zwitterionic or amphoteric surfactants, fillers, polymers, propellants, and acidifying or basifying agents, or any other ingredient usually used in cosmetics and/or dermatology.
Hydrophilic thickeners that are exemplary include carboxyvinyl polymers such as carbopols (carbomers) and the Pemulen products (acrylate/C10-C30-alkylacrylate copolymer) and homopolymers and copolymers of acrylamide and/or of 2-acrylamido-2-methylpropanesulfonic acid (AMPS), for instance sodium polyacryloyldimethyltaurate (and) polysorbate 80 (and) sorbitan oleate marketed under the trademark Simulgel 800 by SEPPIC; cellulose derivatives such as hydroxyethylcellulose; polysaccharides and especially gums such as xanthan gum; and mixtures thereof.
Lipophilic thickeners that are exemplary include modified clays such as hectorite and derivatives thereof, for instance the products marketed under the trademark Bentone.
Preservatives that are exemplary include para-hydroxybenzoic acid esters, also known as Parabens® (in particular methyl paraben, ethyl paraben and propyl paraben), phenoxyethanol, formaldehyde generators, for instance imidazolidinylurea or diazolidinylurea, chlorhexidine digluconate, sodium benzoate, caprylyl glycol, iodopropynyl butyl carbamate, pentylene glycol, alkyltrimethylammonium bromides such as myristyltrimethylammonium bromide (CTFA name: myrtrimonium bromide), dodecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, and mixtures thereof such as the mixture marketed under the trademark Cetrimide® by FEF Chemicals. The preservative may be present in the composition according to the invention in a content ranging from 0.001% to 10% by weight, especially ranging from 0.1% to 5% by weight and in particular ranging from 0.2% to 3% by weight relative to the total weight of the composition.
According to one particular embodiment of the invention, in order to improve the stability of the dehydroascorbic acid or a polymer thereof and/or that of ascorbic acid or a salt or derivative thereof, each of these active agents may be encapsulated according to standard encapsulation techniques.
The processes for artificially coloring the skin and more particularly for artificially tanning the skin may be applied to the various skin types.
According to this scale, the various existing skin types may be distinguished according to the following types:















Type
Skin reactivity
Origin









I
Always burns, never tans
Celtic



II
Always burns, tans very little
Germanic



III
Burns moderately, tans gradually
European



IV
Burns lightly, tans very easily
Mediterranean



V
Rarely burns, tans deeply
Middle Eastern -





South American



VI
Never burns, highly pigmented
African










According to one particularly preferred embodiment of the invention, the composition comprising dehydroascorbic acid or a monomeric derivative thereof of formula (I) and/or an isomer thereof of formula (I′) and/or a polymeric derivative thereof and/or the composition comprising ascorbic acid or a salt or derivative thereof also contain at least one stabilizer and/or at least one photoprotective agent and/or at least one wetting agent and/or at least one penetrant and/or at least one additional dye.
Indeed, in order to improve the stability of dehydroascorbic acid or a monomeri derivative, a polymer or an isomer thereof and/or that of ascorbic acid or a salt or derivative thereof, the compositions in accordance with the invention containing them may also include one or more stabilizers.
Examples of such stabilizers include:
(1) antioxidants,
(2) chelating agents,
(3) non-crosslinked N-vinylimidazole polymers or copolymers such as those described in EP-1-316,302.
According to the invention, the expression “non-crosslinked N-vinylimidazole polymer or copolymer” means any polymer comprising N-vinylimidazole units, and not comprising a crosslinking agent. Copolymers that are suitable for use in the invention are, for example, copolymers comprising N-vinylimidazole units and N-vinylpyrrolidone and/or N-vinylcaprolactam units.
In one advantageous embodiment of the invention, the copolymer has a mole fraction of N-vinylimidazole units of from 0.1 to 1 and more preferentially from 0.4 to 0.9.
According to one advantageous embodiment of the invention, the mole ratio from the N-vinylimidazole unit equivalent and the oxidation-sensitive hydrophilic active agent ranges from 0.004 to 16 and preferentially from 0.01 to 1.
An N-vinylimidazole/N-vinylpyrrolidone copolymer will preferentially be used.
The weight-average molar mass of the N-vinylimidazole polymers will advantageously be from 1000 to 1×107 and preferably from 5,000 to 5×106.
The vinylpyrrolidone/vinylimidazole (50/50) copolymer with a weight-average molar mass of 1,200,000 marketed under the reference Luvitec VPI 55K72W by BASF or the vinylpyrrolidone/vinylimidazole (50/50) copolymer with a weight-average molar mass of 10,000 marketed under the reference Luvitec VPI 55K18P by BASF may be used for this purpose. The polymers or copolymers according to the invention may be prepared, for example, according to the method described in WO 97/45517.
(4) amphiphilic polymers selected from among polyisobutylene-based oligomers or polymers comprising a polyisobutylene apolar portion containing at least 40 carbon atoms and at least one polar end portion constituted of carboxylic or dicarboxylic acids, anhydrides thereof or modified forms thereof in the form of esters, amides or salts, and mixtures thereof as described in U.S. Pat. No. 1,481,677.
These amphiphilic polymers are constituted of a polyisobutylene apolar portion and of at least one polar portion.
The polyisobutylene apolar portion contains at least 40 carbon atoms and preferably from 60 to 700 carbon atoms. It is important for this portion to contain at least 40 carbon atoms in order to achieve the aim of the invention. If there are less than 40 carbon atoms, a satisfactorily stable system is not obtained.
The polar portion of these amphiphilic polymers or oligomers is constituted of carboxylic or dicarboxylic acids, anhydrides thereof or modified forms thereof in the form of esters, amides or salts, and mixtures thereof. Preferably, the polar end portion is constituted of dicarboxylic acids or anhydrides thereof or of modified forms thereof in the form of esters, amides or salts.
The expression “modified forms in the form of esters, amides or salts” is carboxylic or dicarboxylic acids modified with alcohols, amines, alkanolamines or polyols, or, alternatively, in the form of alkali metal, alkaline-earth metal or ammonium salts or, alternatively, in the form of salts of an organic base, for instance the diethanolamine and triethanolamine salts.
The oligomers or polymers derived from succinic acid or anhydride may be selected especially from the polyisobutylene derivatives of succinic acid or anhydride described in U.S. Pat. Nos. 4,234,435, 4,708,753, 5,129,972, 4,931,110, GB-A-2-156,799 and U.S. Pat. No. 4,919,179. The polyisobutylene portion may be hydrogenated or non-hydrogenated, with a molecular weight ranging from 400 to 5,000. In the succinic-terminated polyisobutylene thus obtained, the succinic portion may be esterified, amidated or in salt form, i.e., it may be advantageously modified with alcohols, amines, alkanolamines or polyols, or, alternatively, may be in the form of alkali metal, alkaline-earth metal or ammonium salts or, alternatively, in the form of a salt of an organic base, for instance the diethanolamine and triethanolamine salts. The esterified or amidated succinic-terminated polyisobutylenes are products of reaction of (a) a polyisobutylene containing succinic end groups, and (b) an amine or an alcohol, to form an amide or an ester. The term “amine” used herein includes all types of amines, including alkanolamines. They may be, for example, primary, secondary or tertiary monoamines, these amines possibly being aliphatic, cycloaliphatic, aromatic or heterocyclic, and saturated or unsaturated. Moreover, the alcohols may be monoalcohols or polyalcohols. The monoalcohols comprise primary, secondary or tertiary aliphatic alcohols, and phenols. The polyalcohols may be selected, for example, from aliphatic, cycloaliphatic, aromatic and heterocyclic polyalcohols. The modified (esterified or amidated) succinic-terminated polyisobutylenes and the process for preparing them are described in particular in U.S. Pat. No. 4,708,753.
Succinic-terminated polyisobutylenes that are especially exemplary include modified succinic-terminated polyisobutylenes, such as the products marketed under the trademarks Lubrizol 5603 and Lubrizol 2650 by Lubrizol. According to one preferred embodiment of the invention, the polymer marketed under the trademark Lubrizol 5603 by Lubrizol, which is the diethylethanolamine salt of esterified succinic-terminated polyisobutylene (INCI name: Hydroxyethyldiethonium polyisobutenyl triethylaminosuccinate/diethylethanolamine), is used.
Another example of a polyisobutylene derivative that may be used in the invention is the product of reaction of maleic anhydride with polyisobutylene, such as the product marketed under the trademark Glissopal SA by BASF.
(5) maleic anhydride copolymers comprising one or more maleic anhydride comonomers and one or more comonomers selected from among vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins having from 2 to 20 carbon atoms and styrene, as described in EP-1-374,849.
According to the invention, the term “maleic anhydride copolymer” means any polymer obtained by copolymerization of one or more maleic anhydride comonomers and of one or more comonomers selected from among vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins having from 2 to 20 carbon atoms, for instance octadecene, ethylene, isobutylene, diisobutylene, isooctylene, and styrene, the maleic anhydride comonomers being optionally partially or totally hydrolyzed. Preferably, hydrophilic polymers will be used, i.e., polymers with a solubility in water of greater than or equal to 2 g/l.
Copolymers that are more particularly suitable for use in the invention are copolymers obtained by copolymerization of one or more maleic anhydride units, whose maleic anhydride units are in hydrolyzed form, and preferentially in the form of alkaline salts, for example in the form of ammonium, sodium, potassium or lithium salts.
In one advantageous embodiment of the invention, the copolymer has a mole fraction of maleic anhydride units of from 0.1 and 1 and more preferentially from 0.4 to 0.9.
According to one advantageous embodiment of the invention, the mole ratio from the maleic anhydride unit equivalent and the oxidation-sensitive hydrophilic active agent ranges from 0.005 to 10 and preferentially from 0.01 to 1.
The weight-average molar mass of the maleic anhydride copolymers will advantageously be from 1,000 to 500,000 and preferably from 1,000 to 50,000.
Preferentially, a copolymer of styrene and of maleic anhydride in a 50/50 ratio will be used.
The styrene/maleic anhydride (50/50) copolymer, in the form of the ammonium salt at 30% in water, marketed under the reference SMA1000H® by Atofina, or the styrene/maleic anhydride (50/50) copolymer, in the form of the sodium salt at 40% in water, marketed under the reference SMA1000HNa® by Atofina, may be used, for example.
In order to improve the photostability of dehydroascorbic acid or of a monomeric derivative, a polymeric derivative or an isomer thereof and/or that of ascorbic acid or a salt or derivative thereof, the compositions in accordance with the invention containing them may include one or more photoprotective agents.
The photoprotective agents in accordance with the invention are selected from among UV-A-active and/or UV-B-active organic and/or mineral UV-screening agents that are hydrophilic and/or lipophilic and/or insoluble in the commonly used cosmetic solvents.
The hydrophilic, lipophilic or insoluble organic UV-screening agents are selected especially from anthranilates; dibenzoylmethane derivatives; cinnamic derivatives; salicylic derivatives; camphor derivatives; benzophenone derivatives; β,β-diphenylacrylate derivatives; triazine derivatives; benzotriazole derivatives; benzalmalonate derivatives, especially those cited in U.S. Pat. No. 5,624,663; benzimidazole derivatives; imidazolines; bis-benzazolyl derivatives as described in EP-669,323 and U.S. Pat. No. 2,463,264; p-aminobenzoic acid (PABA) derivatives; methylenebis(hydroxyphenylbenzotriazole) derivatives as described in U.S. Pat. Nos. 5,237,071, 5,166,355, GB-2303549, DE-19726184 and EP-893,119; benzoxazole derivatives as described in EP-0-832,642, EP-1-027,883, EP-1-300,137 and DE-10162844; screening polymers and screening silicones such as those described especially in WO 93/04665; α-alkylstyrene-based dimers, such as those described in DE-19855649; 4,4-diarylbutadienes such as those described in EP-0-967,200, DE-19746654, DE-19755649, EP-A-1-008,586, EP-1-133,980 and EP-133,981, and mixtures thereof.
As examples of organic UV-screening agents, representative are those denoted herein below under their INCI name:
Para-Aminobenzoic Acid Derivatives:
PABA,
Ethyl PABA,
Ethyl dihydroxypropyl PABA,
Ethylhexyl dimethyl PABA marketed in particular under the trademark “Escalol 507” by ISP,
Glyceryl PABA,
PEG-25 PABA marketed under the trademark “Uvinul P25” by BASF.
Dibenzoylmethane Derivatives:
Butylmethoxydibenzoylmethane marketed especially under the trademark “Parsol 1789” by Hoffmann LaRoche,
Isopropyldibenzoylmethane.
Salicylic Derivatives:
Homosalate marketed under the trademark “Eusolex HMS” by Rona/EM Industries,
Ethylhexyl salicylate marketed under the trademark “Neo Heliopan OS” by Haarmann and Reimer,
Dipropylene glycol salicylate marketed under the trademark “Dipsal” by Scher,
TEA salicylate marketed under the trademark “Neo Heliopan TS” by Haarmann and Reimer.
Cinnamic Derivatives:
Ethylhexyl methoxycinnamate marketed in particular under the trademark “Parsol MCX” by Hoffmann LaRoche,
Isopropyl methoxycinnamate,
Isoamyl methoxycinnamate marketed under the trademark “Neo Heliopan E 1000” by Haarmann and Reimer,
Cinoxate,
DEA methoxycinnamate,
Diisopropyl methylcinnamate,
Glyceryl ethylhexanoate dimethoxycinnamate.
β,β-Diphenylacrylate Derivatives:
Octocrylene marketed in particular under the trademark “Uvinul N539” by BASF,
Etocrylene marketed in particular under the trademark “Uvinul N35” by BASF.
Benzophenone Derivatives:
Benzophenone-1 marketed under the trademark “Uvinul 400” by BASF,
Benzophenone-2 marketed under the trademark “Uvinul D50” by BASF,
Benzophenone-3 or Oxybenzone marketed under the trademark “Uvinul M40” by BASF,
Benzophenone-4 marketed under the trademark “Uvinul MS40” by BASF,
Benzophenone-5,
Benzophenone-6 marketed under the trademark “Helisorb 11” by Norquay,
Benzophenone-8 marketed under the trademark “Spectra-Sorb UV-24” by American Cyanamid,
Benzophenone-9 marketed under the trademark “Uvinul DS-49” by BASF,
Benzophenone-12
n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate.
Benzylidenecamphor Derivatives:
3-Benzylidenecamphor marketed under the trademark “Mexoryl SD” by Chimex,
4-Methylbenzylidenecamphor marketed under the trademark “Eusolex 6300” by Merck,
Benzylidenecamphorsulfonic acid marketed under the trademark “Mexoryl SL” by Chimex,
Camphor benzalkonium methosulfate marketed under the trademark “Mexoryl SO” by Chimex,
Terephthalylidenedicamphorsulfonic acid marketed under the trademark “Mexoryl SX” by Chimex,
Polyacrylamidomethylbenzylidenecamphor marketed under the trademark “Mexoryl SW” by Chimex.
Phenylbenzimidazole Derivatives:
Phenylbenzimidazolesulfonic acid marketed in particular under the trademark “Eusolex 232” by Merck,
Disodium phenyl dibenzimidazole tetrasulfonate marketed under the trademark “Neo Heliopan AP” by Haarmann and Reimer.
Phenylbenzotriazole Derivatives:
Drometrizole trisiloxane marketed under the trademark “Silatrizole” by Rhodia Chimie,
Methylenebis(benzotriazolyl)tetramethylbutylphenol marketed in solid form under the trademark “MIXXIM BB/100” by Fairmount Chemical, or in micronized form as an aqueous dispersion under the trademark “Tinosorb M” by Ciba Specialty Chemicals.
Triazine Derivatives:
bis-Ethylhexyloxyphenol methoxyphenyl triazine marketed under the trademark Tinosorb S by Ciba Geigy, Ethylhexyl triazone marketed in particular under the trademark Uvinul T150 by BASF,
Diethylhexyl butamido triazone marketed under the trademark Uvasorb HEB by Sigma 3V,
2,4,6-tris(Dineopentyl 4′-aminobenzalmalonate)-s-triazine the symmetrical triazine screening agents described in U.S. Pat. No. 6,225,467, WO 2004/085 412 (see compounds 6 and 9) or the document “Symmetrical Triazine Derivatives” IP.COM Journal, IP.COM INC WEST HENRIETTA, N.Y., US (20 Sep. 2004), especially 2,4,6-tris(biphenyl)-1,3,5-triazines (in particular 2,4,6-tris(biphenyl-4-yl-1,3,5-triazine) and 2,4,6-tris(terphenyl)-1,3,5-triazine which is also mentioned in WO 06/035 000, WO 06/034 982, WO 06/034 991, WO 06/035 007, WO 2006/034 992 and WO 2006/034 985.
Anthranilic Derivatives:
Menthyl anthranilate marketed under the trademark “Neo Heliopan MA” by Haarmann and Reimer.
Imidazoline Derivatives:
Ethylhexyldimethoxybenzylidenedioxoimidazoline propionate.
Benzalmalonate Derivatives:
Dineopentyl 4′-methoxybenzalmalonate
Polyorganosiloxane containing benzalmalonate functions, for instance Polysilicone-15, marketed under the trademark “Parsol SLX” by Hoffmann LaRoche
4,4-Diarylbutadiene Derivatives:
1,1-Dicarboxy(2,2′-dimethylpropyl)-4,4-diphenylbutadiene
Benzoxazole Derivatives:
2,4-bis[5-(1-dimethylpropyl)benzoxazol-2-yl(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine marketed under the trademark Uvasorb K2A by Sigma 3V
and mixtures thereof.
The preferred organic UV-screening agents are selected from among:
Ethylhexyl methoxycinnamate,
Homosalate,
Ethylhexyl salicylate,
Octocrylene,
Phenylbenzimidazolesulfonic acid,
Benzophenone-3,
Benzophenone-4,
Benzophenone-5,
n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate,
4-Methylbenzylidenecamphor,
Terephthalylidenedicamphorsulfonic acid,
Disodium phenyldibenzimidazoletetrasulfonate,
Ethylhexyl triazone,
bis-Ethylhexyloxyphenol methoxyphenyl triazine,
Diethylhexyl butamido triazone,
2,4,6-tris(Dineopentyl 4′-aminobenzalmalonate)-s-triazine,
2,4,6-tris(Diisobutyl 4′-aminobenzalmalonate)-s-triazine,
2,4,6-tris(Biphenyl-4-yl-1,3,5-triazine),
2,4,6-tris(Terphenyl)-1,3,5-triazine
Methylenebis(benzotriazolyl)tetramethylbutylphenol,
Drometrizole trisiloxane,
Polysilicone-15,
Dineopentyl 4′-methoxybenzalmalonate,
1,1-Dicarboxy(2,2′-dimethylpropyl)-4,4-diphenylbutadiene,
2,4-bis[5-1 (Dimethylpropyl)benzoxazol-2-yl(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine,
and mixtures thereof.
The inorganic screening agents are selected from among pigments (mean size of the primary particles: generally from 5 nm to 100 nm and preferably from 10 nm to 50 nm) of coated or uncoated metal oxides, for instance nanopigments of titanium oxide (amorphous or crystallized in rutile and/or anatase form), of iron oxide, of zinc oxide, of zirconium oxide or of cerium oxide, which are all UV photoprotective agents that are well known per se.
The pigments may be coated or uncoated.
The coated pigments are pigments that have undergone one or more surface treatments of chemical, electronic, mechanochemical and/or mechanical nature with compounds as described, for example, in Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53-64, such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminum salts of fatty acids, metal alkoxides (of titanium or of aluminum), polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.
As is known, silicones are organosilicon polymers or oligomers of linear or cyclic, branched or crosslinked structure, of variable molecular weight, obtained by polymerization and/or polycondensation of suitably functionalized silanes, and consist essentially of a repetition of main units in which the silicon atoms are linked together via oxygen atoms (siloxane bond), optionally substituted hydrocarbon-based radicals being directly attached via a carbon atom to the said silicon atoms.
The term “silicones” also includes the silanes required for their preparation, in particular alkyl silanes.
The silicones used for coating the pigments that are suitable for the present invention are preferably selected from among the group containing alkyl silanes, polydialkylsiloxanes and polyalkylhydrogenosiloxanes. Even more preferentially, the silicones are selected from among the group containing octyltrimethylsilane, polydimethylsiloxanes and polymethylhydrogenosiloxanes.
Indeed, before being treated with silicones, the metal oxide pigments may have been treated with other surface agents, in particular with cerium oxide, alumina, silica, aluminum compounds or silicon compounds, or mixtures thereof.
The coated pigments are more particularly titanium oxides that have been coated:
with silica, such as the product “Sunveil” by Ikeda,
with silica and iron oxide, such as the product “Sunveil F” by Ikeda,
with silica and alumina, such as the products “Microtitanium Dioxide MT 500 SA” and “Microtitanium Dioxide MT 100 SA” by Tayca, “Tioveil” by Tioxide and “Mirasun TiW 60” by Rhodia,
with alumina, such as the products “Tipaque TTO-55 (B)” and “Tipaque TTO-55 (A)” by Ishihara and “UVT 14/4” by Kemira,
with alumina and aluminum stearate, such as the product “Microtitanium Dioxide MT 100 T, MT 100 TX, MT 100 Z and MT-01 by Tayca, the products “Solaveil CT-10 W” and “Solaveil CT 100” by Uniqema, and the product “Eusolex T-AVO” by Merck,
with silica, alumina and alginic acid, such as the product “MT-100 AQ” by Tayca,
with alumina and aluminum laurate, such as the product “Microtitanium Dioxide MT 100 S” by Tayca,
with iron oxide and iron stearate, such as the product “Microtitanium Dioxide MT 100 F” by Tayca,
with zinc oxide and zinc stearate, such as the product “BR351” by Tayca,
with silica and alumina and treated with a silicone, such as the products “Microtitanium Dioxide MT 600 SAS”, “Microtitanium Dioxide MT 500 SAS” or “Microtitanium Dioxide MT 100 SAS” by Tayca,
with silica, alumina and aluminum stearate and treated with a silicone, such as the product “STT-30-DS” by Titan Kogyo,
with silica and treated with a silicone, such as the product “UV-Titan X 195” by Kemira,
with alumina and treated with a silicone, such as the products “Tipaque TTO-55 (S)” by Ishihara or “UV Titan M 262” by Kemira,
with triethanolamine, such as the product “STT-65-S” by Titan Kogyo,
with stearic acid, such as the product “Tipaque TTO-55 (C)” by Ishihara,
with sodium hexametaphosphate, such as the product “Microtitanium Dioxide MT 150 W” by Tayca.
Other titanium oxide pigments treated with a silicone are preferably TiO2 treated with octyltrimethylsilane and for which the mean size of the elementary particles ranges from 25 and 40 nm, such as the product marketed under the trademark “T 805” by Degussa Silices, TiO2 treated with a polydimethylsiloxane and for which the mean size of the elementary particles is 21 nm, such as the product marketed under the trademark “70250 Cardre UF TiO2SI3” by Cardre, anatase/rutile TiO2 treated with a polydimethylhydrogenosiloxane and for which the mean size of the elementary particles is 25 nm, such as the product marketed under the trademark “Microtitanium Dioxide USP Grade Hydrophobic” by Color Techniques.
The uncoated titanium oxide pigments are marketed, for example, by Tayca under the trademarks “Microtitanium Dioxide MT 500 B” or “Microtitanium Dioxide MT 600 B”, by Degussa under the trademark “P 25”, by Wacker under the trademark “Transparent titanium oxide Pw”, by Myoshi Kasei under the trademark “UFTR”, by Tomen under the trademark “ITS” and by Tioxide under the trademark “Tioveil AQ”.
The uncoated zinc oxide pigments are, for example:
those marketed under the trademark “Z-Cote” by Sunsmart;
those marketed under the trademark “Nanox” by Elementis;
those marketed under the trademark “Nanogard WCD 2025” by Nanophase Technologies.
The coated zinc oxide pigments are, for example:
those marketed under the trademark “Zinc Oxide CS-5” by Toshibi (ZnO coated with polymethylhydrogenosiloxane);
those marketed under the trademark “Nanogard Zinc Oxide FN” by Nanophase Technologies (as a 40% dispersion in Finsolv TN, C12-C15 alkyl benzoate);
those marketed under the trademark “Daitopersion ZN-30” and “Daitopersion ZN-50” by Daito (dispersions in cyclopolymethylsiloxane/oxyethylenated polydimethylsiloxane, containing 30% or 50% of nanozinc oxides coated with silica and polymethylhydrogenosiloxane);
those marketed under the trademark “NFD Ultrafine ZNO” by Daikin (ZnO coated with perfluoroalkyl phosphate and copolymer based on perfluoroalkylethyl as a dispersion in cyclopentasiloxane);
those marketed under the trademark “SPD-Z1” by Shin-Etsu (ZnO coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane);
those marketed under the trademark “Escalol Z100” by ISP (alumina-treated ZnO dispersed in an ethylhexyl methoxycinnamate/PVP-hexadecene/meth icone copolymer mixture);
those marketed under the trademark “Fuji ZNO-SMS-10” by Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane);
those marketed under the trademark “Nanox Gel TN” by Elementis (ZnO dispersed at a concentration of 55% in C12-C15 alkyl benzoate with hydroxystearic acid polycondensate).
The uncoated cerium oxide pigments are marketed under the trademark “Colloidal Cerium Oxide” by Rhone-Poulenc.
The uncoated iron oxide nanopigments are marketed, for example, by Arnaud under the trademarks “Nanogard WCD 2002 (FE 45B)”, “Nanogard Iron FE 45 BL AQ”, “Nanogard FE 45R AQ” and “Nanogard WCD 2006 (FE 45R)” or by Mitsubishi under the trademark “TY-220”.
The coated iron oxide pigments are marketed, for example, by Arnaud under the trademarks “Nanogard WCD 2008 (FE 45B FN)”, “Nanogard WCD 2009 (FE 45B 556)”, “Nanogard FE 45 BL 345” and “Nanogard FE 45 BL” or by BASF under the trademark “Transparent Iron Oxide”.
Also exemplary are the mixtures of metal oxides, especially of titanium dioxide and of cerium dioxide, including the silica-coated equal-weight mixture of titanium dioxide and of cerium dioxide, marketed by Ikeda under the trademark “Sunveil A”, and also the alumina, silica and silicone-coated mixture of titanium dioxide and of zinc dioxide, such as the product “M 261” marketed by Kemira, or the alumina, silica and glycerol-coated mixture of titanium dioxide and of zinc dioxide, such as the product “M 211” marketed by Kemira.
The photoprotective agents are generally present in the compositions containing dehydroascorbic acid or a polymer thereof and/or the compositions comprising ascorbic acid or a salt or derivative thereof in proportions ranging from 0.01% to 20% by weight relative to the total weight of the composition, and preferably ranging from 0.1% to 10% by weight relative to the total weight of the composition.
In order to increase the remanence of the skin color and/or the homogeneity of the color, the compositions containing dehydroascorbic acid or a monomeric derivative, a polymeric derivative or an isomer thereof and/or the compositions comprising ascorbic acid or a salt or derivative thereof according to the invention may also additionally comprise at least a wetting agent and/or penetrant, for instance urea, hydroxyethylurea, polyols such as glycerol, alkylene glycols such as propylene glycol or butylene glycol, or alkylene glycol alkyl ethers such as propylene glycol monomethyl ether.
In order to adjust the color obtained via the various artificial coloring processes as described above and to better adapt it to the various types of skin tone, the compositions containing dehydroascorbic acid or a monomeric derivative, a polymeric derivative or an isomer thereof and/or the compositions comprising ascorbic acid or a salt or derivative thereof in accordance with the present invention may also comprise one or more additional coloring agents.
The additional coloring agents may be selected especially from natural and synthetic direct dyes. They may be organic or mineral dyes.
The mineral dyes may be, for example, iron oxide pigments whose mean elementary particle size is less than 100 nm, such as those described in EP-966,953.
The natural or synthetic liposoluble organic dyes are, for example, DC Red 17, DC Red 21, DC Red 27, DC Green 6, DC Yellow 11, DC Violet 2, DC Orange 5, Sudan red, carotenes (β-carotene or lycopene), xanthophylls (capsanthin, capsorubin or lutein), palm oil, Sudan brown, quinoline yellow, annatto and curcumin.
The natural or synthetic water-soluble dyes are, for example, FDC Red 4, DC Red 6, DC Red 22, DC Red 28, DC Red 30, DC Red 33, DC Orange 4, DC Yellow 5, DC Yellow 6, DC Yellow 8, FDC Green 3, DC Green 5, FDC Blue 1, betanin (beetroot), carmine, copper-containing chlorophylline, methylene blue, anthocyanins (enocyanin, black carrot, hibiscus or elder) and riboflavin.
The dyes may also be selected from among anthraquinones, caramel, carmine, carbon black, azulene blues, methoxalene, trioxalene, guajazulene, chamuzulene, rose Bengal, cosine 10B, cyanosin, daphinine, juglone, lawsone, extracts of fermented soya, of algae, of fungi or of microorganisms, flavylium salts not substituted in position 3, for instance those described in EP-1-172,091, extracts of Gesneria fulgens, Blechum procerum or Saxifraga and pigments that may be obtained by extraction with an organic or aqueous-organic solvent of a culture medium of micromycetes of the Monascus type.
These dyes may also be selected from among indole derivatives, for instance the monohydroxyindoles as described in FR-2,651,126 (i.e.: 4-, 5-, 6- or 7-hydroxyindole) or the dihydroxyindoles as described in EP-B-0-425,324 (i.e.: 5,6-dihydroxyindole, 2-methyl-5,6-dihydroxyindole, 3-methyl-5,6-dihydroxyindole or 2,3-dimethyl-5,6-dihydroxyindole).
The compositions according to the invention may also comprise additional active agents selected especially from moisturizers, desquamating agents, agents for improving the barrier function, depigmenting agents, antioxidants, dermo-decontracting agents, anti-glycation agents, agents for stimulating the synthesis of dermal and/or epidermal macromolecules and/or for preventing their degradation, agents for stimulating fibroblast or keratinocyte proliferation and/or keratinocyte differentiation, agents for promoting the maturation of the horny envelope, NO-synthase inhibitors, peripheral benzodiazepine receptor (PBR) antagonists, agents for increasing the activity of the sebaceous glands, agents for stimulating the energy metabolism of cells, tensioning agents, lipo-restructuring agents, slimming agents, agents for promoting the cutaneous capillary circulation, calmatives and/or anti-irritants, sebo-regulators or anti-seborrhoeic agents, astringents, cicatrizing agents, anti-inflammatory agents and anti-acne agents.
One skilled in the art will select the said active agent(s) as a function of the effect desired on the skin, the lips, the nails, the eyelashes or the eyebrows.
The compositions according to the invention may also comprise at least one additional ingredient for complementing the biological effect of these active agents or for providing an immediate visual effect; mention may be made especially of matting agents, fillers with a hazy effect, fluorescers, agents for promoting the naturally pinkish coloration of the skin and abrasive or exfoliant fillers.
Of course, one skilled in the art will take care to select this or these optional additional compound(s), and/or the amount thereof, such that the advantageous properties of the corresponding composition according to the invention are not, or are not substantially, adversely affected by the envisaged addition.
For caring for aged skin, one will preferably choose at least one active agent selected from among moisturizers, desquamating agents, agents for improving the barrier function, depigmenting agents, antioxidants, dermo-decontracting agents, anti-glycation agents, agents for stimulating the synthesis of dermal and/or epidermal macromolecules and/or for preventing their degradation, agents for stimulating fibroblast or keratinocyte proliferation and/or keratinocyte differentiation, agents for promoting the maturation of the horny envelope, NO-synthase inhibitors, peripheral benzodiazepine receptor (PBR) antagonists, agents for increasing the activity of the sebaceous glands, agents for stimulating the energy metabolism of cells, lipo-restructuring agents, and agents for promoting the cutaneous capillary circulation for the area around the eyes.
For caring for greasy skin, one skilled in the art will preferably choose at least one active agent selected from among desquamating agents, sebo-regulating agents or anti-seborrhoeic agents, and astringents.
At least one active agent selected from among anti-acne agents, cicatrizing agents and anti-inflammatory agents will preferably be selected for caring for acne-prone skin.
For slimming care of the body, one will preferably choose an active agent selected from among slimming active agents and active agents for promoting the cutaneous capillary circulation.
Examples of such compounds are described below.
Moisturizers or Humectants:
Moisturizers or humectants that are exemplary include glycerol and derivatives thereof, urea and derivatives thereof, especially Hydrovance® marketed by National Starch, lactic acid, hyaluronic acid, AHAs, BHAs, sodium pidolate, xylitol, serine, sodium lactate, ectoin and derivatives thereof, chitosan and derivatives thereof, collagen, plankton, an extract of Imperata cylindra marketed under the trademark Moist 24® by Sederma, acrylic acid homopolymers, for instance Lipidure-HM® from NOF Corporation, beta-glucan and in particular sodium carboxymethyl beta-glucan from Mibelle-AG-Biochemistry; a mixture of passionflower oil, apricot oil, corn oil and rice bran oil marketed by Nestle under the trademark NutraLipids®; a C-glycoside derivative such as those described in WO 02/051 828 and in particular C-β-D-xylopyranoside-2-hydroxypropane in the form of a solution containing 30% by weight of active material in a water/propylene glycol mixture (60/40% by weight) such as the product marketed by Chimex under the trademark Mexoryl SBB®; an oil of musk rose marketed by Nestlé; an extract of the microalga Prophyridium cruentum enriched with zinc, marketed by Vincience under the trademark Algualane Zinc®; spheres of collagen and of chondroitin sulfate of marine origin (Atelocollagen) marketed by Engelhard Lyon under the trademark Marine Filling Spheres; hyaluronic acid spheres such as those marketed by Engelhard Lyon; and arginine.
The moisturizer is preferably selected from urea and derivatives thereof, especially Hydrovance® marketed by National Starch, hyaluronic acid, AHAs, BHAs, acrylic acid homopolymers, for instance Lipidure-HM® from NOF Corporation, beta-glucan and in particular sodium carboxymethyl beta-glucan from Mibelle-AG-Biochemistry; a mixture of passionflower oil, apricot oil, corn oil and rice bran oil marketed by Nestlé under the trademark NutraLipids®; a C-glycoside derivative such as those described in WO 02/051 828 and in particular C-β-D-xylopyranoside-2-hydroxypropane in the form of a solution containing 30% by weight of active material in a water/propylene glycol mixture (60/40% by weight) such as the product marketed by Chimex under the trademark Mexoryl SBB®; an oil of musk rose marketed by Nestlé; an extract of the microalga Prophyridium cruentum enriched with zinc, marketed by Vincience under the trademark Algualane Zinc®; spheres of collagen and of chondroitin sulfate of marine origin (Atelocollagen) marketed by Engelhard Lyon under the trademark Marine Filling Spheres; hyaluronic acid spheres such as those marketed by Engelhard Lyon; and arginine.
Desquamating Agents:
The term “desquamating agent” means any compound capable of acting:
either directly on desquamation by promoting exfoliation, such as β-hydroxy acids (BHA), in particular salicylic acid and derivatives thereof (including 5-n-octanoylsalicylic acid, also known as capryloyl salicylic acid as the INCI name); α-hydroxy acids (AHA), such as glycolic acid, citric acid, lactic acid, tartaric acid, malic acid or mandelic acid; 8-hexadecene-1,16-dicarboxylic acid or 9-octadecenedioic acid; urea and derivatives thereof; gentisic acid and derivatives thereof; oligofucoses; cinnamic acid; Saphora japonica extract; resveratrol, and certain jasmonic acid derivatives;
or on the enzymes involved in the desquamation or degradation of corneodesmosomes, glycosidases, stratum corneum chymotryptic enzyme (SCCE) or other proteases (trypsin, chymotrypsin-like). Exemplary are aminosulfonic compounds and in particular 4-(2-hydroxyethyl)piperazine-1-propanesulfonic acid (HEPES); 2-oxothiazolidine-4-carboxylic acid (procysteine) and derivatives thereof; derivatives of α-amino acids of glycine type (as described in EP-0-852,949, and also sodium methyl glycine diacetate marketed by BASF under the trademark Trilon M); honey; sugar derivatives such as O-octanoyl-6-D-maltose and N-acetylglucosamine.
As other desquamating agents that may be included in the composition according to the invention, exemplary are:
oligofructoses, EDTA and derivatives thereof, laminaria extracts, o-linoleyl-6D-glucose, (3-hydroxy-2-pentylcyclopentyl)acetic acid, glycerol trilactate, O-octanyl-6′-D-maltose, S-carboxymethylcysteine, siliceous derivatives of salicylate such as those described in EP-0-796,861, oligofucases such as those described in EP-0-218,200, 5-acyl salicylic acid salts, actives with effects on transglutaminase, as in EP-0-899,330,
extract of the flowers of ficus Opuntia indica such as Exfolactive® from Silab,
8-hexadecene-1,16-dicarboxylic acid,
esters of glucose and of vitamin F, and
mixtures thereof.
Preferred desquamating agents include β-hydroxy acids such as 5-n-octanoyl salicylic acid; urea; glycolic acid, citric acid, lactic acid, tartaric acid, malic acid or mandelic acid; 4-(2-hydroxyethyl)piperazine-1-propanesulfonic acid (HEPES); extract of Saphorajaponica; honey; N-acetyl glucosamine; sodium methyl glycine diacetate, and mixtures thereof.
Even more preferentially, a desquamating agent selected from 5-n-octanoyl salicylic acid; urea; 4-(2-hydroxyethyl)piperazine-1-propanesulfonic acid (HEPES); extract of Saphorajaponica; honey; N-acetyl glucosamine; sodium methyl glycine diacetate, and mixtures thereof, will be included in the compositions of the invention.
Agents for Improving the Barrier Function:
As agents for improving the barrier function, especially exemplary are arginine, serine, an extract of Thermus thermophilus such as Venuceane® from Sederma, an extract of the rhizome of wild yam (Dioscorea villosa) such as Actigen Y® from Active Organics, plankton extracts, for instance Omega Plankton® from Secma, yeast extracts, for instance Relipidium® from Coletica, a chestnut extract such as Recoverine® from Silab, a cedar bud extract such as Gatuline Zen® from Gattefossé, sphingosines, for instance salicyloyl sphingosine marketed under the trademark Phytosphingosine® SLC by Degussa, a mixture of xylitol, polyxylityl glycoside and xylitan, for instance Aquaxyl® from SEPPIC, extracts of Solanacea plants, for instance Lipidessence® from Coletica, omega 3 unsaturated oils such as oils of musk rose; and mixtures thereof.
Especially exemplary are ceramides or derivatives thereof, in particular ceramides of type 2 (for instance N-oleoyldihydrosphingosine), of type 3 (for instance stearoyl-4-hydroxysphinganine, as the INCI name) and of type 5 (for instance N-2-hydroxypalmitoyldihydrosphingosine, having the INCI name: hydroxypalmitoyl sphinganine), sphingoid-based compounds, glycosphingolipids, phospholipids, cholesterol and derivatives thereof, phytosterols, essential fatty acids, diacylglycerol, 4-chromanone and chromone derivatives, petroleum jelly, lanolin, shea butter, cocoa butter, lanolin and PCA salts.
As preferred agents having a restructuring effect on the cutaneous barrier, exemplary are an extract of Thermus thermophilus, an extract of wild yam rhizome (Dioscorea villosa), a yeast extract, a chestnut extract, a cedar bud extract, arginine, serine, ceramides especially of type 3 and 5; and mixtures thereof.
Serine, arginine or a mixture thereof will preferably be employed.
Depigmenting Agents:
Depigmenting agents that are especially exemplary include vitamin C and derivatives thereof and especially vitamin CG, CP and 3-O ethyl vitamin C, alpha and beta arbutin, ferulic acid, lucinol and derivatives thereof, kojic acid, resorcinol and derivatives thereof, tranexamic acid and derivatives thereof, gentisic acid, homogentisate, methyl gentisate or homogentisate, dioic acid, calcium D-pantheteine sulfonate, lipoic acid, ellagic acid, vitamin B3, linoleic acid and derivatives thereof, ceramides and homologues thereof, plant derivatives, for instance camomile, bearberry, the aloe family (vera, ferox, bardensis), mulberry or skullcap; a kiwi fruit (Actinidia chinensis) juice marketed by Gattefossé, an extract of Paeonia suffruticosa root, such as the product marketed by Ichimaru Pharcos under the trademark Botanpi Liquid B®, an extract of brown sugar (Saccharum officinarum), such as the molasses extract marketed by Taiyo Kagaku under the trademark Molasses Liquid, without this list being exhaustive.
As preferred depigmenting agents, exemplary are vitamin C and its derivatives and especially vitamin CG, vitamin CP and 3-O-ethyl-vitamin C, alpha- and beta-arbutin, ferulic acid, kojic acid, resorcinol and its derivatives, calcium D-pantetheine sulfonate, lipoic acid, ellagic acid, vitamin B3, a kiwi fruit juice (Actinidia chinensis) marketed by Gattefossé, an extract of Paeonia suffruticosa root such as that marketed by Ichimaru Pharcos under the trademark BOTANPI LIQUID B®.
Antioxidants:
Especially exemplary are tocopherol and esters thereof, in particular tocopherol acetate; ascorbic acid and derivatives thereof, in particular magnesium ascorbyl phosphate and ascorbyl glucoside; ferulic acid; serine; ellagic acid, phloretin, polyphenols, tannins, tannic acid, epigallocatechins and natural extracts containing them, anthocyans, rosemary extracts, olive leaf extracts, for instance those by Silab, green tea extracts, resveratrol and derivatives thereof, ergothioneine, N-acetylcysteine, an extract of the brown alga Pelvetia canaliculata, for instance Pelvetiane® from Secma, chlorogenic acid, biotin, chelating agents, such as BHT and BHA, N,N′-bis(3,4,5-trimethoxybenzyl)ethylenediamine and salts thereof; idebenone, plant extracts, for instance Pronalen BioprotectTM by Provital; coenzyme Q10, bioflavonoids, SODs, phytantriol, lignans, melatonin, pidolates, glutathione, caprylyl glycol, phloretin, TotarolTM or extract of Podocarpus totara containing Totarol (totara-8,11,13-trienol or 2-phenanthrenol, 4b,5,6,7,8,8a,9,10-octahydro-4b,8,8-trimethyl-1-(1-methylethyl)-; a jasmine extract such as the product marketed by Silab under the trademark Helisun®; hesperitin laurate such as Flavagrum PEG® by Engelhard Lyon; an extract of Paeonia suffruticosa root, such as the product marketed by Ichimaru Pharcos under the trademark Botanpi Liquid B® a lychee extract such as the lychee pericarp extract marketed by Cognis under the trademark Litchiderm LS 9704®, a pomegranate extract (Punica granatum), such as the product marketed by Draco Natural Products.
Other anti-aging agents that are exemplary include DHEA and derivatives thereof, boswellic acid, rosemary extracts, carotenoids (β-carotene, zeaxanthin and lutein), cysteic acid, copper derivatives and jasmonic acid.
Preferred antioxidants include ferulic acid; serine; phloretin, a pomegranate extract, biotin, chelating agents such as BHT, BHA, N,N′-bis(3,4,5-trimethoxybenzyl)ethylenediamine and salts thereof; caprylyl glycol, phloretin, TotarolTM, a jasmine extract such as the product marketed by Silab under the trademark Helisun®; hesperitin laurate such as Flavagrum PEG® by Engelhard Lyon; an extract of Paeonia suffruticosa root, such as the product marketed by Ichimaru Pharcos under the trademark Botanpi Liquid B®.
Dermo-Relaxing or Dermo-Decontracting Agents:
Examples thereof include manganese gluconate and other salts, adenosine, alverine citrate and salts thereof, glycine, an extract of Iris pallida, a hexapeptide (Argeriline R from Lipotec) or sapogenins, for instance wild yam and the carbonyl amines described in EP-1-484,052. Examples of sapogenins include those described in WO 02/47650, in particular wild yam, the diosgenin extracted especially from Dioscorea opposita or any extract naturally containing or containing after treatment one or more sapogenins (wild yam rhizome, agave leaf, which contains hecogenin and tigogenin, extracts of Liliacea plants and more particularly yucca or smilax containing smilagenin and sarsapogenin, or sarsaparilla root) or Actigen Y by Actives Organics; or ginger.
Also exemplary are DMAE (dimethyl MEA), extracts of sea fennel, of rockrose, of helichrysum, of anise, of paracress, and an extract of Acmella oleracea, for instance Gatuline® from Gattefossé.
Preferred dermo-relaxing agents include adenosine, manganese gluconate, wild yam, sea fennel, glycine and alverine.
Anti-Glycation Agents:
The term “anti-glycation agent” means a compound that prevents and/or reduces the glycation of skin proteins, in particular dermal proteins such as collagen.
Anti-glycation agents that are exemplary include extracts of plants of the Ericacea family, such as an extract of blueberry (Vaccinium angustifolium or Vaccinium myrtillus), for example the product marketed under the trademark Blueberry Herbasol Extract PG by Cosmetochem, ergothioneine and derivatives thereof, hydroxystilbenes and derivatives thereof, such as resveratrol and 3,3′,5,5′-tetrahydroxystilbene (these anti-glycation agents are described in FR 2,802,425, FR 2,810,548, FR 2,796,278 and FR 2,802,420, respectively), dihydroxystilbenes and derivatives thereof, polypeptides of arginine and of lysine such as the product marketed under the trademark Amadorine® by Solabia, carcinine hydrochloride (marketed by Exsymol under the trademark Alistin®), an extract of Helianthus annuus, for instance Antiglyskin® from Silab, wine extracts such as the extract of powdered white wine on a maltodextrin support marketed under the trademark Vin blanc déshydraté 2F by Givaudan, thioctic acid (or alpha-lipoic acid), a mixture of extract of bearberry and of marine glycogen, for instance Aglycal LS 8777® from Laboratoires Sérobiologiques, and an extract of black tea, for instance Kombuchka® from Sederma, and mixtures thereof.
Preferred anti-glycation agents include extracts of blueberry (Vaccinium myrtillus) and extract of black tea.
Agents for Stimulating the Synthesis of Dermal and/or Epidermal Macromolecules and/or for Preventing their Degradation:
Among the active agents for stimulating the dermal macromolecules or for preventing their degradation, exemplary are those acting:
either on collagen synthesis, such as extracts of Centella asiatica, asiaticosides and derivatives thereof; ascorbic acid or vitamin C and derivatives thereof; synthetic peptides such as iamin, biopeptide CL or palmitoyl oligopeptide marketed by Sederma; peptides extracted from plants, such as the soybean hydrolysate marketed by Coletica under the trademark Phytokine®; rice peptides such as Nutripeptide® from Silab, methylsilanol mannuronate such as Algisium C® marketed by Exsymol; plant hormones such as auxins and lignans; folic acid; and an extract of Medicago sativa (alfalfa) such as the product marketed by Silab under the trademark Vitanol®; a peptide extract of hazelnut such as the product marketed by Solabia under the trademark Nuteline C®; and arginine;
or on the inhibition of collagen degradation, in particular agents acting on the inhibition of metalloproteases (MMP) more particularly such as MMP 1, 2, 3 and 9. Mention may be made of: retinoids and derivatives, extracts of Medicago sativa such as Vitanol® from Silab, an extract of Aphanizomenon flos-aquae (Cyanophyceae) marketed under the trademark Lanablue® by Atrium Biotechnologies, oligopeptides and lipopeptides, lipoamino acids, the malt extract marketed by Coletica under the trademark Collalift®; blueberry or rosemary extracts; lycopene; isoflavones, derivatives thereof or plant extracts containing them, in particular extracts of soybean (marketed, for example, by Ichimaru Pharcos under the trademark Flavosterone SB®), of red clover, of flax or of kakkon; an extract of lychee such as the lychee pericarp extract marketed by Cognis under the trademark Litchiderm LS 9704®; Dipalmitoyl Hydroxyproline marketed by SEPPIC under the trademark Sepilift DPHP®: Baccharis genistelloide or Baccharine marketed by Silab, an extract of moring a such as Arganyl LS 9781® from Cognis; the sage extract described in FR-A-2 812 544 from the Labiatae family (Salvia officinalranges by Flacksmann), an extract of rhododendron, a blueberry extract, and an extract of Vaccinium myrtillus such as those described in FR-A-2 814 950;
or on the synthesis of molecules belonging to the elastin family (elastin and fibrillin), such as: retinol and derivatives, in particular retinol palmitate; the extract of Saccharomyces cerevisiae marketed by LSN under the trademark Cytovitin®; and the extract of the alga Macrocystis pyrifera marketed by Secma under the trademark Kelpadelie®; a peptide extract of hazelnut such as the product marketed by Solabia under the trademark Nuteline C®;
or on inhibition of elastin degradation, such as the peptide extract of seeds of Pisum sativum marketed by LSN under the trademark Parelastyl®; heparinoids; and the N-acylamino amide compounds described in WO 01/94381, such as {2-[acetyl(3-trifluoromethylphenyl)amino]-3-methylbutyrylamino}acetic acid, also known as N—[N-acetyl, N′-(3-trifluoromethyl)phenylvalyl]glycine, or N-acetyl-N-[3-(trifluoromethyl)phenyl] valyl glycine or acetyl trifluoromethyl phenyl valylglycine, or an ester thereof with a C1-C6 alcohol; an extract of rice peptides such as Colhibin® from Pentapharm, or an extract of Phyllanthus emblica such as Emblica® from Rona;
or on the synthesis of glycosaminoglycans, such as the product of fermentation of milk with Lactobacillus vulgaris, marketed by Brooks under the trademark Biomin Yoghurt®; the extract of the brown alga Padina pavonica marketed by Alban Müller under the trademark HSP3®; the Saccharomyces cerevisiae extract available especially by Silab under the trademark Firmalift® or by LSN under the trademark Cytovitin®; an extract of Laminaria ochroleuca such as Laminaine® from Secma; essence of Mamaku from Lucas Meyer, and an extract of cress (Odraline® from Silab);
or on the synthesis of fibronectin, such as the extract of the zooplankton Salina marketed by Seporga under the trademark GP4G®; the yeast extract available especially by Alban Müller under the trademark Drieline®; and the palmitoyl pentapeptide marketed by Sederma under the trademark Matrixil®.
Among the active agents for stimulating epidermal macromolecules, such as fillagrin and keratins, especially exemplary are the extract of lupin marketed by Silab under the trademark Structurine®; the extract of Fagus sylvatica beech buds marketed by Gattefossé under the trademark Gatuline® RC; and the extract of the zooplankton Salina marketed by Seporga under the trademark GP4G®; the copper tripeptide from Procyte; a peptide extract of Voandzeia substerranea such as the product marketed by Laboratoires Sérobiologiques under the trademark Filladyn LS 9397®.
Preferably, an active agent that stimulates the synthesis of dermal and/or epidermal macromolecules and/or that prevents their degradation, selected from agents for stimulating the synthesis of glycosaminoglycans, agents for inhibiting elastin degradation, agents for stimulating fibronectin synthesis, agents for stimulating the synthesis of epidermal macromolecules, and mixtures thereof, will be employed.
Even more preferentially, an active agent that stimulates the synthesis of the glycosaminoglycans, selected from an extract of the brown alga Padina pavonica, an extract of Saccharomyces cerevisiae, an extract of Laminaria ochroleuca, essence of Mamaku, and an extract of cress, and mixtures thereof, will even more preferentially be employed.
As preferred active agents for stimulating the synthesis of dermal and/or epidermal macromolecules and/or for preventing their degradation, exemplary are:
synthetic peptides such as iamin, the biopeptide CL or palmitoyloligopeptide marketed by Sederma; peptides extracted from plants, such as the soybean hydrolysate marketed by Coletica under the trademark Phytokine®; rice peptides such as Nutripeptide® from Silab, methylsilanol mannuronate such as Algisium C® marketed by Exsymol; folic acid; an extract of Medicago sativa (alfalfa), such as the product marketed by Silab under the trademark Vitanol®; a peptide extract of hazelnut, such as the product marketed by Solabia under the trademark Nuteline C®; arginine; an extract of Aphanizomenon flos-aquae (Cyanophyceae) marketed under the trademark Lanablue® by Atrium Biotechnologies, the malt extract marketed by Coletica under the trademark Collalift®, lycopene; an extract of lychee; an extract of moring a such as Arganyl LS 9781® from Cognis; an extract of Vaccinium myrtillus such as those described in FR-A-2 814 950; retinol and derivatives thereof, in particular retinyl palmitate; the extract of Saccharomyces cerevisiae marketed by LSN under the trademark Cytovitin®; a peptide extract of hazelnut such as the product marketed by Solabia under the trademark Nuteline C®; {2-[acetyl(3-trifluoromethylphenyl)amino]-3-methylbutyrylamino}acetic acid, also known as N—[N-acetyl, N′-(3-trifluoromethyl)phenylvalyl]glycine, or N-acetyl-N-[3-(trifluoromethyl)phenyl]valylglycine or acetyl trifluoromethyl phenyl valylglycine, or an ester thereof with a C1-C6 alcohol; an extract of rice peptides such as Colhibin® from Pentapharm, or an extract of Phyllanthus emblica such as Emblica® from Rona; the extract of the brown alga Padina pavonica marketed by Alban Müller under the trademark HSP3®; the extract of Saccharomyces cerevisiae available especially by Silab under the trademark Firmalift® or by LSN under the trademark Cytovitin®; an extract of Laminaria ochroleuca such as Laminaine® from Secma; the essence of Mamaku from Lucas Meyer, the extract of lupin marketed by Silab under the trademark Structurine®(D; the extract of Fagus sylvatica beech buds marketed by Gattefossé under the trademark Gatuline® RC.
Agents for Stimulating Fibroblast or Keratinocyte Proliferation and/or Keratinocyte Differentiation:
The agents for stimulating fibroblast proliferation that may be included in the compositions according to the invention may be selected, for example, from plant proteins or polypeptides, extracted especially from soybean (for example a soybean extract marketed by LSN under the trademark Eleseryl SH-VEG 8® or marketed by Silab under the trademark Raffermine®); an extract of hydrolyzed soybean proteins such as Ridulisse® from Silab; and plant hormones such as gibberellins and cytokinins; a peptide extract of hazelnut such as the product marketed by Solabia under the trademark Nuteline C®.
Preferably, an agent that promotes keratinocyte proliferation and/or differentiation will be employed.
The agents for stimulating keratinocyte proliferation that may be included in the compositions according to the invention especially comprise adenosine; phloroglucinol, the extract of Hydrangea macrophylla leaves, for instance Amacha Liquid E® from Ichimaru Pharcos, a yeast extract such as Stimoderm® from CLR; the extract of Larrea divaricata such as Capislow® from Sederma, mixtures of extracts of papaya, of olive leaves and of lemon, such as Xyleine® from Vincience, the extract of Hydrangea macrophylla leaves, for instance Amacha Liquid E® from Ichimaru Pharcos, retinol and esters thereof, including retinyl palmitate, phloroglucinol, the nut cake extracts marketed by the Gattefossé and the extracts of Solanum tuberosum such as Dermolectine® marketed by Sederma.
Among the agents for stimulating keratinocyte differentiation are, for example, minerals such as calcium; sea fennel, a peptide extract of lupin, such as the product marketed by Silab under the trademark Structurine®; sodium beta-sitosteryl sulfate, such as the product marketed by Seporga under the trademark Phytocohesine®; and a water-soluble extract of corn, such as the product marketed by Solabia under the trademark Phytovityl®; a peptide extract of Voandzeia substerranea such as the product marketed by Laboratoires Serobiologiques under the trademark Filladyn LS 9397®; and lignans such as secoisolariciresinol, and retinol and esters thereof, including retinyl palmitate.
As agents for stimulating keratinocyte proliferation and/or differentiation, exemplary are the oestrogens such as oestradiol and homologues; cytokines.
As preferred active agents for stimulating fibroblast or keratinocyte proliferation and/or keratinocyte differentiation, exemplary are plant proteins or polypeptides, extracted especially from soybean (for example a soybean extract marketed by LSN under the trademark Eleseryl SH-VEG 8® or marketed by Silab under the trademark Raffermine®); an extract of hydrolyzed soybean proteins such as Ridulisse® from Silab; a peptide extract of hazelnut such as the product marketed by Solabia under the trademark Nuteline C®; adenosine; phloroglucinol, a yeast extract such as Stimoderm® from CLR; a peptide extract of lupin such as the product marketed by Silab under the trademark Structurine®; a water-soluble corn extract, such as the product marketed by Solabia under the trademark Phytovityl®; a peptide extract of Voandzeia substerranea, such as the product marketed by Laboratoires Sérobiologiques under the trademark Filladyn LS 9397®; retinol and esters thereof, including retinyl palmitate.
Agents for Promoting the Maturation of the Horny Envelope:
Agents that participate in the maturation of the horny envelope, which becomes impaired with age and induces a decrease in transglutaminase activity, may be included in the compositions of the invention. Examples are urea and derivatives thereof and in particular Hydrovance® from National Starch and the other active agents mentioned in L'Oréal FR 2 877 220 (unpublished).
NO-Synthase Inhibitors:
The agent with an inhibitory action on NO synthase may be selected from OPCs (procyannidol oligomers); plant extracts of the species Vitis vinifera marketed especially by Euromed under the trademark “Leucocyanidines de raisins extra”, or by Indena under the trademark Leucoselect®, or finally by Hansen under the trademark “Extrait de marc de raisin”; plant extracts of the species Olea europaea preferably obtained from olive tree leaves and marketed especially by Vinyals in the form of a dry extract, or by Biologia & Technologia under the trademark Eurol® BT; and plant extracts of the species Gingko biloba, preferably a dry aqueous extract of this plant marketed by Beaufour under the trademark “Ginkgo biloba extrait standard”, and mixtures thereof.
Peripheral Benzodiazepine Receptor (PBR) Antagonists:
Exemplary are 1-(2-chlorophenyl)-N-(1-methylpropyl)-3-isoquinoline carboxamide; the compounds described in WO 03/030 937 and WO 03/068 753, pyridazino[4,5-b]indole-1-acetamide derivatives of general formula (VII) as described in WO 00/44384.
Agents for Increasing the Activity of the Sebaceous Glands:
Exemplary are methyl dehydrojasmonate, hecogenin, hedione and O-linoleyl-6D-glucose, and mixtures thereof.
Agents for Stimulating the Energy Metabolism of Cells:
The active agent for stimulating the energy metabolism of cells may be selected, for example, from biotin, an extract of Saccharomyces cerevisiae such as Phosphovital® from Sederma, the mixture of sodium, manganese, zinc and magnesium salts of pyrrolidonecarboxylic acid, for instance Physiogenyl® from Solabia, a mixture of zinc, copper and magnesium gluconate, such as Sepitonic M3® from SEPPIC, and mixtures thereof; a beta-glucan derived from Saccharomyces cerevisiae, such as the product marketed by Mibelle AG Biochemistry.
Tensioning Agents:
The term “tensioning agent” according to the invention means compounds having a tensioning effect, i.e., being able to make the skin taut.
According to the invention, the term “tensioning agent” generally means any compound that is soluble or dispersible in water at a temperature ranging from 25° C. to 50° C. at a concentration of 7% by weight in water or at the maximum concentration at which a medium of uniform appearance is formed and producing at this concentration of 7% or at this maximum concentration in water a shrinkage of more than 15% in the test described below.
The maximum concentration at which a medium of uniform appearance forms is determined to within ±10% to preferably to within ±5%.
The expression “medium of uniform appearance” means a medium that does not contain any aggregates that are visible to the naked eye.
For the determination of the said maximum concentration, the tensioning agent is gradually added to the water with deflocculating stirring at a temperature ranging from 25° C. to 50° C., and the mixture is then stirred for one hour. The mixture thus prepared is then examined after 24 hours to see if it is of uniform appearance (absence of aggregates visible to the naked eye).
The tensioning effect may be characterized by an in vitro shrinkage test.
A homogeneous mixture of the tensioning agent in water, at a concentration of 7% by weight or at the maximum concentration described above, is prepared beforehand and as described previously.
30 μl of the homogeneous mixture are placed on a rectangular sample (10×40 mm, thus having an initial width L0 of 10 mm) of elastomer with a modulus of elasticity of 20 MPa and a thickness of 100 μm.
After drying for 3 hours at 22±3° C. and 40±10% relative humidity RH, the elastomer sample has a shrunken width, noted L3h, due to the tension exerted by the applied tensioning agent.
The tensioning effect (TE) of the said polymer is then quantified in the following manner:

‘TE’=(L0−L3h/L0)×100 as % with L0=initial width 10 mm and L3h=width after 3 hours of drying

The tensioning agent may be selected from:
plant or animal proteins and hydrolysates thereof;
polysaccharides of natural origin;
mixed silicates;
colloidal particles of mineral fillers;
synthetic polymers;
and mixtures thereof.
One skilled in this art will know how to choose, from the chemical categories listed above, the materials corresponding to the tensioning test as described above.
Especially exemplary are:
(a) plant proteins and protein hydrolysates, in particular of corn, rye, wheat, buckwheat, sesame, spelt, pea, bean, lentil, soybean and lupin,
(b) polysaccharides of natural origin, especially (a) polyholosides, for example (i) in the form of starch derived especially from rice, corn, potato, cassaya, pea, wheat, oat, etc. or (ii) in the form of carrageenans, alginates, agars, gellans, cellulose polymers and pectins, advantageously as an aqueous dispersion of gel microparticles, and (b) latices consisting of shellac resin, sandarac gum, dammar resins, elemi gums, copal resins, cellulose derivatives, and mixtures thereof,
(c) mixed silicates, especially phyllosilicates and in particular Laponites,
(d) colloidal particles of mineral fillers with a number-average diameter of from 0.1 and 100 nm and preferably from 3 and 30 nm, and selected, for example, from: silica, silica-alumina composites, cerium oxide, zirconium oxide, alumina, calcium carbonate, barium sulfate, calcium sulfate, zinc oxide and titanium dioxide. As silica-alumina composite colloidal particles that may be included in the compositions according to the invention, examples include those marketed by Grace under the trademarks Ludox AM, Ludox AM-X 6021, Ludox HSA and Ludox TMA,
(e) synthetic polymers, such as polyurethane latices or acrylic-silicone latices, in particular those described in EP-1-038,519, such as a polydimethylsiloxane grafted with propylthio(polymethyl acrylate), propylthio(polymethyl methacrylate) and propylthio(polymethacrylic acid), or, alternatively, a polydimethylsiloxane grafted with propylthio(polyisobutyl methacrylate) and propylthio(polymethacrylic acid). Such grafted silicone polymers are especially marketed by 3M under the trademarks VS 80, VS 70 and LO21.
The tensioning agent will be present in the composition in an amount that is effective for obtaining the desired biological effect according to the invention.
By way of example, the tensioning agent may be included in the compositions according to the invention in a content ranging from 0.01% to 30% by weight of active material and preferably from 1% to 30% by weight of active material relative to the total weight of the composition.
The term “active material” is intended to exclude the medium in which the tensioning agent may be dissolved or dispersed in its commercial form, for example in the case of dispersions of colloidal particles.
It is also possible, especially for complementing and/or potentializing the effect of tensioning agents, to employ agents which increase the expression of mechanoreceptors, such as agents which increase the expression of integrins.
An example is a rye seed extract, such as that marketed by Silab under the trademark Coheliss®.
Fat Restructuring Agents:
“Fat restructuring agents” are, according to the invention, agents which are capable of stimulating lipogenesis and promoting adipocyte differentiation, thereby making it possible to prevent or slow down the wasting of the fats contained in the support tissues of the skin, as is also called ‘wasting of the fat structure of the skin’.
‘Fat structure of the skin’ means the network of fat cells which form the volumes over which the facial skin rests and moulds itself to.
These agents are useful for lessening the loss of skin density and/or the wasting of the fat structure of the skin, more particularly on the cheeks and in the area around the eye, and/or for preventing the collapse and/or hollowing of the volumes of the face, the loss of consistency of the skin and/or its maintenance, more particularly on the cheeks and in the area around the eye, and/or for improving the underlying volumes of the skin of the face and/or neck, more particularly on the cheeks, of the oval of the face and of the area around the eye, and/or for improving the density, springiness and maintenance of the skin, more particularly on the cheeks, of the oval of the face and of the area around the eye, and/or of remodeling the features of the face, more particularly the oval of the face.
Examples of fat restructuring agents include, especially, a black tea extract, such as the extract of fermented black tea that is marketed by Sederma under the trademark Kombuchka®, and an extract of Artemisia abrotanum, such as that marketed by Silab under the trademark Pulpactyl®.
Slimming Agents:
Slimming (lipolytic) agents that are especially exemplary include caffeine, theophylline and its derivatives, theobromine, sericosine, asiatic acid, acefylline, aminophylline, chloroethyltheophylline, diprofylline, diniprophylline, etamiphylline and its derivatives, etofylline and proxyphylline; extracts of tea, of coffee, of guarana, of maté, of cola (Cola nitida) and especially the dry extract of guarana fruit (Paulina sorbilis) containing 8% to 10% caffeine; extracts of climbing ivy (Hedera helix), of arnica (Arnica montana L), of rosemary (Rosmarinus officinalis N), of marigold (Calendula officinalis), of sage (Salvia officinalis L), of ginseng (Panax ginseng), of St.-John's wort (Hypericum perforatum), of butcher's-broom (Ruscus aculeatus L), of meadowsweet (Filipendula ulmaria L), of orthosiphon (Orthosiphon stamincus Benth), of birch (Betula alba), of pumpwood and of argan tree, extracts of ginkgo biloba, extracts of horsetail, extracts of escin, extracts of cangzhu, extracts of Chrysanthellum indicum, extracts of diosgenin-rich Dioscorea plants or pure diosgenin or hecogenin and derivatives thereof, extracts of Ballota, extracts of Guioa, of Davallia, of Terminalia, of Barringtonia, of Trema or of Antirobia, the extract of bitter orange pips; an extract of husks of cocoa beans (Theobroma cacao) such as the product marketed by Solabia under the trademark Caobromine®.
Agents for Promoting the Cutaneous Microcirculation:
The active agent acting on the cutaneous microcirculation may be used for preventing dulling of the complexion and/or for improving the appearance of the area around the eye, especially for reducing shadows. It may be selected, for example, from an extract of maritime pine bark, for instance Pycnogenol® from Biolandes, manganese gluconate (Givobio GMn® from SEPPIC), an extract of Ammi visnaga such as Visnadine from Indena, extract of lupin (Eclaline® from Silab), the protein coupling of hydrolyzed wheat/palmitic acid with palmitic acid, such as Epaline 100 from Laboratoires Carilène, the extract of bitter orange blossom (Remoduline® from Silab), vitamin P and derivatives thereof, for instance methyl-4 esculetol sodium monoethanoate marketed under the trademark Permethol® by Sephytal, extracts of Ruscus, of common horse chestnut, of ivy, of ginseng and of melilot, caffeine, nicotinate and derivatives thereof, lysine and derivatives thereof, for instance Asparlyne® from Solabia, an extract of black tea such as Kombuchka from Sederma; rutin salts; an extract of the alga Corallina officinalis, such as the product marketed by Codif; and mixtures thereof.
As preferred agents for promoting the cutaneous microcirculation, exemplary are caffeine, an extract of bitter orange blossom, an extract of black tea, rutin salts and an extract of the alga Corallina officinalis. 
Calmatives or Anti-Irritants:
The term “calmative” means a compound that reduces the sensation of stinging, itching or tautness of the skin.
As calmatives that may be included in the compositions according to the invention, exemplary are:
procyannidol oligomers, vitamins E, C, B5 and B3, caffeine and derivatives thereof, pentacylic triterpenes and plant extracts containing them, β-glycyrrhetinic acid and salts or derivatives thereof (stearyl glycyrrhetate, 3-stearoyloxyglycyrrhetic acid or glycyrrhetinic acid monoglucuronide) and also plants containing them (e.g., Glycyrrhiza glabra), oleanolic acid and salts thereof, ursolic acid and salts thereof, boswellic acid and salts thereof, betulinic acid and salts thereof, an extract of Paeonia suffruticosa and/or lactiflora, an extract of Laminaria saccharina, extracts of Centella asiatica, Canola oil, bisabolol, the phosphoric diester of vitamin E and C, for instance Sepivital EPC® from SEPPIC, camomile extracts, allantoin, omega-3 unsaturated oils such as musk rose oil, blackcurrant oil, Ecchium oil, fish oil or beauty-leaf oil, plankton extracts, capryloyl glycine, a mixture of water lily blossom extract and of palmitoylproline, such as the product marketed under the trademark Seppicalm VG® by SEPPIC, an extract of Boswellia serrata, an extract of Centipeda cunninghami, such as the product marketed under the trademark Cehami PF® by TRI-K Industries, an extract of sunflower seeds, in particular Hélioxine® from Silab, an extract of Linum usitatissimum seeds, for instance Sensiline® from Silab, tocotrienols, piperonal, an extract of Epilobium angustifolium, such as the product marketed under the trademark Canadian Willowherb Extract by Fytokem Products, Aloe vera, phytosterols, cornflower water, rose water, an extract of mint, in particular of mint leaves, for instance Calmiskin® from Silab, anise derivatives, filamentous bacteria, for instance Vitreoscilla filiformis as described in EP-761,204 and marketed by Chimex under the trademark Mexoryl SBG®, an extract of rose petals, for instance Rose Flower Herbasole extract by Cosmetochem, shea butter, a mixture of the waxy fraction of barley seeds obtained by supercritical CO2, of shea butter and of argan oil, for instance Stimu-tex AS® from Pentapharm, alkaline-earth metal salts, especially of strontium, a fermented extract of Alteromonas marketed under the trademark Abyssine® by Atrium Biotechnologies; spring water from the Vichy basin, such as waters originating from the Célestins, Chomel, Grande-Grille, Hopital, Lucas and Parc sources, and preferably water from the Lucas source; an extract of Eperua falcata bark, such as the product marketed by Cognis under the trademark Eperuline®; an extract of Paeonia suffruticosa root, such as the product marketed by Ichimaru Pharcos under the trademark Botanpi Liquid B®; and mixtures thereof.
Preferred calmatives according to the invention include:
β-glycyrrhetinic acid and salts or derivatives thereof (stearyl glycyrrhetate, 3-stearoyloxyglycyrrhetic acid or glycyrrhetinic acid monoglucuronide) and also plants containing them (e.g. Glycyrrhiza glabra); ursolic acid and salts thereof; extracts of Centella asiatica, Canola oil, bisabolol; camomile extracts, allantoin; a mixture of extract of water lily blossom and of palmitoylproline, such as the product marketed under the trademark Seppicalm VG® by SEPPIC; Aloe vera, rose water, extract of mint, in particular of mint leaves, such as Calmiskin® from Silab, filamentous bacteria such as Vitreoscilla filiformis as described in EP-761,204 and marketed by Chimex under the trademark Mexoryl SBG®, an extract of rose petals such as Rose Flower Herbasol® extract by Cosmetochem, shea butter, a fermented extract of Alteromonas marketed under the trademark Abyssine® by Atrium Biotechnologies; spring water from the Vichy basin, such as waters originating from the Celestins, Chomel, Grande-Grille, Hôpital, Lucas and Parc sources, and preferably water from the Lucas source; an extract of Eperua falcata bark, such as the product marketed by Cognis under the trademark Eperuline®; an extract of Paeonia suffruticosa root, such as the product marketed by Ichimaru Pharcos under the trademark Botanpi Liquid B®; and mixtures thereof.
Sebo-Regulating or Anti-Seborrhoeic Agents:
The term “sebo-regulating or anti-seborrhoeic agents” especially means agents capable of regulating the activity of the sebaceous glands.
Especially exemplary are:
retinoic acid, benzoyl peroxide, sulfur, vitamin B6 (or pyridoxine), selenium chloride and sea fennel;
mixtures of extract of cinnamon, of tea and of octanoylglycine such as Sepicontrol A5 TEA® from SEPPIC;
the mixture of cinnamon, sarcosine and octanoylglycine marketed especially by SEPPIC under the trademark Sepicontrol A5®;
zinc salts such as zinc gluconate, zinc pyrrolidonecarboxylate (or zinc pidolate), zinc lactate, zinc aspartate, zinc carboxylate, zinc salicylate and zinc cysteate;
copper derivatives and in particular copper pidolate such as Cuivridone® from Solabia;
extracts of plants of the species Arnica montana, Cinchona succirubra, Eugenia caryophyllata, Humulus lupulus, Hypericum perforatum, Mentha piperita, Rosmarinus officinalis, Salvia oficinalis and Thymus vulgaris, all marketed, for example, by Maruzen;
extracts of meadowsweet (Spiraea ulmaria), such as the product marketed under the trademark Sebonormine® by Silab;
extracts of the alga Laminaria saccharina, such as the product marketed under the trademark Phlorogine® by Biotechmarine;
mixtures of extracts of salad burnet root (Sanguisorba officinalis/Poterium officinale), of ginger rhizomes (Zingiber officinalis) and of cinnamon bark (Cinnamomum cassia), such as the product marketed under the trademark Sebustop® by Solabia;
linseed extracts, such as the product marketed under the trademark Linumine® by Lucas Meyer;
Phellodendron extracts, such as those marketed under the trademark Phellodendron extract BG by Maruzen or Oubaku liquid B by Ichimaru Pharcos;
mixtures of argan oil, of Serenoa serrulata (saw palmetto) extract and of sesame seed extract, such as the product marketed under the trademark Regu SEB® by Pentapharm;
mixtures of extracts of willowherb, of Terminalia chebula, of nasturtium and of bioavailable zinc (microalgae), such as the product marketed under the trademark Seborilys® by Green Tech;
extracts of Pygeum afrianum, such as the product marketed under the trademark Pygeum afrianum sterolic lipid extract by Euromed;
extracts of Serenoa serrulata, such as the products marketed under the trademark Viapure Sabal by Actives International or those marketed by Euromed;
mixtures of extracts of plantain, of Berberis aquifolium and of sodium salicylate, such as the product marketed under the trademark Seboclear® by Rahn;
clove extract, such as the product marketed under the trademark Clove extract powder by Maruzen;
argan oil, such as the product marketed under the trademark Lipofructyl® by Laboratoires Sérobiologiques;
lactic protein filtrates, such as the product marketed under the trademark Normaseb® by Sederma;
extracts of the alga Laminaria, such as the product marketed under the trademark Laminarghanee by Biotechmarine;
oligosaccharides of the alga Laminaria digitata, such as the product marketed under the trademark Phycosaccharide AC by Codif;
sugar cane extracts, such as the product marketed under the trademark Policosanol® by Sabinsa;
sulfonated shale oil, such as the product marketed under the trademark lchthyol Pale® by Ichthyol;
European meadowsweet (Spiraea ulmaria) extracts, such as the product marketed under the trademark Cytobiol® Ulmaire by Libiol;
sebacic acid, especially marketed in the form of a sodium polyacrylate gel under the trademark Sebosoft® by Sederma;
glucomannans extracted from konjac tuber and modified with alkylsulfonate chains, such as the product marketed under the trademark Biopol Beta by Arch Chemical;
extracts of Sophora angustifolia, such as those marketed under the trademark Sophora powder or Sophora extract by Bioland;
extracts of Cinchona succirubra bark, such as the product marketed under the trademark Red Bark HS by Alban Muller;
extracts of Quillaja saponaria, such as the product marketed under the trademark Panama wood HS by Alban Muller;
glycine grafted onto an undecylenic chain, such as the product marketed under the trademark Lipacide UG OR by SEPPIC;
the mixture of oleanolic acid and of nordihydroguaiaretic acid, such as the product marketed in the form of a gel under the trademark AC.Net by Sederma;
phthalimidoperoxyhexanoic acid;
tri(C12-C13)alkyl citrate marketed under the trademark Cosmacol® ECI by Sasol; tri(C14-C15)alkyl citrate marketed under the trademark Cosmacol® ECL by Sasol;
10-hydroxydecanoic acid, and especially mixtures of 10-hydroxydecanoic acid, of sebacic acid and of 1,10-decanediol, such as the product marketed under the trademark Acnacidol® BG by Vincience; and
mixtures thereof.
Preferred anti-seborrhoeic active agents include:
benzoyl peroxide and vitamin B6 (or pyridoxine),
zinc salts such as zinc gluconate, zinc pyrrolidonecarboxylate (or zinc pidolate), zinc lactate, zinc aspartate, zinc carboxylate, zinc salicylate and zinc cysteate;
meadowsweet (Spiraea ulmaria) extracts, such as the product marketed under the trademark Sebonormine® by Silab;
extracts of the alga Laminaria saccharina, such as the product marketed under the trademark Phlorogine® by Biotechmarine;
mixtures of extracts of salad burnet root (Sanguisorba officinalis/Poterium officinale), of ginger rhizomes (Zingiber officinalis) and of cinnamon bark (Cinnamomum cassia), such as the product marketed under the trademark Sebustop® by Solabia;
clove extract, such as the product marketed under the trademark Clove extract powder by Maruzen;
lactic protein filtrates, such as the product marketed under the trademark Normaseb® by Sederma;
European meadowsweet (Spiraea ulmaria) extracts, such as the product marketed under the trademark Cytobiol® Ulmaire by Libiol;
sebacic acid, especially marketed in the form of a sodium polyacrylate gel under the trademark Sebosoft® by Sederma;
glycine grafted onto an undecylenic chain, such as the product marketed under the trademark Lipacide UG OR by SEPPIC;
tri(C12-C13)alkyl citrate marketed under the trademark Cosmacol® ECI by Sasol; tri(C14-C15)alkyl citrate marketed under the trademark Cosmacol® ECL by Sasol;
10-hydroxydecanoic acid, and especially mixtures of 10-hydroxydecanoic acid, of sebacic acid and of 1,10-decanediol, such as the product marketed under the trademark Acnacidol® BG by Vincience; and
mixtures thereof.
Preferentially, the anti-seborrhoeic active agent is selected from:
zinc salts such as zinc gluconate, zinc pyrrolidonecarboxylate (or zinc pidolate), zinc lactate, zinc aspartate, zinc carboxylate, zinc salicylate and zinc cysteate; and preferably zinc pyrrolidonecarboxylate (or zinc pidolate) or zinc salicylate;
clove extract, such as the product marketed under the trademark Clove extract powder by Maruzen;
glycine grafted onto an undecylenic chain, such as the product marketed under the trademark Lipacide UG OR by SEPPIC;
tri(C12-C13)alkyl citrate marketed under the trademark Cosmacol® ECI by Sasol; tri(C14-C15)alkyl citrate marketed under the trademark Cosmacol® ECL by Sasol;
and mixtures thereof.
The anti-seborrhoeic active agent is, for example, present in a content ranging from 0.1% to 10% by weight, preferably from 0.1% to 5% by weight and preferentially from 0.5% to 3% by weight relative to the total weight of the composition.
Astringents:
According to the invention, the term “astringents” means agents for combating the dilation of the sebaceous follicles.
As astringents that may be included in the compositions according to the invention, exemplary are extracts of mushroom pulp (Polyporus officinalis), for instance Laricyl LS8865® from Cognis, extracts of Terminalia catappa and Sambucus nigra, for instance Phytofirm LS9120® from Cognis, extracts of gall nut, for instance Tanlex VE® from Ichimaru Pharcos, aluminum hydroxychloride, centella extracts (e.g. Plantactiv centella from Cognis), dicetyl dimethylammonium chloride, for instance Varisoft 432 CG® from Degussa, common horsechestnut extracts, mallow extracts, witch-hazel extracts, sweet almond extracts, marsh mallow root extracts and linseed extracts, for instance Almondermin LS 3380® from Cognis, burdock extracts, nettle extracts, birch extracts, horsetail extracts, camomile extracts, for instance those marketed under the trademark Extrapone 9 Special® by Symrise, skullcap extracts, European meadowsweet extracts (for example Cytobiol Ulmaire from Libiol), a mixture of extracts of white ginger, of horsetail, of nettle, of rosemary and of yucca, for instance Herb extract B1348® from Bell Flavors & Fragrances, extracts of acacia, of elm, of white willow, of cinnamon, of birch and of meadowsweet, Panama sapogenins, zinc phenolsulfonate from Interchemical, extracts of gentian, of cucumber and of walnut, the mixture of extracts of Ratanhia, of grapefruit, of gumweed and of oak gall, for instance Epilami® from Alban Muller.
Preferred astringents according to the invention, include skullcap extracts, European meadowsweet extracts, meadowsweet extracts, gentian extracts and burdock extracts, and mixtures thereof.
Cicatrizing Agents:
Examples of cicatrizing agents include:
allantoin, urea, certain amino acids, for instance hydroxyproline, arginine, and serine, and also extracts of white lily (for instance Phytelene Lys 37EG 16295 from Indena), a yeast extract, for instance the cicatrizing agent LS LO/7225B from Laboratoires Sérobiologiques), tamanu oil, extract of Saccharomyces cerevisiae, for instance Biodynes® TRF® from Arch Chemical, oat extracts, chitosan and derivatives, for instance chitosan glutamate, carrot extracts, artemia extract, for instance GP4G® from Vincience, sodium acexamate, lavandin extracts, propolis extracts, ximeninic acid and salts thereof, rose hip oil, marigold extracts, for instance Souci Ami® Liposolible from Alban Muller, horsetail extracts, lemon peel extracts, for instance Herbasol® citron from Cosmetochem, helichrysum extracts, common yarrow extracts and folic acid.
Preferred cicatrizing agents according to the invention include arginine, serine, folic acid, tamanu oil, sodium acexamate, horsetail extracts and helichrysum extracts, and mixtures thereof.
Anti-Inflammatory Agents:
As particular anti-inflammatory agents according to the invention, exemplary are cortisone, hydrocortisone, indomethacin, betamethasone, azelaic acid, acetaminophen, diclofenac, clobetasol propionate, folic acid; an extract of Eperua falcata bark, such as the product marketed by Cognis under the trademark Eperuline®; an extract of Paeonia suffruticosa root, such as the product marketed by Ichimaru Pharcos under the trademark Botanpi Liquid B®; and mixtures thereof.
Preferred anti-inflammatory agents are azelaic acid, folic acid, an extract of Eperua falcata bark, such as the product marketed by Cognis under the trademark Eperuline®; an extract of Paeonia suffruticosa root, such as the product marketed by Ichimaru Pharcos under the trademark Botanpi Liquid B®; and mixtures thereof.
Anti-Acne Agents:
In one advantageous embodiment of the invention, the composition may also comprise at least one anti-acne active.
The term “anti-acne active” especially means any active agent that has effects on the specific flora of greasy skin, for instance Propionibacterium acnes (P. acnes).
These effects may be bactericidal.
Antibacterial actives that are exemplary include:
actives and preservatives with antimicrobial activity mentioned in DE 103 24 567, which is incorporated into the present invention by reference,
asiatic acid,
the monoethanolamine salt of 1-hydroxy-4-methyl 6-trimethylpentyl-2-pyridone (INCI name: piroctone olamine), marketed especially under the trademark Octopirox® by Clariant;
citronellic acid, perillic acid (or 4-isopropenylcyclohex-1-enecarboxylic acid),
glyceryl 2-ethylhexyl ether (INCI name: ethylhexylglycerine), for example marketed under the trademark Sensiva SC 50® by Schulke & Mayr,
glyceryl caprylate/caprate, for example marketed under the trademark Capmul MCM® by Abitec;
sodium calcium phosphosilicate, especially marketed under the trademarks Bioactive Glasspowder® and Actysse Premier BG® by Schott Glass;
silver-based particles, for example those marketed under the trademark Metashine ME 2025 PS® by Nippon Sheet Glass;
hop cone extract (Humulus lupulus) obtained by supercritical CO2 extraction, such as the product marketed under the trademark HOP CO2-TO Extract® by Flavex Naturextrakte,
St. John's Wort extract obtained by supercritical CO2 extraction, such as the product marketed under the trademark St. John's Wort CO2-TO Extract® by Flavex Naturextrakte,
the mixture of extracts of roots of Scutellaria baicalensis, of Paeonia suffruticosa and Glycyrrhiza glabra, such as the product marketed under the trademark BMB-CF® by Naturogin,
argan tree extract, for instance Argapure LS9710® from Cognis;
bearberry leaf extracts, for instance the product marketed under the trademark Melfade-J by Pentapharm;
10-hydroxy-2-decanoic acid such as Acnacidol P® from Vincience, sodium ursolate, azelaic acid, diiodomethyl p-tolyl sulfone such as Amical Flowable® from Angus, malachite powder, zinc oxide such as Zincare® from Elementis GMBH, octadecenedioic acid such as Arlatone dioic DCA® from Uniqema; ellagic acid; 2,4,4′-trichloro-2′-hydroxydiphenyl ether (or triclosan), 1-(3′,4′-dichlorophenyl)-3-(4′-chlorophenyl)urea (or triclocarban), 3,4,4′-trichlorocarbanilide, 3′,4′,5′-trichlorosalicylanilide, phenoxyethanol, phenoxypropanol, phenoxyisopropanol, hexamidine isethionate, metronidazole and salts thereof, miconazole and salts thereof, itraconazole, terconazole, econazole, ketoconazole, saperconazole, fluconazole, clotrimazole, butoconazole, oxiconazole, sulfaconazole, sulconazole, terbinafine, ciclopirox, ciclopiroxolamine, undecylenic acid and salts thereof, benzoyl peroxide, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, phytic acid, N-acetyl-L-cysteine, lipoic acid, azelaic acid and salts thereof, arachidonic acid, resorcinol, 3,4,4′-trichlorocarbanalide, octoxyglycerine or octoglycerine, octanoylglycine such as Lipacid C8G® from SEPPIC, caprylyl glycol, 10-hydroxy-2-decanoic acid, dichlorophenylimidazoldioxolane and derivatives thereof described in WO 93/18743, iodopropynyl butylcarbamate, 3,7,11-trimethyldodeca-2,5,10-trienol or farnesol, phytosphingosines; quaternary ammonium salts, for instance cetyltrimethylammonium salts and cetylpyridinium salts, and
mixtures thereof.
Also exemplary are certain surfactants with an antimicrobial effect, for instance sodium cocoamphoacetate or disodium diacetate such as Miranol C2M Conc. NP, betaines, for instance the cocoyl betaine Genagen KB from Clariant, sodium lauryl ether sulfate, for instance Emal 270 D from Kao, decyl glucoside, for instance Plantacare 2000 UP, branched C12-13 dialkyl malates, for instance Cosmacol EMI, propylene glycol monoesters, for instance propylene glycol monolaurate, monocaprylate or monocaprate, lauryldimethylamine betaine, for instance Empigen BB/LS, and also polyquaternary ammoniums such as Quaternium-24 or Bardac 2050 from Lonza and those described in FR 0 108 283, and mixtures thereof.
Preferred antimicrobial agents are octoglycerine or octoxyglycerine, and 10-hydroxy-2-decanoic acid, and mixtures thereof.
Other additional anti-acne actives may be added to the abovementioned anti-acne actives.
Especially exemplary are actives with bacterial anti-adhesion effects or agents that act on the biofilm of bacteria to prevent them from multiplying.
As agents for preventing and/or reducing the adhesion of microorganisms, especially exemplary are:
phytantriol and derivatives thereof as described in EP-1-529,523, plant oils such as wheatgerm oil, calendula oil, castor oil, olive oil, avocado oil, sweet almond oil, groundnut oil, jojoba oil, sesame seed oil, apricot kernel oil, sunflower oil and macadamia oil, described in EP-1-133,979, or certain surfactants such as disodium cocoamphodiacetate, oxyethylenated (7 EO) glyceryl cocoate, 18-hexadecenyl succinate, octoxyglyceryl palmitate, octoxyglyceryl behenate, dioctyl adipate, PPG-15 stearyl ether, and the branched C12-C13 dialkyl tartrates described in EP-1-129,694, and mixtures thereof.
In particular with regard to the propagation of P. acnes, or as active agents that act on the biofilm of bacteria to prevent them from proliferating, exemplary are pentylene glycol, Nylon-66 (polyamide 66 fibers), rice bran oil, polyvinyl alcohol such as Celvol 540 PV Alcohol® from Celanese Chemical, rapeseed oil such as Akorex L® from Karlshamns, and fructose derivatives, and mixtures thereof.
The anti-acne active may be present in a content ranging from 0.01% to 10% by weight and preferably from 0.05% to 5% by weight relative to the total weight of the composition.
As a function of the nature and/or solubility of the abovementioned active agents, one skilled in this art will know how to select the most suitable embodiment according to the invention.
As lipophilic active agents that may be used in the kit or at least one of the compositions of the invention, especially exemplary are D-α-tocopherol, DL-α-tocopherol, D-α-tocopheryl acetate, DL-α-tocopheryl acetate, ascorbyl palmitate, vitamin F glycerides, D vitamins, vitamin D2, vitamin D3, retinol, retinol esters, retinyl palmitate, retinyl propionate, carotenes including β-carotene, D-panthenol, farnesol, farnesyl acetate, salicylic acid and derivatives thereof, for instance 5-n-octanoylsalicylic acid, α-hydroxy acid alkyl esters such as citric acid, lactic acid, glycolic acid, asiatic acid, madecassic acid, asiaticoside, the total extract of Centella asiatica, α-glycyrrhetinic acid, α-bisabolol, ceramides, for instance 2-oleoylamino-1,3-octadecane, phytantriol, phospholipids of marine origin rich in polyunsaturated essential fatty acids, ethoxyquine, rosemary extract, balm extract, quercetin, extract of dried microalgae, essential oil of bergamot, octyl methoxycinnamate, butylmethoxydibenzoylmethane, octyl triazone, 3,5-di-tert-butyl-4-hydroxy-3-benzylidenecamphor, antibiotics, antifungal agents, anaesthetics, analgesics, antiseptics, antiviral agents, pesticides and herbicides, and mixtures thereof.
The cosmetic and/or dermatological active agents will be present in the kit or one of the compositions according to the invention in a content ranging from 0.001% to 20% relative to the total weight of the composition, preferably from 0.01% to 10%, even more preferentially from 0.5% to 5% to more preferably from 0.1% to 1% by weight relative to the total weight of the composition.
For peeling applications, the contents of cosmetic and/or dermatological active agents may range from 1% to 50% by weight relative to the total weight of the composition and preferably from 1% to 30% by weight relative to the total weight of the composition.
Peels are a well-known means for improving the appearance and/or texture of the skin and/or the scalp, especially for improving the radiance and homogeneity of the complexion and/or for reducing the visible and/or tactile irregularities of the skin, and in particular for improving the surface appearance of the skin, for attenuating actinic lentigo, acne or chicken pox marks, and also for preventing, attenuating or combating the signs of aging of the skin, and especially for smoothing out irregularities in the texture of the skin, such as wrinkles and fine lines.
They have the effect of removing a surface part of the skin to be treated (epidermis and possibly the upper layer of the dermis), via chemical methods.
Other Additional Ingredients:
To complement and/or optimize the effects imparted by the cosmetic and/or dermatological actives mentioned above on the keratin materials, it may be advantageous to incorporate into the compositions of the invention other additional ingredients.
In particular, these additional ingredients may impart an immediate visual effect that will be taken up by the biological effect of the actives mentioned above. They may also, via a mechanical action (e.g.: abrasive fillers), amplify the effect of the biological actives mentioned above.
Thus, the compositions according to the invention may further comprise at least one agent selected from matting agents, soft-focus effect fillers, fluorescers, agents for promoting the naturally pinkish coloration of the skin, abrasive fillers or exfoliants, and mixtures thereof.
Matting Agents:
The term “matting agent” means agents intended to make the skin visibly more matt and less shiny.
The matting effect of the agent and/or composition containing it may especially be evaluated using a gonioreflectometer, by measuring the ratio R from the specular reflection and the scattered reflection. A value of R of less than or equal to 2 generally reflects a matting effect.
The matting agent may especially be selected from a rice starch or a corn starch, kaolinite, talc, a pumpkin seed extract, cellulose microbeads, plant fibers, synthetic fibers, in particular polyamide fibers, expanded acrylic copolymer microspheres, polyamide powders, silica powders, polytetrafluoroethylene powders, silicone resin powders, acrylic polymer powders, wax powders, polyethylene powders, powders of elastomeric crosslinked organopolysiloxane coated with silicone resin, talc/titanium dioxide/alumina/silica composite powders, amorphous mixed silicate powders, silicate particles and especially mixed silicate particles, and mixtures thereof.
Examples of matting agents that are especially representative include:
rice or corn starch, in particular an aluminum starch octenyl succinate marketed under the trademark Dry Flo® by National Starch;
kaolinite;
silicas;
talc;
a pumpkin seed extract as marketed under the trademark Curbilene® by Indena;
cellulose microbeads as described in EP-1-562,562;
fibers, such as silk fiber, cotton fiber, wool fiber, flax fiber, cellulose fiber extracted especially from wood, from vegetables or from algae, polyamide fiber (Nylon®), modified cellulose fiber, poly-p-phenyleneterephthamide fiber, acrylic fiber, polyolefin fiber, glass fiber, silica fiber, aramid fiber, carbon fiber, Teflon® fiber, insoluble collagen fiber, polyester fiber, polyvinyl chloride or polyvinylidene chloride fiber, polyvinyl alcohol fiber, polyacrylonitrile fiber, chitosan fiber, polyurethane fiber, polyethylene phthalate fiber, fibers formed from a mixture of polymers, resorbable synthetic fibers, and mixtures thereof described in EP-1-151,742;
expanded acrylic copolymer microspheres such as those marketed by EXPANCEL under the trademark Expancel 551®;
fillers with an optical effect as described in FR 2 869 796, in particular:
polyamide powders (Nylon®), for instance Nylon 12 particles of the Orgasol type from Arkema, with a mean size of 10 microns and a refractive index of 1.54,
silica powders, for instance Silica beads SB150 from Miyoshi with a mean size of 5 microns and a refractive index of 1.45,
polytetrafluoroethylene powders, for instance PTFE Ceridust 9205F from Clariant, with a mean size of 8 microns and a refractive index of 1.36,
silicone resin powders, for instance the silicone resin Tospearl 145A from GE Silicone with a mean size of 4.5 microns and a refractive index of 1.41,
acrylic copolymer powders, especially of polymethyl(meth)acrylate, for instance the PMMA particles Jurymer MBI from Nihon Junyoki, with a mean size of 8 microns and a refractive index of 1.49, or the Micropearl M100® and F 80 ED® particles by Matsumoto Yushi-Seiyaku,
wax powders, for instance the paraffin wax particles Microease 114S from Micropowders, with a mean size of 7 microns and a refractive index of 1.54,
polyethylene powders, especially comprising at least one ethylene/acrylic acid copolymer, and in particular consisting of ethylene/acrylic acid copolymers, for instance the particles Flobeads EA 209 from Sumitomo (with a mean size of 10 microns and a refractive index of 1.48),
elastomeric crosslinked organopolysiloxane powders coated with silicone resin, especially with silsesquioxane resin, as described, for example, in U.S. Pat. No. 5,538,793. Such elastomeric powders are marketed under the trademarks KSP-100, KSP-101, KSP-102, KSP-103, KSP-104 and KSP-105 by Shin-Etsu, and
talc/titanium dioxide/alumina/silica composite powders such as those marketed under the trademark Coverleaf® AR-80 by Catalyst & Chemicals,
mixtures thereof,
compounds that absorb and/or adsorb sebum as described in FR 2 869 796. Mention may be made especially of:
silica powders, for instance the porous silica microspheres marketed under the trademark Silica Beads SB-700 marketed by Miyoshi, the products Sunsphere® H51, Sunsphere® H33 and Sunsphere® H53 marketed by Asahi Glass; the polydimethylsiloxane-coated amorphous silica microspheres marketed under the trademark SA Sunsphere® H-33 and SA Sunsphere® H-53 marketed by Asahi Glass;
amorphous mixed silicate powders, especially of aluminum and magnesium, for instance the product marketed under the trademark Neusilin UFL2 by Sumitomo;
polyamide (Nylon®) powders, for instance Orgasol® 4000 marketed by Arkema, and
acrylic polymer powders, especially of polymethyl methacrylate, for instance Covabead® LH85 marketed by Wacker; of polymethyl methacrylate/ethylene glycol dimethacrylate, for instance Dow Corning 5640 Microsponge® Skin Oil Adsorber marketed by Dow Corning, or Ganzpearl® GMP-0820 marketed by Ganz Chemical; of polyallyl methacrylate/ethylene glycol dimethacrylate, for instance Poly-Pore® L200 or Poly-Pore® E200 marketed by Amcol; of ethylene glycol dimethacrylate/lauryl methacrylate copolymer, for instance Polytrap® 6603 marketed by Dow Corning;
silicate particles, such as alumina silicate;
mixed silicate particles, such as:
magnesium aluminum silicate particles, such as saponite or hydrated magnesium aluminum silicate with a sodium sulfate marketed under the trademark Sumecton® by Kunimine;
the magnesium silicate, hydroxyethylcellulose, black cumin oil, marrow oil and phospholipids complex or Matipure® from Lucas Meyer, and
mixtures thereof.
Preferred matting agents according to the invention include a pumpkin seed extract, a rice or corn starch, kaolinite, silicas, talc, polyamide powders, polyethylene powders, acrylic copolymer powders, expanded acrylic copolymer microspheres, silicone resin microbeads and mixed silicate particles, and mixtures thereof.
Fillers with a Soft-Focus Effect:
These fillers may be any material capable of modifying and hiding wrinkles by virtue of their intrinsic physical properties. These fillers may especially modify wrinkles via a tensioning effect, a covering effect or a soft-focus effect.
Examples of such fillers include the following compounds:
porous silica microparticles, for instance Silica Beads® SB150 and SB700 from Miyoshi with a mean size of 5 μm; the series-H Sunspheres® from Asahi Glass, for instance Sunspheres H33, H51 with respective sizes of 3.5 and 5 μm;
hollow hemispherical silicone resin particles such as NLK 500®, NLK 506® and NLK 510® from Takemoto Oil and Fat, especially described in EP-A-1-579,849;
silicone resin powders, for instance the silicone resin Tospearl® 145A from GE Silicone, with a mean size of 4.5 μm;
acrylic copolymer powders, especially of polymethyl (meth)acrylate, for instance the PMMA particles Jurimer MBI® from Nihon Junyoki, with a mean size of 8 μm, the hollow PMMA spheres marketed under the trademark Covabead® LH85 by Wackherr, and vinylidene/acrylonitrile/methylene methacrylate expanded microspheres marketed under the trademark Expancel®;
wax powders, for instance the paraffin wax particles MicroEases 114S from MicroPowders, with a mean size of 7 μm;
polyethylene powders, especially comprising at least one ethylene/acrylic acid copolymer, for instance the Flobeads® EA 209 from Sumitomo, with a mean size of 10 μm;
crosslinked elastomeric organopolysiloxane powders coated with silicone resin and especially with silsesquioxane resin, marketed under the trademarks KSP-100®, KSP-101®, KSP-102®, KSP-103®, KSP-104® and KSP-105® by Shin-Etsu;
talc/titanium dioxide/alumina/silica composite powders, for instance Coverleaf AR 80® by Catalyst & Chemical;
talc, mica, kaolin, lauryl glycine, starch powders crosslinked with octenyl succinate anhydride, boron nitride, polytetrafluoroethylene powders, precipitated calcium carbonate, magnesium carbonate, magnesium hydrogen carbonate, barium sulfate, hydroxyapatite, calcium silicate, cerium dioxide and glass or ceramic microcapsules;
hydrophilic or hydrophobic, synthetic or natural, mineral or organic fibers such as silk fibers, cotton fibers, wool fibers, flax fibers, cellulose fibers extracted especially from wood, vegetables or algae, polyamide (Nylon®) fibers, modified cellulose fibers, poly-p-terephthamide fibers, acrylic fibers, polyolefin fibers, glass fibers, silica fibers, aramid fibers, carbon fibers, polytetrafluoroethylene (Teflon®) fibers, insoluble collagen fibers, polyester fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyvinyl alcohol fibers, polyacrylonitrile fibers, chitosan fibers, polyurethane fibers, polyethylene phthalate fibers, fibers formed from a mixture of polymers, resorbable synthetic fibers, and mixtures thereof described in EP-1-151,742;
spherical elastomeric crosslinked silicones, for instance Trefil E-505C® or E-506C® from Dow Corning;
abrasive fillers, which, via a mechanical effect, smooth out the skin microrelief, such as abrasive silica, for instance Abrasif SP® from Semanez or nutshell powders (for example of apricot or walnut, from Cosmetochem).
The fillers with an effect on the signs of aging are especially selected from porous silica microparticles, hollow hemispherical silicone particles, silicone resin powders, acrylic copolymer powders, polyethylene powders, crosslinked elastomeric organopolysiloxane powders coated with silicone resin, talc/titanium dioxide/alumina/silica composite powders, precipitated calcium carbonate, magnesium carbonate, magnesium hydrogen carbonate, barium sulfate, hydroxyapatite, calcium silicate, cerium dioxide, glass or ceramic microcapsules, and silk fibers or cotton fibers, and mixtures thereof.
The filler may be a soft-focus filler.
The term “soft-focus” filler means a filler which in addition gives the complexion transparency and a hazy effect. Preferably, the soft-focus fillers have a mean particle size of less than or equal to 15 microns. These particles may be in any form and in particular may be spherical or non-spherical. These fillers are more preferably non-spherical.
The soft-focus fillers may be selected from silica and silicate powders, especially alumina powder, powders of polymethyl methacrylate (PMMA) type, talc, silica/TiO2 or silica/zinc oxide composites, polyethylene powders, starch powders, polyamide powders, styrene/acrylic copolymer powders and silicone elastomers, and mixtures thereof.
Particularly exemplary is a talc with a number-average size of less than or equal to 3 microns, for example talc with a number-average size of 1.8 microns and especially the product marketed under the trademark Talc P3® by Nippon Talc, Nylon® 12 powder, especially the product marketed under the trademark Orgasol 2002 Extra D Nat Cos® by Atochem, silica particles 1% to 2% surface-treated with a mineral wax (INCI name: hydrated silica (and) paraffin) such as the products marketed by Degussa, amorphous silica microspheres, such as the products marketed under the trademark Sunsphere, for example of reference H-53® by Asahi Glass, and silica microbeads such as those marketed under the trademark SB-700® or SB-150® by Miyoshi, this list not being limiting.
The concentration of these fillers with an effect on the signs of aging in the compositions according to the invention may be from 0.1% to 40%, or even from 0.1% to 20% by weight, relative to the total weight of the composition.
Fluorescers:
The term “fluorescer” means a substance which, under the effect of ultraviolet rays and/or visible light, re-emits in the visible region the portion of light that it has absorbed under the same color as that which it naturally reflects. The naturally reflected color is thus reinforced by the re-emitted color and appears extremely bright.
Examples thereof include colored polyamide and/or formaldehyde/benzoguanamine and/or melamine/formaldehyde/sulfonamide resins, from colored aminotriazine/formaldehyde/sulfonamide co-condensates and/or from metallized polyester flakes and/or mixtures thereof. These fluorescent pigments may also be present in the form of aqueous dispersions of fluorescent pigments.
Also exemplary are pink-colored fluorescent aminotriazine/formaldehyde/sulfonamide co-condensate with a mean particle size of 3-4 microns marketed under the trademark “Fiesta Astral Pink FEX-1” and the blue-colored fluorescent aminotriazine/formaldehyde/sulfonamide co-condensate with a mean particle size of 3-4.5 microns marketed under the trademark “Fiesta Comet Blue FTX-60” by Swada, or, alternatively, the yellow-colored benzoguanamine/formaldehyde resin covered with formaldehyde/urea resin marketed under the trademark “FB-205 Yellow” and the red-colored benzoguanamine/formaldehyde resin covered with formaldehyde/urea resin marketed under the trademark “FB-400 Orange Red” by UK Seung Chemical, and the orange-colored polyamide resin marketed under the trademark “Flare 911 Orange 4” by Sterling Industrial Colors.
The fluorescent substances are preferably present in the composition in a content ranging from 0.1% to 20%, preferably from 0.1% to 15% to more preferably from 0.5% to 3% by weight relative to the total weight of the composition.
When the organic fluorescent substances are white, they are also known as optical brighteners.
The optical brightener has the effect of intensifying the radiance and reviving the shades of cosmetic compositions comprising them on application to the skin.
Among the optical brighteners that are more particularly exemplary are stilbene derivatives, in particular polystyrylstilbenes and triazinestilbenes, coumarin derivatives, in particular hydroxycoumarins and aminocoumarins, oxazole, benzoxazole, imidazole, triazole and pyrazoline derivatives, pyrene derivatives and porphyrin derivatives, and/or mixtures thereof.
Such compounds are available, for example, under the trademarks Tinopal SOP® and Uvitex OB® by Ciba Geigy.
The optical brighteners preferentially used are sodium 4,4′-bis[(4,6-dianilino-1,3,5-triazin-2-yl)amino]stilbene-2,2′-disulfonate, 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole) and disodium 4,4′-distyrylbiphenylsulfonate, and/or mixtures thereof.
Agents for Promoting the Naturally Pinkish Coloration of the Skin:
Especially exemplary are:
a self-tanning agent, i.e., an agent which, when applied to the skin, especially to the face, can produce a tan effect that is more or less similar in appearance to that which may result from prolonged exposure to the sun (natural tan) or under a UV lamp;
an additional coloring agent, i.e., any compound that has a particular affinity for the skin, which allows it to give the skin a lasting, non-covering coloration (i.e., that does not have a tendency to opacify the skin) and that is not removed either with water or using a solvent, and that withstands both rubbing and washing with a solution containing surfactants. Such a lasting coloration is thus distinguished from the superficial and transient coloration provided, for example, by a makeup pigment; and mixtures thereof.
Examples of self-tanning agents include:
dihydroxyacetone (DHA),
erythrulose, and
the combination of a catalytic system formed from:
manganese and/or zinc oxide salts, and
alkali metal and/or alkaline-earth metal hydrogen carbonates.
The self-tanning agents are generally selected from monocarbonyl or polycarbonyl compounds, for instance isatin, alloxan, ninhydrin, glyceraldehyde, mesotartaric aldehyde, glutaraldehyde, erythrulose, pyrazoline-4,5-dione derivatives as described in FR 2,466,492 and WO 97/35842, dihydroxyacetone (DHA) and 4,4-dihydroxypyrazolin-5-one derivatives as described in EP-903,342. DHA will preferably be used.
The DHA may be used in free and/or encapsulated form, for example in lipid vesicles such as liposomes, especially described in WO 97/25970.
In general, the self-tanning agent is present in an amount ranging from 0.01% to 20% by weight and preferably in an amount of from 0.1% to 10% of the total weight of the composition.
Other dyes that allow modification of the color produced by the self-tanning agent may also be used.
These dyes may be selected from synthetic or natural direct dyes.
These dyes may be selected, for example, from red or orange dyes of the fluoran type such as those described in FR 2,840,806.
Exemplary are the following dyes:
tetrabromofluoresceine or eosin known under the CTFA name: CI 45380 or Red 21;
phloxin B known under the CTFA name: C145410 or Red 27;
diiodofluoresceine known under the CTFA name: C145425 or Orange 10;
dibromofluoresceine known under the CTFA name: C145370 or Orange 5;
the sodium salt of tetrabromofluoresceine known under the CTFA name: CI 45380 (Na salt) or Red 22;
the sodium salt of phloxin B known under the CTFA name: CI 45410 (Na salt) or Red 28;
the sodium salt of diiodofluoresceine known under the CTFA name: CI 45425 (Na salt) or Orange 11;
erythrosine known under the CTFA name: C145430 or Acid Red 51;
phloxin known under the CTFA name: CI 45405 or Acid Red 98.
These dyes may also be selected from anthraquinones, caramel, carmine, carbon black, azulene blues, methoxalene, trioxalene, guajazulene, chamuzulene, Bengal rose, cosin 10B, cyanosin and daphinin.
These dyes may also be selected from indole derivatives, for instance the monohydroxyindoles as described in FR 2 651 126 (i.e., 4-, 5-, 6- or 7-hydroxyindole) or the dihydroxyindoles as described in EP-B-0,425,324 (i.e., 5,6-dihydroxyindole, 2-methyl-5,6-dihydroxyindole, 3-methyl-5,6-dihydroxyindole or 2,3-dimethyl-5,6-dihydroxyindole).
Abrasive Fillers or Exfoliants:
As exfoliants that may be included in rinse-out compositions according to the invention, examples thereof include exfoliant or scrubbing particles of mineral, plant or organic origin. Thus, polyethylene beads or powder, Nylon powder, polyvinyl chloride powder, pumice powder, ground apricot kernel or walnut shell, sawdust, glass beads and alumina, and mixtures thereof, may be used, for example.
Also exemplary are Exfogreen® from Solabia (bamboo extract), extracts of strawberry akenes (Strawberry Akenes from Greentech), peach kernel powder, apricot kernel powder, and finally, in the field of plant powders with an abrasive effect, mention may be made of cranberry kernel powder.
As abrasive fillers or exfoliants that are preferred according to the invention, exemplary are peach kernel powder, apricot kernel powder, cranberry kernel powder, strawberry akene extracts and bamboo extracts.
In order to further illustrate the present invention and the advantages thereof, the following specific examples are given, it being understood that same are intended only as illustrative and in nowise limitative. In said examples to follow, all parts and percentages are given by weight, unless otherwise indicated.
Example 1
The products are evaluated on the Episkin model of reconstructed skin after 18 days of culturing. The crucibles are placed on Whatman paper. 20 μl of a 5 wt % solution of test product in a 50% water/50% ethanol mixture. After 24 hours, washing is performed with 1 ml of water containing 1% sodium lauryl ether sulfate, with stirring for 1 minute. A second rinse is performed with 1 ml of water. The residual liquid is absorbed using a soft paper tissue. The measurements are taken using a Minolta CM-2600d spectrocolorimeter.
Material:
Spectrocolorimeter Minolta CM2600d
Illuminating agent: D65
Observer: 10°
SCE: specular excluded
The results are expressed in the system (L*, a*, b*) dans lequel L* is the luminance, a* is the red-green axis (−a*=green, +a*=red) and b* is the yellow/blue axis (−b*=blue, +b*=yellow). Therefore, a* and b* express the coloring of the skin.
The color deviation is obtained with the color deviation formula of Hunter in the calorimetric domain L, a, b:

(ΔE)2=[(ΔL)2+(Δa)2+(Δb)2].

ΔE is the darkening, the global intensity of the color: The more ΔE is important the more the color darkened.

Results after Washing:














Test product
L*
a*
b*
ΔE*ab



















Dehydroascorbic acid
77.7
4.8
35
14.6


Dihydroxyacetone (DHA)
82.6
1.3
30.0
11.1


Episkin alone
86.2
−1.2
24.7





L = intensity, a red component, b yellow component






It is observed that, at a concentration equal to 5 wt %, dehydroascorbic acid makes it possible to obtain a stronger shade with a more pronounced dominant red than that obtained with DHA.
Example 2: Coloring from Vitamin C
Example 2a: (Chemical Oxidation)
is carried out by mixing 5.7 mmols of hydrogen peroxide with 5.7 mmols of sodium ascorbate. The resulting mixture is left during 2 hours at 30° C.
Example 2b: (Enzymatic Oxidation with a Free Enzyme)
An oxidation of the vitamin C under the form of sodium ascorbate by enzymatic reaction is carried out by mixing extemporaneously 5 μl of a 5 units/ml of ascorbate oxidize solution in a phosphate buffer of 0.1 M and pH 7.5 with 20 μl of a sodium ascorbate solution of 10 mM in a phosphate buffer of 0.1 M and pH 7.5.
Example 2c: (Enzymatic Oxidation with an Immobilized Enzyme)
An oxidation of the vitamin C under the form of sodium ascorbate by enzymatic reaction is carried out by a percolation of 1 ml of 5% sodium ascorbate solution in a phosphate buffer of 0.1 M and pH 7.5 on ascorbate oxidize immobilized on an epoxy resin of the type EUPERGIT C®.
25 μl of each resulting solution is applied on BLENDERM® which is stratum sampled by a polymer of the type 3M Scotch. The color was measured after 4 hours with the colormeter Minolta. The evolution of the color is evaluated over non-treated control samples.
Material:
Spectrocolorimeter Minolta CM2600d
Illuminating agent: D65
Observer: 10°
SCE: specular excluded
The results are expressed in the system (L*, a*, b*) dans lequel L* is the luminance, a* is the red-green axis (−a*=green, +a*=red) and b* is the yellow/blue axis (−b*=blue, +b*=yellow). Therefore, a* and b* express the coloring of the skin.
The color deviation is obtained with the color deviation formula of Hunter in the colorimetric domain L, a, b:

(ΔE)2=[(ΔL)2+(Δa)2+(Δb)2].

ΔE is the darkening, the global intensity of the color: The more ΔE is important the more the color darkened.

Results:

















Product to be tested
L*
a*
b*
ΔE*






















Ex 2a
84.26
−1.78
21.7
17.0



Chemical oxidation of



vitamin C



Ex2b
87.16
−0.26
10.4
5.4



Oxidation of vitamin C



by a free enzyme



Ex 2 c
85.61
1.84
21.27
16.5



Oxidation of vitamin C



by an immobilized



enzyme










Example 3: Care Cream (Oil-in-Water Emulsion)














A.
Glyceryl stearate (and) PEG-100 stearate
2.00%



Dimyristyl tartrate (and) cetearyl alcohol (and) C12-15
1.50%



Pareth-7 (and) PP %-25 Laureth-25



Cyclohexasiloxane:
10.00% 



Stearyl alcohol:
1.00%


B.
Water:
80.75% 



Phenoxyethanol:
1.00%



Pentasodium ethylenediaminetetramethylenephosphate
0.05%



Ammonium polyacryldimethyltauramide
0.40%



Xanthan gum
0.20%


C.
Dehydroascorbic acid
3.00%









Procedure:
Heat phase B to about 75° C. and incorporate the ammonium polyacryldimethyltauramide therein; stir until a homogeneous gel is obtained.
Heat phase A to about 75° C.
Prepare the emulsion by incorporating phase A into phase B.
At 40-45° C., incorporate phase C and keep stirring until fully cooled.
Example 4: Cream Gel














A.
Cyclomethicone
5%



Hydrogenated polyisobutene
5%



Xanthan gum
0.4%  



Acrylates/C10-30 alkyl acrylate crosspolymer
0.25%  



Preservatives
1%


B.
Water
77.65%   



Glycerol
5%



Dimethicone PEG-7 phosphate
2%



Carbomer
0.4%  



Sodium hydroxide
0.3%  



Dehydroascorbic acid dimer
3%









Procedure:
Phases A and B are homogenized at room temperature, and the emulsion is then prepared by introducing phase A into phase B with vigorous stirring.
Example 5: Two-Component Formulation
Component (1): Oil-in-Water Emulsion with Ascorbic Acid:














A.
Polyethylene glycol stearate (20 EO)
0.8%



Glyceryl mono/distearate/polyethylene glycol stearate
  2%



(100 EO)



Cetyl alcohol
0.7%



Stearyl alcohol
0.7%



Stearic acid
  1%



Isocetyl stearate
  6%



Beeswax
  1%



Preservatives
0.6%


B.
Glycerol
  7%



Water
qs



Triethanolamine
0.23% 


C.
Cyclopentadimethylsiloxane
 10%


D.
Acrylamide/sodium acryloyldimethyltaurate copolymer
1.6%



(and) isohexadecane (and) Polysorbate 80


E.
Ascorbic acid
  5%









Procedure:
Heat phases A and B to about 75° C.
Prepare the emulsion by introducing phase A into phase B with vigorous stirring
At 40-45° C., incorporate phase C, followed by D, and maintain the stirring until fully cooled
Incorporate phase E when cold
Component (2): Aqueous Gel Containing Ascorbate Oxidize:














A.
Water
qs



Glycerol
7%



1,3-Butylene glycol
5%


B.
Synthetic laponite (Magnesium/lithium/sodium mixed
3%



silicate)


C.
Ethyl alcohol
10% 



1,2-Octanediol
0.4%  









Procedure:
Heat phase A to 65° C.
Add phase B and then allow to cool to room temperature
Incorporate Phase C
The two components are conditioned in double-body packaging with a separate dispensing pump allowing mixing on application.
Example 6: Three-Component Formulation
Component (1): Oil-in-Water Emulsion with Ascorbic Acid:














A.
Polyethylene glycol stearate (20 EO)
0.8%



Glyceryl mono/distearate/polyethylene glycol stearate
  2%



(100 EO)



Cetyl alcohol
0.7%



Stearyl alcohol
0.7%



Stearic acid
  1%



Isocetyl stearate
  6%



Beeswax
  1%



Preservatives
0.6%


B.
Glycerol
  7%



Water
qs



Triethanolamine
0.23% 


C.
Cyclopentadimethylsiloxane
 10%


D.
Acrylamide/sodium acryloyldimethyltaurate copolymer
1.6%



(and) isohexadecane (and) Polysorbate 80


E.
Ascorbic acid
  5%









Procedure:
Heat phases A and B to about 75° C.
Prepare the emulsion by introducing phase A into phase B with vigorous stirring
At 40-45° C., incorporate phase C, followed by D, and maintain the stirring until fully cooled
Incorporate phase E when cold
Component (2): Water-in-Oil Emulsion Containing Dehydroascorbic Acid:

















A.
Glyceryl monostearate/polyethylene glycol stearate (100
2%




EO)




Arachidyl polyglucoside/arachidyl, behenyl alcohols
3%




Isohexadecane
4%




Polydimethylsiloxane
1%




C12-15 alkyl benzoate
4%




Trialkyl citrate
3%




Preservatives
0.5%  



B.
Ethylenediaminetetraacetic acid
0.1%  




Glycerol
4%




Propylene glycol
6%




Water
10% 




Preservatives
0.2%  



C.
Polyacrylamide/C13-14 isoparaffin/Laureth-7
1%



D.
Mixture of natural tocopherols in soybean oil (50/50)
0.1%  



E.
Dehydroascorbic acid dimer
5%




Microbiologically pure deionized water (qs)
qs



F.
Ethyl alcohol
5%










Procedure:
Heat phases A and B to about 75° C.
Prepare the emulsion by introducing phase A into phase B with vigorous stirring and while incorporating phase D therein; stir until a homogeneous gel is obtained
At 40-45° C., incorporate phase D, followed by E, and maintain the stirring until fully cooled
Incorporate phase F when cold
Component (3): Aqueous Gel Containing Ascorbate Oxidize:














A.
Water
qs



Glycerol
7%



1,3-Butylene glycol
5%


B.
Synthetic laponite (magnesium/lithium/sodium mixed
3%



silicate)


C.
Ethyl alcohol
10% 



1,2-Octanediol
0.4%  









Procedure:
Heat phase A to 65° C.
Add phase B and then allow to cool to room temperature
Incorporate Phase C
Each patent, patent application, publication, text and literature article/report cited or indicated herein is hereby expressly incorporated by reference in its entirety.
While the invention has been described in terms of various specific and preferred embodiments, the skilled artisan will appreciate that various modifications, substitutions, omissions, and changes may be made without departing from the spirit thereof. Accordingly, it is intended that the scope of the present invention be limited solely by the scope of the following claims, including equivalents thereof.

## Claims

1. A regime or regimen for artificially coloring the skin, comprising topically applying onto the skin of an individual seeking such treatment, a composition containing a thus effective amount of dehydroascorbic acid and/or a monomeric derivative thereof of formula (I) below and/or an isomer thereof of formula (I′) below and/or a polymer derivative thereof:



in which OR1 and OR2, which may be identical or different, are each OH; a linear or branched, saturated or unsaturated C1-C30 alkoxy radical; a glycoside; a linear or branched, saturated or unsaturated C1-C30 aliphatic carboxylic acid ester, which may be substituted with an aryl group or a heterocycle; an aryl or heterocyclic carboxylic acid ester which may be substituted with at least one linear or branched, saturated or unsaturated C1-C30 alkyl radical; a phosphate group; a sulfate group, and also polymeric derivatives thereof, formulated into a topically applicable physiologically acceptable medium therefor;
wherein the dehydroascorbic acid and/or a monomeric derivative thereof of formula (I) and/or an isomer thereof of formula (I′) and/or a polymer derivative thereof is combined with ascorbic acid or a derivative or salt thereof.

2. The regime or regimen as defined by claim 1, said composition comprising a dehydroascorbic acid compound of formula (I) having the structural formula:

3. The regime or regimen as defined by claim 1, said composition comprising the compound of formula (I′), 3a,6-dihydroxy-tetrahydro-furo[3,2-b]furan-2,3-dione having the structural formula:

4. The regime or regimen as defined by claim 1, said composition comprising a polymeric dimeric compound having the structural formula (II) below:



in which OR1, OR2, OR3 and OR4, which may be identical or different, are each OH; a linear or branched, saturated or unsaturated C1-C30 alkoxy radical; a glycoside; a linear or branched, saturated or unsaturated C1-C30 aliphatic carboxylic acid ester, which may be substituted with an aryl group or a heterocycle; an aryl or heterocyclic carboxylic acid ester which may be substituted with at least one linear or branched, saturated or unsaturated C1-C30 alkyl radical; a phosphate group; or a sulfate group.

5. The regime or regimen as defined by claim 4, said composition comprising a compound having the following structural formula:

6. The regime or regimen as defined by claim 1, said composition comprising dehydroascorbic acid formed “in situ” from ascorbic acid or a derivative or salt thereof via chemical oxidation and/or via enzymatic oxidation.

7. The regime or regimen as defined by claim 1, said composition further comprising one or more additional stabilizers, and/or a photoprotective agent and/or a wetting agent and/or penetrant and/or at least one additional colorant.

8. The regime or regimen as defined by claim 1, said composition further comprising at least one additional active agent selected from the group consisting of organic UV screening agents, inorganic UV screening agent, moisturizers, desquamating agents, agents improving the skin barrier function, depigmenting agents, antioxidants, dermo-decontracting agents, anti-glycation agents, agents stimulating the synthesis of dermal and/or epidermal macromolecules and/or preventing their degradation, agents stimulating fibroblast or keratinocyte proliferation and/or keratinocyte differentiation, agents promoting the maturation of the horny envelope, NO synthase inhibitors, peripheral benzodiazepine receptor (PBR) antagonists, agents increasing the activity of the sebaceous gland, agents stimulating the energy metabolism of cells, tensioning agents, fat restructuring agents, slimming agents, agents promoting the cutaneous microcirculation, calmatives and/or anti-irritants, sebo-regulating or anti-seborrheic agents, astringents, cicatrizing agents, anti-inflammatory agents and anti-acne agents.

9. The regime or regimen as defined by claim 1, said composition further comprising at least one additional active agent selected from the group consisting of matting agents, soft-focus effect fillers, fluorescers, agents promoting the naturally pinkish coloring of the skin, abrasive fillers and exfoliants.