Patent Application
20130034509
The present invention relates to a method for the cosmetic treatment of the skin involving a compound, or set of compounds, capable of condensing in situ.
In cosmetics, particular properties (for example optical, mechanical, and/or tactile) are conferred to the skin. However, one of the main problems in cosmetics is to confer these particular properties quickly and durably. A person skilled in the art may notably be faced with the following problems:
In order to increase the kinetics of color development, DHA has been used in conjunction with amino acids. In this case, coloration is visible on the skin in about 1 hour, but this coloration is not tenacious and disappears at the first washing.
Consequently, it is not possible at present to offer a cosmetic composition for conferring a color change on the skin quickly (in about one hour) and that is tenacious (for example lasting 2 to 5 days).
This problem connected with the use of coloring products is also encountered to a varying degree in all cosmetic cutaneous applications.
Patent application FR2929112 describes the use of a combination of alkoxysilanes with a solubilizing group and at least one cyclanone derivative in hair coloring. However, as far as to the applicant knowledge, the prior art does not disclose the possibility of using a compound capable of condensing in situ, i.e. in or on the skin, in a method of cosmetic treatment enabling to confer to the skin a particular property in a localized, rapid and tenacious manner.
Surprisingly, the applicant has shown that it is possible to form, in the surface layers of the skin or on the skin, a condensate that confer to the skin the property of capturing compounds of cosmetic interest. This so-called “capture” layer is formed by condensation in situ of at least one compound or set of compounds A that will be described later.
Particularly surprisingly, the applicant was also able to show that very good cosmetic results could be obtained when the compounds of cosmetic interest (called C hereinafter) are selected in such a way that they decrease the water-solubility of the condensate of A (also called “material resulting from the condensation of A” hereinafter).
The advantageous properties obtained as a result of the method according to the invention are notably:
The present invention therefore relates to a method for the cosmetic treatment of the skin, comprising application on the skin of:
The applicant was indeed able to demonstrate that application of these two types of compounds on the skin makes it possible to confer localized, rapid and tenacious cosmetic properties.
The capture layer is formed in situ in the surface layers of the skin by condensation of a compound or of a set of compounds A.
The invention also relates to the use of a compound or set of compounds A capable of condensing in situ and having at least one free reactive function FA after condensation, as an agent for capturing a compound of cosmetic interest on or in the skin.
The invention therefore also relates to the use of a compound or set of compounds A capable of condensing in situ and having at least one free reactive function FA after condensation, for capturing, on or in the skin, a compound C of cosmetic or dermatological interest comprising a reactive function FC that is able to form a covalent bond by reaction with the function FA.
According to particular embodiments of the methods, uses and sets according to the invention, the material resulting from the condensation of A is soluble in water and compound C of cosmetic interest is selected so that reaction of said compound C on the material resulting from the condensation of A leads to a decrease in the solubility of said material in water.
According to another aspect, the invention relates to a method of insolubilizing a condensate in the skin, comprising application on the skin:
The invention also relates to a method for decreasing the solubility of (or even making insoluble), on or in the skin, the material resulting from the condensation of a compound or set of compounds A capable of condensing in situ and having at least one free reactive function FA after condensation, said material being soluble in water, comprising application, on said material, of a compound C of cosmetic interest comprising a reactive function FC that is able to form a chemical bond, which can be covalent or ionic, by reaction with the function FA, C being selected so that reaction of said compound C on the material resulting from the condensation of A leads to a decrease in the solubility of said material in water.
The invention also relates to a method for obtaining, on or in the skin, an insoluble condensate having cosmetic properties, comprising application on the skin:
The invention also relates to the use of a compound C for decreasing the solubility of (or even making insoluble) a material resulting from the condensation of a compound or set of compounds A capable of condensing in situ and having at least one free reactive function FA after condensation, said material being soluble in water, C being a compound of cosmetic interest comprising a reactive function FC that is able to form a covalent or ionic bond by reaction with the function FA.
The applicant was indeed able to demonstrate that application of these two types of compounds on the skin makes it possible to confer localized, rapid and tenacious cosmetic properties. The decrease in solubility of the material resulting from the condensation of A makes it possible, moreover, to further increase its permanence on and/or in the skin (resistance to water, sweat, sebum, etc.) while maintaining, or even reinforcing, the cosmetic property conferred by compound C.
Each element of the invention will now be described in detail.
In the context of the present invention, the term “skin” describes the skin or the scalp.
According to a first particular embodiment, a compound A capable of condensing in situ is used. In this embodiment, compound A must comprise at least two reactive functions: a function enabling compound A to condense on itself and at least one so-called capturing reactive function FA, or a function leading to the formation of a function FA after condensation.
According to a second embodiment, a set of compounds A is used. This embodiment comprises implementation of at least two molecules capable of condensing with one another. In this case, and according to the invention, the molecules constituting the set of compounds must comprise one or more functions permitting condensation of set A, and one or more functions permitting the presence of a capturing reactive function FA after condensation. According to a particular embodiment, the function or functions FA is/are present on only one of the compounds of the set of compounds A. In another embodiment, the reactive function or functions is/are present on at least two compounds of the set of compounds.
In other words, with a set of compounds A consisting of the molecules A1 and A2, A2 need not contain a capturing function. In this case, either A1 has capturing functions, or the latter appear at the end of the condensation reaction. Alternatively, compound A2 can contain capturing functions. In this case, compound A1 need not contain any capturing function.
As an illustration, the condensation of the set of compounds A can be represented as follows.
Set of compounds A comprising two compounds: A1 and A2
It is to be understood that this particularly simplified schematic example is only presented for purposes of illustration and must not be regarded as limiting the invention.
According to a preferred embodiment, the method according to the invention comprises:
The condensation and capturing functions will be described hereinafter referring to A, which will denote indiscriminately a compound A or a set of compounds A (for example A1+A2) described above.
The capturing function or capturing functions must be at least partially free after condensation of A so as to be able to react with compound C. Alternatively, the capturing function or capturing functions are not present or are not in free form in the compound or set of compounds A but may appear or become free at the end of condensation thereof. They may for example be primary amine functions, which could appear following the action of an enzyme naturally present on the skin.
Preferably, the capturing functions that are free after condensation must be in proportions such that Fcapt/A>0.1 and preferably >0.5, Fcapt and A representing, respectively, the amounts in number of free capturing functions after condensation and of molecules of A. In other words, after condensation there is at least one free capturing function for every 10 molecules of A, preferably at least 5 free capturing functions.
The capturing functions FA of the compound or set of compounds A are typically selected from amines and other nucleophilic functions, such as hydroxyl functions, thiols, sulfates and phosphates. Preferably, they are amines; preferably, primary amines.
The condensation of A can arise from the reaction of a nucleophilic species on an electrophilic species. According to a first alternative, the condensation functions are typically those permitting the creation of a bond by elimination of a molecule of water according to the following equation:
R—OH+HO—R′→R—O—R′+H2O
In a particular embodiment, the compounds employed are organosilanes.
According to a second alternative, condensation can arise from the reaction of a species by stripping of a proton from a second species, notably according to one of the following equations:
R—CH═CH2+H—R′→R—CH2—CH2—R′
and
R—CH═NH+H—R′→R—CH2—NH—R′
In the above equations, R and R′ denote, independently of one another, any group of atoms, it being understood that the condensation product of A must comprise at least one free function FA.
Preferably, condensation takes place according to the first alternative described above.
In a particular embodiment, compound A is an organic compound of silicon comprising 1 to 3 silicon atoms, and at least two hydroxyl or hydrolyzable groups per molecule. Compound A is therefore selected from the organosilanes comprising one silicon atom and the organosiloxanes having two or three silicon atoms, preferably two silicon atoms.
According to a preferred embodiment, compound A is an organosilane. Compound A can notably be an alkoxysilane, and preferably a functionalized alkoxysilane.
The set of compounds A can be a mixture of an organosilicon compound as described above (compound A1) and of at least one other compound (compound A2) such that the set comprising the organosilicon compound and compound A2 is capable of condensing in situ.
Preferably, compound A (or at least one of the molecules of the set of compounds A) corresponds to the formula:
in which:
The organosiloxanes that are preferred in the compositions of the present invention can be represented by the formula:
in which:
Preferably, the halogen is chlorine.
A particularly preferred class of organic compounds of silicon consists of the compounds of formula:
in which the radicals R, which may be identical or different, are selected from the C1-C6 alkyl radicals such as methyl, ethyl, propyl, butyl and n is an integer from 1 to 6, preferably from 2 to 4.
In particular, compound A is an alkoxysilane comprising at least one nucleophilic capturing function, and in particular γ-aminopropyl triethoxysilane, called APTES hereinafter, or a derivative thereof.
Compound A2 that may be involved in the method according to the present invention, when a set of compounds A is applied on the skin, can for example correspond to the same definition as compound A given above. Compound A2 can notably be selected from molecules having the capacity to form an Si—O—Si bond. As an illustration, we may mention methyl-triethoxysilane (MTES).
A is selected so that condensation only takes place once it has reached the region where said condensation is to take place. For example, compound A may be very reactive, and its condensation may take place on the surface of the skin. Alternatively, condensation may take place once compound A has penetrated to a certain depth in the skin.
In general, compound A, or the set of compounds A, is soluble in water owing to the reactive functions that it comprises. Owing to these properties, the material resulting from the condensation of A is also generally soluble in water.
The compound of cosmetic interest (compound C) is a compound capable of conferring at least one specific property on the skin, or a mixture of such compounds, and comprises at least one chemical function FC capable of reacting with at least one of the free capturing functions of the material resulting from the condensation of compound A or of the set of compounds A.
Compound C can also be capable of reacting with itself.
As chemical functions FC capable of reacting with at least one of the free capturing functions of the material resulting from the condensation of compound A or of the set of compounds A, we may notably mention halogen atoms and carbonyl, carboxylic acid, ester, amine and hydroxyl functions.
In particular, they are functions including a carbonyl group. In a preferred embodiment of the invention, compound C contains at least one aldehyde or ketone function and is capable of reacting with a primary amine (representing the function FA of the compound or set of compounds A) as follows:
Compound C can be selected from simple aldehydes, conjugated aldehydes, aromatic aldehydes such as benzaldehydes and activated ketones, notably by an attracting group, or conjugation functions.
The carbonyl functions can be in the form of enols. The carbonyl functions can also be engaged, for example in the case of acetals, hemiacetals, ketals, and their sulfur-containing equivalents.
Among other carbonyl functions conceivable in this context, we may mention for example esters, acid halides, anhydrides, isocyanates.
More generally, the functions FC of compound C are typically electron-accepting groups and thus can be selected from:
A person skilled in the art knows perfectly the chemical functions that are to be used in the compound or set of compounds A as a capturing function (FA) and capable of reacting with each of the chemical functions described in the preceding paragraph.
The following scheme represents the case when a compound C comprising an imine function FC is reacted with a primary amine capturing function.
Compounds C that react with the free capturing functions after condensation of A by a physicochemical effect such as complexation, formation of salts that can crystallize, formation of water-insoluble complexes or salts or the formation of ionic liquids also fall within the scope of the invention.
In a particular embodiment, compounds C capable of reacting more than once with the material resulting from the condensation of A are preferred. For example, we may mention:
The following section describes, non-exhaustively, examples of properties that can be conferred to the skin by applying the method according to the invention.
The invention relates to treatment of the skin in general. Then compound A, or the set of compounds A, and compound C are selected according to the desired effect on the skin:
In a particular embodiment of the invention, an active molecule can be fixed by means of the invention. Compounds A and C are selected so that release can be triggered either by a natural effect (for example in the case of released triggered by sweating), or by a human action (as in the case of particular irradiation, for example light (notably UV, visible) or heat. Thus, compounds A and C can be used that have a fragile bond, such as thermo- or photocleavable.
The invention also covers more precise aspects and methods, for example:
As we have seen above, the compounds or sets of compounds A generally have properties of water solubility. Compound A can thus be transported and can penetrate the first layers of the skin. Thus, quite often, the materials resulting from the condensation of the compounds or sets of compounds A retain high water solubility. This is the case for example when compound A is an aminoalkylalkoxysilane such as APTES (cf. below). This water solubility of the material resulting from compound A lessens its capture effect and more particularly the durability of capture.
It is in theory conceivable to use a compound A that is soluble in water and sufficiently reactive to give, after condensation, a compound that is insoluble in water. However, this is difficult in practice because:
Thus, in a particular embodiment of the invention, compounds A and compound C are selected so that:
To make this choice, a person skilled in the art can use the method for selecting suitable compounds A and C described below.
According to a particular embodiment, compounds A and C are selected so that the material resulting from the condensation of A is soluble in water, and once C has reacted with the material resulting from the condensation of A, said material is insoluble in water.
Compounds A and C are selected as follows:
a) A is applied in the appropriate aqueous medium in a Petri dish in conditions in which A can condense;
b) after evaporation of the medium, compound C is applied in conditions permitting its reaction with the material resulting from the condensation of A;
c) the weight of the material resulting from the condensation of A that has reacted with C is then measured;
d) the water solubility of the condensate that has reacted with compound C is measured by putting it in water for 30 minutes, then recovering the undissolved portion and determining the value PPA+C, which corresponds to the weight loss of the material expressed as a percentage; a value PPx=0 indicates complete insolubility of the material tested in water; a value PPx=100% indicates complete solubility of the material tested in water;
e) steps c) and d) are also applied to the material resulting from the condensation of A in the absence of compound C. The value PPA is thus measured.
f) the value PPA+C is compared with the value PPA.
According to this method of selection, compounds A and C are used which make it possible to obtain a value of PPA+C lower than the value of PPA, as A has been made insoluble by adding C.
A person skilled in the art will select the compounds to use in the method according to the invention from the equation: PPA+C=PPA−n, or n=PPA−PPA+C, it being understood that PPA−n>0. Thus, more particularly, combinations of compounds A and C will be used that give a value of n above 15%, preferably n>30% and even more preferably n>50%.
According to a particular embodiment of the invention, PPA+C is less than 15% and PPA is greater than 50%.
Preferably, compound A is selected so that its reactivity is moderate. Compound A remains mostly in the form of monomer, and does not form more monomer+dimer+trimer.
The following test is used for verifying this point:
Color
In a particular embodiment, the method according to the invention is a cosmetic method of coloring the skin, in which compound C is a molecule that can confer a color on the skin.
In the present invention, the property “color” denotes at least one coloring effect on the skin, which can be for example an increase or a change of color, a modification of chromaticity, development of fluorescence, of phosphorescence, of chemiluminescence, of brightness or dulling.
In order to confer a property of color, typically compounds A and C are used which, in addition to the requirements described above, give a chromophore. It is also possible to use a compound A that is colored, and/or a compound C that is colored, or a compound A and/or a compound C which, although colorless, gradually becomes colored. It is also possible to use compounds A and/or C that have a bleaching, decolorizing or depigmenting effect.
In particular, the final color can be more aesthetic than compound C would have given in the absence of compound A. For example, it can be more in tune with the complexion or can give a more natural appearance. Compounds C that do not give any color in applications outside of the present invention, give interesting color effects in the present invention.
Compound C can be colored. In this case, the invention can notably serve for improving the durability of the color.
Compound C can be colorless. In this case, the invention serves for making the color appear, and optionally for giving durability to this color.
Finally, compound C can be colorless and does not provide a color after reaction with compound A. In this case, compound C is selected so that it can give, by a transformation after application, prior to, simultaneously with or subsequent to the reaction with the material resulting from the condensation of A, a colored species. In particular, compound C can give a colored species by an oxidation reaction. C can be, in this context, a polyphenol, a diamine compound, or a hydroxylamino compound. Compound C can transform naturally to a colored species, or it is possible to initiate or assist the transformation for example by adding an oxidant, a catalyst or an oxidation enzyme.
According to a particularly surprising embodiment of the invention, it is also possible, by means of the method described above, to obtain effects such as fluorescent effects, which are often very difficult to obtain, even non-permanently (see below in the description of compounds C that can be used for conferring a coloring effect).
The applicant was also able to show that it was possible to modulate the durability of the coloring effect over time by adjusting the interval between application of A and of C on the skin. This property can be exploited to obtain higher or intermediate durability, which cannot be achieved with the methods of coloring used conventionally. For example, a tanned effect can be obtained for a period of 2 days. This durability is surprising compared to that obtained conventionally with existing methods, notably compared to existing colorations obtained with DHA. It may be suitable for those who want to be attractive over a weekend, for example.
Compounds C for conferring a color effect on the skin according to the invention can notably be selected from the lists given below.
Self-Tanning Agents:
Self-tanning agents are generally selected from certain mono- or polycarbonylated compounds, for example isatin, alloxan, ninhydrin, glyceraldehyde, mesotartaric aldehyde, glutaraldehyde, erythrulose, the derivatives of pyrazoline-4,5-diones as described in patent application FR 2 466 492 and WO 97/35842, dihydroxyacetone (DHA), the derivatives of 4,4-dihydroxypyrazolin-5-ones as described in patent application EP 903 342. DHA will preferably be used.
DHA can be used in free form and/or encapsulated for example in lipid vesicles such as liposomes, notably described in application WO 97/25970.
The self-tanning agent or agents are generally present in proportions in the range from 0.1 to 15 wt. % and preferably from 0.2 to 10 wt. %, and more preferably from 1 to 8 wt. % relative to the total weight of the composition containing them.
Other Compounds C Usable for Conferring a Color Effect:
Compound C can also be selected from molecules which, although colorless, are able to form colored compounds after being used according to the invention, in particular in the case when compound A is APTES (or a PolyAPTES film, the condensation product of APTES). We may mention in particular cinnamaldehyde, citronellal and citral.
Compound C can also be selected from molecules that are able to form fluorescent compounds under UV (optical brighteners) after application thereof according to the invention, in particular in the case when compound A is APTES. We may mention in particular nonanal and hydroxycitronellal.
In fact, the applicant observed the surprising appearance of fluorescence in regions of the skin where the method according to the invention was used.
For conferring a property of brightness to the skin, typically compounds A and C are used which, in addition to the requirements described above, give a diffusing material or on the contrary one that is very smooth. For example, C can react with the material resulting from the condensation of A to give a powder.
Conditioning of the Skin
In a particular embodiment, the method according to the invention is a cosmetic method of skin conditioning, in which compound C is a molecule capable of modifying the physicochemical properties of the skin.
It is notably possible to use agents for modifying the physicochemical surface properties of the skin. Then typically compounds A and C are used which, in addition to the requirements described above, give a material whose characteristics of surface tension are different from those of the skin. It is also possible to use compounds A and C which, in addition to the requirements described above, give a material that forms a barrier to the passage of certain molecules.
The conditioning of the skin can be obtained using a compound C selected from conditioning polymers.
Conditioning Polymers:
The conditioning polymers that can be used in the context of the invention can be selected from the lists given below:
The hydrophobic monomers with an ethylenic unsaturation of the invention are preferably selected from the acrylates or acrylamides of the following formula (1):
in which R27 denotes a hydrogen atom, a linear or branched C1-C6 alkyl radical (preferably methyl); Y denotes O or NH; R28 denotes a hydrophobic radical comprising a fatty chain having from 7 to 30, preferably from 7 to 22, and more particularly from 12 to 22 carbon atoms.
The hydrophobic radical R28 is preferably selected from saturated or unsaturated linear C7-C22 alkyl radicals (for example n-octyl, n-decyl, n-hexadecyl, n-dodecyl, oleyl), branched (for example isostearic) or cyclic (for example cyclododecane or adamantane); C7-C18 alkyl-perfluorinated radicals (for example the group of formula —(CH2)2—(CF2)9—CF3); the cholesteryl radical or a cholesterol ester such as cholesteryl hexanoate; polycyclic aromatic groups such as naphthalene or pyrene. Among these radicals, the linear and branched alkyl radicals are more particularly preferred.
According to a particularly preferred embodiment of the invention, the hydrophobic radical R28 further comprises at least one alkylene oxide unit and preferably a polyalkoxylated chain. The polyalkoxylated chain preferably consists of ethylene oxide units and/or propylene oxide units and even more particularly is constituted solely of ethylene oxide units. The number of moles of alkoxylated units generally varies from 1 to 30 moles and more preferably from 1 to 25 moles and even more preferably from 3 to 20 moles.
Among these polymers, we may mention:
We may mention more particularly the crosslinked or noncrosslinked amphiphilic copolymers consisting of:
in which X+ is a proton, an alkali metal cation, an alkaline-earth cation or the ammonium ion;
in which n and p, independently of one another, denote a number of moles and vary from 0 to 30, preferably from 1 to 25 and more preferably from 3 to 20 provided that n+p is less than or equal to 30, preferably less than 25 and better still less than 20; R27 has the same meaning as given above in formula (1) and R29 denotes a linear or branched alkyl having m carbon atoms, m being in the range from 7 to 22, preferably from 12 to 22.
In formula (2), the cation X+ denotes more particularly sodium or ammonium.
Among the monomers of formula (3), we may mention
As mentioned above, these hydrophobized AMPS polymers as described can be used as additives in an emulsion, and in this case will preferably be dissolved in the aqueous phase of the latter, or else as emulsifiers. In this case, they permit the formation of 0/W emulsions as described in applications WO02/055039, WO02/055038, EP 1353642, EP 1353633, WO02/055052, FR2853544, EP1466587.
Oxyethylenated PDMS Derivatives (or Water-Soluble Silicones)
The water-soluble silicones usable in the invention are preferably selected from compounds of general formulas (I) and (II):
in which:
The water-soluble silicones according to the invention are known and notably are described in U.S. Pat. No. 5,338,352 and their manner of preparation is described notably in U.S. Pat. No. 4,847,398.
Such silicones are sold for example by the company OSI under the trade names Silwet L-720®, Silwet L-7002®, Silwet L-7600®, Silwet L-7604®, Silwet L-7605®, Silwet L-7607®, Silwet 1614, Silwet L-7657®, Silwet L-7200®, Silwet L7230, Silsoft 305, Silsoft 820, Silsoft 880, Tegowet 260, Tegowet 500, Tegowet 505 and Tegowet 510®.
Amphiphilic Block Polymers
The block copolymers used in the method according to the invention are notably amphiphilic block, nonionic, diblock or triblock polymers, which can form, in contact with water, micelles, particles of the vesicle type (for example liposomes) or lyotropic liquid crystal phases of the lamellar, cubic (direct or inverted) or hexagonal (direct or inverted) type in contact with water. They are notably of the diblock (A-B) or triblock (A-B-A) type, with A corresponding to a hydrophilic nonionic polymer block and B to a hydrophobic polymer block. The molecular weight of the polymers can be between 1000 and 100 000 and the ratio AB can be between 1/100 and 50/1.
The block copolymers used can notably be selected from the polystyrene-based amphiphilic block polymers.
The hydrophobic polymer block can then be selected from polystyrene and poly(tert-butylstyrene).
The hydrophilic nonionic polymer block is preferably selected from poly(ethylene oxide) (PEO) and polyvinylpyrrolidone (PVP).
As examples, we may mention Tegomer SE 1010 and SE 1030 from the company Goldschmidt (cf. applications EP1555984 and EP1413290 which describe the use of block polymers in sun cream compositions).
The block copolymers used can also be selected from amphiphilic polyethoxylated block polymers.
The hydrophobic polymer block of the invention can correspond to:
Hydrophobic vinyl monomers of the following formula (A):
in which:
The block copolymer is preferably selected from the following block copolymers:
As an example, we may mention TegomerBE 1010 and BE 1030 as well as Tegomer ME 1010 and ME 1030 from the company Goldschmidt (cf. applications EP1555984 and EP1413290 which describe the use of block polymers in sun cream compositions)
in which R1 is a C1-C4 lower alkyl radical, and preferably an ethyl group and n has a value such that the molecular weight is at least equal to 10000.
The oxazoline polymers of formula (I) have a molecular weight above 10000, generally between 20000 and 1000000, and preferably between 50000 and 500000 and are prepared by polymerization of 2-alkyl-2-oxazoline. The preferred polymers are the homopolymers of ethyloxazoline having a molecular weight between 20000 and 1000000, and more particularly those sold under the designation PEOX by the company DOW CHEMICAL having molecular weights from 50000 to 500000.
A polymer that is more particularly preferred according to the invention is represented by a homopolymer of ethyloxazoline of molecular weight 50000.
As a nonlimiting example, we may mention the products from Dow Chemical, marketed under the name PEOX (MW 50000), PEOX (MW 200000), PEOX (MW 500000), POLYMER XAS-10874.01, or from Sigma-Aldrich, marketed under the names Poly(2-ethyloxazoline) MW 50000, Poly(2-ethyloxazoline) MW 200000 and Poly(2-ethyloxazoline) MW 500000.
The polymers comprising a methacryloyloxethyl-phosphorylcholine (MPC) group are particularly effective for improving the properties of water retention on the surface of the skin and of the hair. Their use in the cosmetic field is the object of applications from Pola, JP2832119 (corresponding to U.S. Pat. No. 5,468,475 and FR2698003) as a means for hydrating the skin and the hair and can be used as conditioning polymers in the context of the present invention. Acrylic polymer with a group of the phosphorylcholine type, means a polymer having an acrylic skeleton and comprising pendant groups (or side chains) containing a group of the following formula (I):
in which R1, R2 and R3 denote independently an alkyl group having from 1 to 8 carbon atoms; R4 denotes —(CH2—CHR60)m—(CH2—CHR6)— with R6 denoting a hydrogen atom, a group or ethyl methyl, and m denotes an integer in the range from 0 to 10; R5 denotes —(CH2)g—, g being an integer in the range from 2 to 10.
A polymer of this kind can be obtained by polymerization of an acrylic monomer comprising the group of formula (I) described above, called acrylic monomer PC hereinafter.
Advantageously, the acrylic monomer PC is a monomer corresponding to the following formula (II):
in which R′, R2 and R3 denote independently an alkyl group having from 1 to 8 carbon atoms; n represents an integer in the range from 2 to 4; R7 denotes a hydrogen atom or a methyl group.
As the acrylic monomer PC, we may mention the following monomers: 2-(meth)acryloyloxyethyl-2′-(trimethylammonio)ethyl phosphate, 3-(meth)acryloyloxypropyl-2′-(trimethylammonio)ethyl phosphate, 4-(meth)acryloyloxybutyl-2′-(trimethylammonio)ethyl phosphate, 5-(meth)acryloyloxypentyl-2′-(trimethylammonio)ethyl phosphate, 2-(meth)acryloyloxyethyl-2′-(triethylammonio)ethyl phosphate, 3-(meth)acryloyloxypropyl-2′(triethylammonio)ethyl phosphate, 4-(meth)acryloyloxybutyl-2′-(triethylammonio)ethyl phosphate, 5-(meth)acryloyloxypentyl-2′-(triethylammonio)ethyl phosphate, 2-(meth)acryloyloxyethyl-2′-(tripropylammonio)ethyl phosphate, 3-(meth)acryloyloxypropyl-2′-(tripropylammonio)ethyl phosphate, 4-(meth)acryloyloxybutyl-2′-(tripropylamonnio)ethyl phosphate, 5-(meth)acryloyloxypentyl-2′-(tripropylammonio)ethyl phosphate, 2-(meth)acryloyloxyethyl-2′-(tributylammonio)ethyl phosphate, 3-(meth)acryloyloxypropyl-2′-(tributylammonio)ethyl phosphate, 4-(meth)acryloyloxybutyl-2′-(tripropylammonio)ethyl phosphate, 5-(meth)acryloyloxypentyl-2′-(tributylammonio)ethyl phosphate, 2-(meth)acryloyloxyethyl-3′-(trimethylammonio)propyl phosphate, 2-(meth)acryloyloxyethyl-4′-(trimethylammonio)butyl ethyl phosphate, 2-(meth)acryloyloxyethyl-3′-(triethylammonio)propyl phosphate, 2-(meth)acryloyloxyethyl-4′(triethylammonio)butyl phosphate, 2-(meth)acryloyloxyethyl-3′-(tripropylammonio)propyl phosphate, 2(meth)acryloyloxyethyl-4′-(tripropylammonio)butyl phosphate, 2-(meth)acryloyloxyethyl-3′-(tributylammonio)propyl phosphate, 2-(meth)acryloyloxyethyl-4′-(tributylammonio)butyl phosphate, 3-(meth)acryloyloxyethyl-3′-(trimethylammonio)propyl phosphate, 3-(meth)acryloyloxypropyl-4′-(trimethylammonio)butyl phosphate, 3-(meth)acryloyloxypropyl-3-(triethylammonio)propyl phosphate, 3-(meth)acryloyloxypropyl-4′-(triethylammonio)butyl phosphate, 3-(meth)acryloyloxypropyl-3′-(tripropylammonio)propyl phosphate, 3-(meth)acryloyloxypropyl-4′-(tripropylammonio)butyl phosphate, 3-(meth)acryloyloxypropyl-3′-(tributylammonio)propyl phosphate, 3-(meth)acryloyloxypropyl-4′-(tributylammonio)butyl phosphate, 4-(meth)acryloyloxybutyl-3′-(trimethylammonio)propyl phosphate, 4-(meth)acryloyloxybutyl-4′-(trimethylammonio)butyl phosphate, 4-(meth)acryloyloxybutyl-3′-(triethylammonio)propyl ethyl phosphate, 4-(meth)acryloyloxybutyl-4′-(triethylammonio)butyl phosphate, 4-(meth)acryloyloxybutyl-3′-(tripropylammonio)propyl phosphate, 4-(meth)acryloyloxybutyl-4′-(tripropylammonio)butyl phosphate, 4-(meth)acryloyloxybutyl-3′-(tributylammonio)propyl phosphate, and 4-(meth)acylolyloxybutyl-4′(tributylammonio)butyl phosphate.
Preferably 2-(meth)acryloyloxyethyl-2′-(trimethylammonio)ethyl phosphate, also called 2-(methacryloyloxyethyl)phosphorylcholine, is used as acrylic monomer PC.
Preferably, the acrylic polymer PC used according to the invention is a polymer obtained by polymerization of an acrylic monomer PC as described above and optionally of one or more additional monomers different from the acrylic monomer PC.
The additional monomers can be selected from methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylic acid, (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, ethyl vinyl ether, butyl vinyl ether, N-vinylpyrrolidone, vinyl chloride, ethylene, isobutylene, acrylonitrile, styrene, methylstyrene, chloromethylstyrene.
The acrylic polymer PC can comprise from 40 to 100 mol. % of units derived from the acrylic monomer PC as described above and from 0 to 60 mol. % of units derived from an additional monomer.
Preferably, the polymer with a group of the phosphorylcholine type is selected from 2-(methacryloyloxyethyl)phosphorylcholine homopolymer, 2-(methacryloyloxyethyl)phosphorylcholine/butyl methacrylate copolymer, 2-(methacryloyloxyethyl)phosphorylcholine/2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride copolymer, 2-(methacryloyloxyethyl) phosphorylcholine/butyl methacrylate/sodium methacrylate terpolymer, 2-(methacryloyloxyethyl)phosphorylcholine/stearyl methacrylate copolymer. Preferably, the 2-(methacryloyloxyethyl)phosphorylcholine homopolymer or the 2-(methacryloyloxyethyl)phosphorylcholine/butyl methacrylate copolymer is used, and more preferably the 2-(methacryloyloxyethyl)phosphorylcholine homopolymer.
These polymers are described in documents EP-A-1163905, EP-A-1095665, FR-A-2698003, EP-A6767212, the contents of which are incorporated by reference in the present application.
The acrylic polymer PC preferably has a weight-average molecular weight in the range from 50 000 to 1 000 000, and preferably in the range from 80 000 to 800 000.
The following may be used as acrylic polymers with a phosphorylcholine group according to the invention:
In the present invention, PVA is used in its hydrolyzed form, i.e. as polyvinyl alcohol hydrolyzed to 88%. It is possible in particular to use the PVA sold under the name CELVOL 540 PV ALCOHOL by the company CELANESE CHEMICALS.)
Biological Activity
In a particular embodiment, the method according to the invention is a cosmetic method for modifying a biological activity of the skin.
Compound A can be selected so as to allow the material resulting from the condensation of A to retain active molecules (compound C).
The molecules can be active once fixed on the material resulting from the condensation of A. It is possible in this case to have the benefit of a prolonged effect of the activity of the active molecule.
Alternatively, the active molecules can be deactivated by fixation but can be released from the condensate of A and optionally B over time. In this case, it is also possible to have the benefit of prolonged activity.
The invention therefore also relates to the use of a compound or set of compounds A capable of condensing in situ and having at least one free reactive function FA after condensation, for capture on the skin and sustained release of a compound C of cosmetic or dermatological interest comprising a reactive function FC that is able to form a covalent bond by reaction with the function FA. The invention also relates to a method of cosmetic or dermatological treatment of the skin with prolonged activity, the application, on the skin, of a compound or set of compounds A capable of condensing in situ and having at least one free reactive function FA after condensation, and of a compound C of cosmetic or dermatological interest comprising a reactive function FC that is able to form a covalent bond by reaction with the function FA, which can be released from the material obtained from the condensate of A.
In a particular embodiment of the invention, an active molecule can be fixed by means of the invention. In a particular embodiment, compounds A and C are selected so that release can be triggered, either by a natural effect (for example in the case of release triggered by sweating), or by a human action (in the case of particular irradiation, for example light (notably UV, visible) or heat. Thus, compounds A and C can be used in such a way that they are provided with a fragile bond, such as thermo- or photocleavable.
Skin Treatment Agents
Compound C can be a skin treatment agent selected from the following lists.
As other desquamating agents usable in the composition according to the invention, we may mention:
We may also notably mention the ceramides or derivatives thereof, in particular ceramides of type 2 (such as N-oleoyldihydrosphingosine), of type 3 (such as stearoyl-4-hydroxysphinganine as the INCI name) and of type 5 (such as N-2-hydroxypalmitoyldihydrosphingosine, having the INCI name hydroxypalmytoyl sphinganine), compounds based on sphingoids, glycosphingolipids, phospholipids, cholesterol and derivatives thereof, phytosterols, essential fatty acids, diacylglycerol, 4-chromanone and derivatives of chromone, petroleum jelly, lanolin, shea butters, cocoa butter, lanolin, the PCA salts.
As other antiaging agents, we may mention DHEA and derivatives thereof, boswellic acid, extracts of rosemary, carotenoids (beta carotene, zeaxanthin, lutein), cysteic acid, derivatives of copper and jasmonic acid.
We may also mention DMAE (dimethyl MEA), extracts of samphire, of Montpellier rockrose, of helichrysum, of anise, of Para cress, an extract of Acmella oleracea such as Gatuline® expression from Gattefossé.
“Antiglycation agent” means a compound preventing and/or decreasing the glycation of proteins of the skin, in particular of the proteins of the dermis, such as collagen.
As antiglycation agents, we may notably mention vegetable extracts of the family Ericaceae, such as a blueberry extract (Vaccinium angustifolium, Vaccinium myrtillus), for example that sold under the name “BLUEBERRY HERBASOL EXTRACT PG” by the company COSMETOCHEM, ergothioneine and derivatives thereof, hydroxystilbenes and derivatives thereof, such as resveratrol and 3,3′,5,5′-tetrahydroxystilbene (these antiglycation agents are described in applications 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 that sold under the name “AMADORINE®” by the company SOLABIA, carcinine hydrochloride (marketed by Exsymol under the name “ALISTIN®”), an extract of Helianthus annuus such as Antiglyskin® from Silab, wine extracts such as extract of white wine in powder form on maltodextrin support sold under the name “Vin blanc déshydraté 2F” by the company Givaudan, thioctic acid (or alpha lipoic acid), a mixture of extract of bearberry and of marine glycogen such as Aglycal LS 8777® from Laboratoires Sériobiologiques, an extract of black tea such as Kombuchka® from Sederma and mixtures thereof.
or on the synthesis of fibronectin, such as the extract of zooplankton Salina marketed by the company SEPORGA under the trade name GP4G®; yeast extract available notably from the company ALBAN MÜLLER under the trade name Drieline®; and palmitoyl pentapeptide marketed by the company SEDERMA under the trade name Matrixil®.
Among the active ingredients stimulating epidermal macromolecules, such as filaggrin and the keratins, we may notably mention the lupine extract marketed by the company SILAB under the trade name Structurine®; extract of beech buds Fagus sylvatica marketed by the company GATTEFOSSE under the trade name Gatuline® RC; and the extract of zooplankton Salina marketed by the company SEPORGA under the name GP4G®; the copper tripeptide from PROCYTE; a peptide extract of Voandzeia subterranea such as that marketed by the company Laboratoires Serobiologiques under the trade name Filladyn LS 9397®.
As preferred active ingredients stimulating the synthesis of dermal and/or epidermal macromolecules and/or preventing their degradation, we may mention synthetic peptides such as iamin, the biopeptide CL or palmitoyloligopeptide marketed by the company SEDERMA; the peptides extracted from plants, such as the soya hydrolyzate marketed by the company COLETICA under the name Phytokine®; the 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 that marketed by SILBA under the name Vitanol®; a peptide extract of hazelnut such as that marketed by the company Solabia under the name Nuteline C®); arginine; an extract of Aphanizomenon flos-aquae (Cyanophyceae) marketed under the name Lanablue® by Atrium Biotechnologies, the malt extract marketed by the company COLETICA under the name Collalift®; lycopene; a lychee extract; an extract of moringa such as Arganyl LS 9781® from Cognis; an extract of Vaccinium myrtillus such as those described in application FR-A-2814950; retinol and derivatives, in particular retinyl palmitate; {2-[acetyl-(3-trifluoromethyl-phenyl)-amino]-3-methyl-butyrylamino}acetic acid, otherwise called N—[N-acetyl, N′-(3-trifluoromethyl)phenylvalyl]glycine or N-acetyl-N-[3-(trifluoromethyl)phenyl]valyl-glycine or acetyl trifluoromethylphenylvalylglycine, or an ester of the latter 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 brown alga Padina pavonica marketed by the company ALBAN MÜLLER under the trade name HSP3®; the extract of Saccharomyces cerevisiae available notably from the company SILAB under the trade name Firmalift® or from the company LSN under the trade name Cytovitin®; an extract of Laminaria ochroleuca such as Laminaïne® from Secma; the essence of Mamaku from Lucas Meyer, the lupine extract marketed by the company SILAB under the trade name Structurine®; the extract of beech buds Fagus sylvatica marketed by the company GATTEFOSSE under the trade name Gatuline® RC.
An agent promoting the proliferation and/or differentiation of keratinocytes will preferably be used.
The agents stimulating keratinocyte proliferation usable in the composition according to the invention notably comprise adenosine; phloroglucinol, the leaf extract of Hydrangea macrophylla such as Amacha liquid E® from Ichimaru Pharcos, a yeast extract such as Stimoderm® from CLR, extract of Larrea divaricata such as Capislow® from Sederma, the mixtures of extracts of papaya, of olive leaves and of lemon such as Xyléine® from Vincience, the leaf extract of Hydrangea macrophylla such as Amacha liquid E® from Ichimaru Pharcos, retinol and its esters including retinyl palmitate, phloroglucinol, extracts of nut cakes marketed by Gattefosse and the extracts of Solanum tuberosum such as Dermolectin® marketed by Sederma.
The agents stimulating the differentiation of keratinocytes comprise for example minerals such as calcium; samphire, a peptide extract of lupine such as that marketed by the company SILAB under the trade name Structurine®, sodium beta-sitosteryl sulfate such as that marketed by the company SEPORGA under the trade name Phytocohésinee, a water-soluble maize extract such as that marketed by the company SOLABIA under the trade name Phytovityl®; a peptide extract of Voandzeia subterranea such as that marketed by the company Laboratoires Sérobiologiques under the trade name Filladyn LS 9397®; and lignans such as secoisolariciresinol, retinol and its esters including retinyl palmitate.
As agents stimulating the proliferation and/or differentiation of keratinocytes, we may further mention estrogens such as estradiol and homologs; cytokines.
As active ingredients stimulating the proliferation of fibroblasts or of keratinocytes and/or the differentiation of keratinocytes, we may mention plant proteins or polypeptides, extracts notably of soya (for example a soya extract marketed by the company LSN under the name Eleseryl SH-VEG 8® or marketed by the company SILAB under the trade name Raffermine®); an extract of hydrolyzed soya proteins such as RIDULISSE® from SILAB; a peptide extract of hazelnut such as that marketed by the company Solabia under the name Nuteline C®; adenosine; phloroglucinol, a yeast extract such as Stimoderm® from CLR; a peptide extract of lupine such as that marketed by the company SILAB under the trade name Structurine®; a water-soluble maize extract such as that marketed by the company SOLABIA under the trade name Phytovityl®; a peptide extract of Voandzeia subterranea such as that marketed by the company Laboratoires Sérobiologiques under the trade name Filladyn LS 9397®; retinol and its esters including retinyl palmitate.
Agents for Treating the Scalp
The agents for treating the scalp can notably be antidandruff agents, for example Zinc Pyrithione in aqueous dispersion such as Zinc Omadine Pyrithione from Arch Personal Care, or octopyrox, or ketoconazole, or selenium disulfide, or Tea Tree Oil.
The applicant was able to demonstrate that contacting a dispersion of Zinc Pyrithione on a film of APTES is accompanied by almost immediate flocculation of the dispersion of Zinc Pyrithione. This flocculation can improve the deposition of active ingredient on the scalp.
Photoprotective Agents and Filters
In a particular embodiment, the method according to the invention is a cosmetic method of protection against radiation, notably against UV radiation, in which compound C is selected from photoprotective agents, in particular from UV filters.
The organic UV filters are notably selected from cinnamic derivatives; anthranilates; salicylic derivatives, dibenzoylmethane derivatives, camphor derivatives; benzophenone derivatives; derivatives of β,β-diphenylacrylate; triazine derivatives; benzotriazole derivatives; benzalmalonate derivatives notably those mentioned in U.S. Pat. No. 5,624,663; benzimidazole derivatives; imidazolines; bis-benzoazolyl derivatives such as described in patents EP669323 and U.S. Pat. No. 2,463,264; derivatives of p-aminobenzoic acid (PABA); derivatives of methylene bis(hydroxyphenyl benzotriazole) such as described in applications U.S. Pat. No. 5,237,071, U.S. Pat. No. 5,166,355, GB2303549, DE 197 26 184 and EP893119; benzoxazole derivatives such as described in patent applications EP0832642, EP1027883, EP1300137 and DE10162844; polymer filters and silicone filters such as those described notably in application WO-93/04665; dimers derived from α-alkylstyrene such as those described in patent application DE19855649; 4,4-diarylbutadienes such as described in applications EP0967200, DE19746654, DE19755649, EP-A-1008586, EP1133980 and EP133981; merocyanine derivatives such as those described in applications WO04/006878, WO05/058269 and WO06/032741 and mixtures thereof.
As additional examples of organic photoprotective agents, we may mention those designated below with their INCI name:
Ethylhexyl Methoxycinnamate sold notably under the trade name PARSOL MCX by DSM NUTRITIONAL PRODUCTS
Isoamyl Methoxycinnamate sold under the trade name NEO HELIOPAN E 1000 by Symrise
Butyl Methoxydibenzoylmethane sold notably under the trade name PARSOL 1789 by DSM, Isopropyl Dibenzoylmethane.
Ethylhexyl Dimethyl PABA sold notably under the name “ESCALOL 507” by ISP,
PEG-25 PABA sold under the name “UVINUL P25” by BASF.
Homosalate sold under the name “Eusolex HMS” by Rona/EM Industries,
Ethylhexyl Salicylate sold under the name “NEO HELIOPAN BONE” by Symrise,
Dipropyleneglycol Salicylate sold under the name “DIPSAL” by SCHER,
TEA Salicylate, sold under the name “NEO HELIOPAN TS” by Symrise.
Derivatives of β,β-diphenylacrylate:
Octocrylene sold notably under the trade name “UVINUL N539” by BASF,
Etocrylene, sold notably under the trade name “UVINUL N35” by BASF.
Benzophenone-1 sold under the trade name “UVINUL 400” by BASF,
Benzophenone-2 sold under the trade name “UVINUL D50” by BASF,
Benzophenone-3 or Oxybenzone, sold under the trade name “UVINUL M40” by BASF,
Benzophenone-4 sold under the trade name “UVINUL MS40” by BASF,
Benzophenone-6 sold under the trade name “Helisorb 11” by Norquay,
Benzophenone-8 sold under the trade name “Spectra-Sorb UV-24” by American Cyanamid,
Benzophenone-9 sold under the trade name “UVINUL DS-49” by BASF,
n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)-benzoate sold under the trade name “UVINUL A+” or mixed with octylmethoxycinnamate under the trade name “UVINUL A+B” by the company BASF.
3-Benzylidene camphor manufactured under the name “MEXORYL SD” by CHIMEX,
4-Methylbenzylidene camphor sold under the name “EUSOLEX 6300” by MERCK,
Benzylidene Camphor Sulfonic Acid manufactured under the name “MEXORYL SL” by CHIMEX,
Camphor Benzalkonium Methosulfate manufactured under the name “MEXORYL SO” by CHIMEX,
Terephthalylidene Dicamphor Sulfonic Acid manufactured under the name “MEXORYL SX” by CHIMEX,
Polyacrylamidomethyl Benzylidene Camphor manufactured under the name “MEXORYL SW” by CHIMEX.
Phenylbenzimidazole Sulfonic Acid sold notably under the trade name “EUSOLEX 232” by MERCK,
Disodium Phenyl Dibenzimidazole Tetra-sulfonate sold under the trade name “NEO HELIOPAN AP” by Symrise.
Drometrizole Trisiloxane sold under the name “Silatrizole” by RHODIA CHIMIE, Methylene bis-Benzotriazolyl Tetramethylbutylphenol, sold in solid form under the trade name “MIXXIM BB/100” by FAIRMOUNT CHEMICAL or in micronized form in aqueous dispersion under the trade name “TINOSORB M” by CIBA SPECIALTY CHEMICALS.
Menthyl anthranilate sold under the trade name “NEO HELIOPAN MA” by SYMRISE.
Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate.
Polyorganosiloxane with benzalmalonate functions such as Polysilicone-15 sold under the trade name “PARSOL SLX” by DSM NUTRITIONAL PRODUCTS
Derivatives of 4,4-diarylbutadiene:
-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 sold under the name Uvasorb K2A by Sigma 3V and mixtures thereof.
The preferred organic filters are selected from
n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)-benzoate,
4-Methylbenzylidene camphor,
Methylene bis-Benzotriazolyl Tetramethylbutylphenol
Ethylhexyl triazone,
2,4,6-tris(dineopentyl 4′-aminobenzalmalonate)-s-triazine
2,4,6-tris-(diisobutyl 4′-aminobenzalmalonate)-s-triazine
2,4-bis(dineopentyl 4′-aminobenzalmalonate)-6-(n-butyl 4′-aminobenzoate)-s-triazine,
2,4,6-tris(biphenyl-4-yl)-1,3,5-triazine
2,4,6-tris(terphenyl)-1,3,5-triazine
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 UV filters used according to the present invention are metal oxide pigments. More preferably, the inorganic UV filters of the invention are metal oxide particles having an average size of individual particle less than or equal to 500 nm, more preferably between 5 nm and 500 nm, and even more preferably between 10 nm and 100 nm, and preferably between 15 and 50 nm.
They can notably be selected from titanium oxides, of zinc, of iron, of zirconium, of cerium or mixtures thereof.
Metal oxide pigments of this kind, coated or uncoated, are described in particular in patent application EP-A-0 518 773. As commercial pigments, we may mention the products sold by the companies Kemira, Tayca, Merck and Degussa.
The metal oxide pigments can be coated or uncoated.
The coated pigments are pigments that have undergone one or more surface treatments of a chemical, electronic, mechanical-chemical and/or mechanical nature with compounds 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.
The coated pigments are more particularly coated titanium oxides:
The uncoated titanium oxide pigments are sold for example by the company TAYCA under the trade names “MICROTITANIUM DIOXIDE MT 500 B” or “MICROTITANIUM DIOXIDE MT600 B”, by the company DEGUSSA under the name “P 25”, by the company WACKHER under the name “Oxyde de titane transparent PW”, by the company MIYOSHI KASEI under the name “UFTR”, by the company TOMEN under the name “ITS” and by the company TIOXIDE under the name “TIOVEIL AQ”.
The uncoated zinc oxide pigments are for example:
The coated zinc oxide pigments are for example:
The uncoated cerium oxide pigments can be for example those sold under the name “COLLOIDAL CERIUM OXIDE” by the company RHONE POULENC.
The uncoated iron oxide pigments are for example sold by the company ARNAUD under the names “NANOGARD WCD 2002 (FE 45B)”, “NANOGARD IRON FE 45 BL AQ”, “NANOGARD FE 45R AQ”, “NANOGARD WCD 2006 (FE 45R)”, or by the company MITSUBISHI under the name “TY-220”.
The coated iron oxide pigments are for example sold by the company ARNAUD under the names “NANOGARD WCD 2008 (FE 45B FN)”, “NANOGARD WCD 2009 (FE 45B 556)”, “NANOGARD FE 45 BL 345”, “NANOGARD FE 45 BL”, or by the company BASF under the name “OXYDE DE FER TRANSPARENT”.
We may also mention the mixtures of metal oxides, notably of titanium dioxide and of cerium dioxide, including the equal-weight mixture of titanium dioxide and cerium dioxide coated with silica, sold by the company IKEDA under the name “SUNVEIL A”, as well as the mixture of titanium dioxide and zinc dioxide coated with alumina, silica and silicone such as the product “M 261” sold by the company KEMIRA or coated with alumina, silica and glycerin such as the product “M 211” sold by the company KEMIRA.
The titanium oxide pigments, coated or uncoated, are particularly preferred according to the invention.
The photoprotective system according to the invention is preferably present in the compositions according to the invention at a content in the range from 0.1 to 40 wt. % and in particular from 5 to 25 wt. %, relative to the total weight of the composition.
Odor
To impart an odor to the skin, it is possible to use odoriferous molecules C, whose odorous character can be deactivated by the fixation but can be released of the material resulting from the condensation of A over time, thus regenerating their odorous character. As the release can be gradual over time, it is possible to have the benefit of a prolonged odorant effect.
Compound C can typically be selected from aldehyde compounds such as terpene aldehyde derivatives or ketones, for example menthone, citronellal or citral.
Perfumes are compositions notably containing the raw materials described in S. Arctander, Perfume and Flavor Chemicals (Montclair, N.J., 1969), in S. Arctander, Perfume and Flavor Materials of Natural Origin (Elizabeth, N.J., 1960) and in “Flavor and Fragrance Materials—1991”, Allured Publishing Co. Wheaton, Ill.
They can be natural products (essential oils, absolutes, resinoids, resins, concrete and/or synthetic) more particularly comprising at least one aldehyde compound and/or a ketone compound, saturated or unsaturated, aliphatic or cyclic.
According to the definition given in international standard ISO 9235 and adopted by the Commission of the European Pharmacopoeia, an essential oil is an odorant product generally of complex composition, obtained from a botanically defined plant raw material, either by entrainment with steam, or by dry distillation, or by a suitable mechanical process without heating (cold expression). The essential oil is most often separated from the aqueous phase by a physical process that does not lead to significant change of the composition.
The essential oils are generally volatile and liquid at room temperature, which differentiates them from the so-called fixed oils. They are colored to a varying extent and their density is generally less than that of water. They have a high refractive index and most of them refract polarized light. They are fat-soluble and soluble in the usual organic solvents, can be entrained by steam, and have very low solubility in water.
Among essential oils usable according to the invention, we may mention those obtained from plants belonging to the following botanical families:
Abietaceae or Pinaceae: conifers
Annonaceae: ylang ylang
Apiaceae (for example umbelliferae): dill, angelica, coriander, samphire, carrot, parsley
Asteraceae: yarrow, artemisia, chamomile, helichrysum
Burseraceae: incense
Caesalpiniaceae: copaifera (copahu)
Cistaceae: rockrose
Ericaceae: wintergreen
Geraniaceae: geranium
Hypericaceae: St John's wort
Lamiaceae: thyme, oregano, horsemint, savory, basil, marjorams, mints, patchouli, lavenders, sages, catmint, rosemary, hyssop, lemon balm, rosemary
Lauraceae: ravensara, bay, rosewood, cinnamon, litsea
Liliaceae: garlic
Magnoliaceae: magnolia
Moraceae: hemp, hop
Myristicaceae: nutmeg
Myrtaceae: eucalyptus, tea tree, niaouli, cajeput, backousia, clove, myrtle
Piperaceae: pepper
Poaceae: citronella, lemongrass, vetiver
Rosaceae: roses
Rutaceae: all the citrus plants
Santalaceae: sandalwood
Styracaceae: benzoin
Thymelaeaceae: agar wood
Valerianaceae: valerian, nard
Verbenaceae: lantana, verbena
Zingiberaceae: galanga, curcuma, cardamom, ginger
We may also mention the essential oils extracted from flowers (lily, lavender, rose, jasmine, ylang-ylang, neroli), from stems and leaves (patchouli, geranium, orange-leaf oil), from fruits (coriander, anise, cumin, juniper), from fruit peel (bergamot, lemon, orange), from roots (angelica, celery, cardamom, iris, sweet rush, ginger), from wood (pinewood, sandalwood, guaiacum, pink cedar, camphor), from herbs and grasses (tarragon, rosemary, basil, lemon grass, sage, thyme), from needles and from branches (spruce, fir, pine, dwarf pine), from resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opopanax).
Examples of perfuming substances are notably: alpha-hexylcinnamaldehyde, 2-methyl-3-(p-tert-butylphenyl)propanal, 2-methyl-3-(p-isopropylphenyl)propanal, 3-(p-tert-butylphenyl)-propanal, 2,4-dimethylcyclohex-3-enyl-carboxaldehyde, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarboxaldehyde, 4-(4-methyl-3-pentenyl)-3-cyclohexenecarboxaldehyde, 4-acetoxy-3-pentyl-tetrahydropyran, 3-carboxymethyl-2-pentylcyclopentane, 2-n-4-heptylcyclopentanone, 3-methyl-2-pentyl-2-cyclopentenone, menthone, carvone, tagetone, geranyl acetone, n-decanal, n-dodecanal, 9-decenol-1, phenyl-acetaldehyde dimethyl-acetal, phenylacetaldehyde diethylacetal, citral, citronellal, hydroxycitronellal, damascone, ionones, methylionones, isomethylionones, solanone, irones, macrocyclic ketones, macrolactone musks, ethylene brassylate and mixtures thereof.
According to a preferred embodiment of the invention, a mixture of various perfuming substances is used, together producing a pleasing note for the user.
Perfuming substances will preferably be selected in such a way that they produce notes (top, middle and basic) in the following families
hesperides,
aromatics,
floral notes,
spicy,
woody,
gourmands,
chypre types,
ferns,
leathery,
musks.
Compound A (or the set of compounds A) and compound C are selected in relation to the property or properties that one wish to confer on the skin.
According to a particular embodiment of the invention, compound A is an alkoxysilane with primary amine capturing function and compound C is a molecule bearing a function capable of reacting with a free amine. In a preferred embodiment of the invention, compound A is APTES and compound C is selected from the group consisting of DHA, cinnamic aldehyde (or cinammaldehyde), mexoryl SX (INCI: terephthalylidene dicamphor sulfonic acid), zinc pyrithione, vitamin C, citronellal, citral, nonanal, hydroxycitronellal and a polymer of maleic anhydride. According to a particularly preferred embodiment, compound A is APTES and compound C is DHA.
The method according to the invention comprises application, on the skin, of a compound or set of compounds A capable of condensing, in particular when it is submitted to an increase in concentration obtained by evaporation of the medium containing it. The compound or set of compounds A therefore comprises reactive functions to permit this condensation, as was mentioned above.
This condensation leads to the formation of a deposit on and/or in the skin. This deposit is not necessarily continuous but may consist of a multitude of connected regions. Compound A is selected so that material resulting from its condensation has reactive functions called free “capturing functions”.
A compound C of cosmetic interest is also applied on the skin.
Compound C can react with the condensation product of A, via the capturing function FA that is free after condensation, and a function FC present on compound C.
The method according to the invention comprises the sequential or concomitant application of compound A (or of the set of compounds A) and of compound C.
In one embodiment of the invention, firstly compound A (or the set of compounds A) is applied on an area of the skin. Then, after a variable length of time, which can be between 1 minute and 5 hours, preferably from 1 minute to 1 hour, even more preferably between 2 and 10 minutes, compound C is applied on the same area of the skin. In the context of this embodiment, the condensation of compound A (or of the set of compounds A) can have taken place spontaneously, or can have been triggered, before application of compound C.
Compound C can then react on the condensate via the free capturing function or functions on the condensate. Compound C can also react with one or more reactive functions different from the capturing functions, in particular with reactive functions that could have participated in the reaction of A with itself but have not reacted.
Thus, in the particular case when compound A is an organosilane bearing a capturing function, it is to be understood that compound C can react on the capturing function as well as on uncondensed silanols of the condensate.
A chemical reaction then takes place, with formation of covalent bonds between C and one or more reactive functions, more particularly with the capturing functions FA present on the condensate of compound A or of the set of compounds A. This can have the effect of modifying the material on and/or in the skin. This reaction can notably make the condensate insoluble and thus further increase its permanence on and/or in the skin (resistance to water, sweat, sebum, etc.) while maintaining, or even reinforcing, the cosmetic property conferred by compound C.
The invention can be implemented with the use of methods that accelerate or inhibit the reactions employed in the invention and/or the diffusion of the molecules in the skin, for example heat or cold, microwaves, pH agents or catalysts.
It is also possible to act from the surface of the skin on the reaction between compound C and the compound or set of compounds A, for example to control it or make it quicker.
According to a variant of the method according to the invention, compound A is applied first, then we wait for the reaction of condensation of A to take place. The latter can be quick or slow, may or may not involve drying of the skin, may or may not involve activation with, for example, the use of a heat source or some other source of energy. At this stage, it is possible to apply compound C, or rinse and then apply compound C. Compound C can be left to react with the material resulting from the condensation of A. The reaction between A and C can also be activated. After reaction between A and C, rinsing may or may not be carried out.
According to a particular embodiment, compound A is applied in a form or in conditions not permitting the condensation reaction. We wait for compound A to penetrate. Then the reaction is started, either by adding an aid (for example a pH agent) or by changing the conditions, for example by changing the temperature (notably by increasing it). Once condensation has begun, and optionally after a rinsing step, compound C is applied, as previously.
In another variant, compound A or the set of compounds is applied, then compound C is applied in conditions in which the capture reaction cannot take place. The condensation takes place. Once condensation has begun, the reaction of compound C on the condensate of A is started.
In a particular embodiment, compounds A and C are mixed prior to application on the skin (extemporaneous mixing). This mixing can take place before application or during application on the skin (mixing directly on the area of the skin to be treated).
Compound A (or the set of compounds A) and compound C can therefore be applied concomitantly. In this case,
In a particular embodiment, the result of condensation of A is applied on the skin. For example, a film of poly APTES can be applied. Then compound C is applied.
In another embodiment, compound C is applied first, then compound A is applied.
In a particular embodiment of the invention, compound A (or the set of compounds A) and/or compound C can also be injected in the skin. For example, compound A (or the set of compounds A) can be injected, then compound C is applied, or compound A (or the set of compounds A) is applied, then compound C is injected, or compounds A (or the set of compounds A) and C are injected.
In this configuration, the invention serves for example to create a new way of tattooing. Compound A is injected. Then, a compound C can be applied, and by reaction with the capturing function it produces a decorative pattern.
Later, if the pattern fades or is removed, as the capture layer is still trapped on and/or in the skin, it is possible to repeat the operation to reproduce the same decorative pattern, or to create a new pattern.
In general, the reactions can be accelerated by using suitable catalysts, for example pH agents, salts, metals and/or enzymes.
The present invention also relates to the combined use of a cosmetic composition containing an effective amount of a compound A capable of condensing in situ on the skin and of a cosmetic composition containing an effective amount of a compound C that will react with one or more free reactive functions of the material resulting from the condensation of compound A. The compositions are for example in the form of a serum, a lotion, a direct (O/W), inverse (W/O) or multiple (O/W/O and W/O/W) emulsion, a stick or a compact. They can use compartmentation systems (two incompatible solvents, encapsulation). These systems make it possible, for example, to put compound A, or the set of compounds A, and compound C, in one and the same product, while limiting their interaction.
Compound A, or the set of compounds A, and compound C can be formulated in compositions containing a physiologically acceptable medium. These compositions can be according to any pharmaceutical forms conventionally used in the application envisaged. Of course, a person skilled in the art will take care to select the components and optional additional ingredients and/or active substances, and/or the amount thereof, in such a way that the advantageous properties of compound A (or of the set of compounds A) and of compound C, are not, or substantially not, altered by the addition envisaged.
In a particular embodiment, the compositions used according to the invention are aqueous compositions.
The compositions containing compound C used for coloring the skin, in particular to obtain a self-tanning effect, can be prepared according to techniques that are well known by a person skilled in the art, in particular those intended for the preparation of emulsions of the oil-in-water or water-in-oil type.
This composition can in particular be in the form of a simple or complex emulsion (O/W, W/O, O/W/O or W/O/W) such as a cream, a milk or in the form of a gel or of a gel cream, in the form of a lotion, of powder, of a solid stick and optionally can be packaged as an aerosol and can be in the form of mousse or spray.
Preferably, the compositions according to the invention are in the form of an oil-in-water or water-in-oil emulsion.
When it is an emulsion, the aqueous phase of the latter can comprise a nonionic vesicular dispersion prepared according to the known methods (Bangham, Standish and Watkins, J. Mol. Biol. 13, 238 (1965), FR 2 315 991 and FR 2 416 008).
In a particular embodiment, compound C is DHA. The latter can be used in free form and/or encapsulated for example in lipid vesicles such as liposomes, notably described in application WO 97/25970.
The self-tanning compositions according to the invention can be in the form of creams, milks, gels, gel-creams, oil-in-water emulsions, vesicular dispersions, fluid lotions, in particular vaporizable fluid lotions or any other forms generally used in cosmetics, in particular those usually suitable for self-tanning cosmetic compositions.
The compositions according to the present invention can further comprise conventional cosmetic aids notably selected from fats, organic solvents, ionic or nonionic thickeners, softeners, antioxidants, antifree radical agents, opacifiers, stabilizers, emollients, silicones, α-hydroxy acids, antifoaming agents, hydrating agents, vitamins, insect repellents, antagonists of substance P, anti-inflammatories, perfumes, preservatives, surfactants, fillers, polymers, propellants, alkanizing or acidifying agents, and additional colorants (in addition to compound C used according to the invention), or any other ingredient usually employed in the cosmetic and/or dermatological field, in particular for manufacturing self-tanning compositions in the form of emulsions. These cosmetic aids can be incorporated either in the composition containing A, in the composition containing compound C, or in both compositions.
The fats can consist of an oil or a wax or mixtures thereof “Oil” means a compound that is liquid at room temperature. “Wax” means a compound that is solid or substantially solid at room temperature, and whose melting point is generally above 35° C.
As oils, we may mention mineral oils (paraffin); vegetable oils (sweet almond oil, macadamia oil, blackcurrant seed oil, jojoba oil); synthetic oils such as perhydrosqualene, fatty alcohols, acids or esters (such as the benzoate of C12-C15 alcohols sold under the trade name “Finsolv TN” by the company Finetex, octyl palmitate, isopropyl lanolate, triglycerides including those of capric/caprylic acids, ethoxylated or propoxylated fatty esters and ethers; silicone oils (cyclomethicone, polydimethylsiloxanes or PDMS) or fluorinated oils; polyalkylenes and mixtures thereof.
As waxy compounds, we may mention paraffin, carnauba wax, beeswax, hydrogenated castor oil.
Among the organic solvents, we may mention the lower alcohols and polyols having at most 8 carbon atoms.
The thickeners can be selected notably from crosslinked polyacrylic acids, guar gums and modified or unmodified celluloses such as hydroxypropylated guar gum, methylhydroxyethylcellulose and hydroxypropylmethylcellulose.
It is also possible to use additional dyes that make it possible to modify the color produced by the self-tanning agent.
These additional dyes can be selected from synthetic or natural direct dyes.
These additional dyes can be selected for example from red or orange dyes of the fluorane type such as those described in patent application FR2840806. We may mention for example the following dyes:
These additional dyes can also be selected from anthraquinones, caramel, carmine, carbon black, azulene blues, methoxalene, trioxalene, guajazulene, chamuzulene, rose bengal, cosine 10B, cyanosine, daphinine
These additional dyes can also be selected from indole derivatives such as monohydroxyindoles as described in patent FR2651126 (i.e.: 4-, 5-, 6- or 7-hydroxyindole) or the dihydroxyindoles as described in patent EP-B-0425324 (i.e.: 5,6-dihydroxyindole, 2-methyl-5,6-dihydroxyindole, 3-methyl-5,6-dihydroxyindole, 2,3-dimethyl-5,6-dihydroxyindole).
The additional coloring agents can also be iron oxide pigments with average size of the individual particles below 100 nm such as those described in patent application EP 966 953.
The compositions comprising a compound C used for photoprotection or care of the skin can be prepared according to techniques that are well known by a person skilled in the art. It should be noted that the pharmaceutical forms and active ingredients described below can be used for formulating compound A, whatever the cosmetic application required.
The compositions used according to the invention can comprise conventional cosmetic aids notably selected from fats, organic solvents, ionic or nonionic, hydrophilic or lipophilic thickeners, softeners, humectants, opacifiers, stabilizers, emollients, silicones, antifoaming agents, perfumes, preservatives, anionic, cationic, nonionic, zwitterionic or amphoteric surfactants, active ingredients, fillers, polymers, propellants, alkalizing or acidifying agents or any other ingredient usually employed in the cosmetic and/or dermatological field. These cosmetic aids can be incorporated either in the composition containing A, in the composition containing compound C, or in both compositions.
The fats can consist of an oil or a wax other than the nonpolar waxes as defined above or mixtures thereof. Oil means a compound that is liquid at room temperature. Wax means a compound that is solid or substantially solid at room temperature, and whose melting point is generally above 35° C.
As oils, we may mention mineral oils (paraffin); vegetable oils (sweet almond oil, macadamia oil, blackcurrant seed oil, jojoba oil); synthetic oils such as perhydrosqualene, fatty alcohols, amides (such as isopropyl lauroyl sarcosinate sold under the designation “Eldew SL-205” by the company Ajinomoto), fatty acids or esters such as benzoate of C12-C15 alcohols sold under the trade name “Finsolv TN” or “Witconol TN” by the company WITCO, 2-ethylphenyl benzoate such as the commercial product sold under the name X-TEND 226® by the company ISP, octyl palmitate, isopropyl lanolate, triglycerides including those of capric/caprylic acids, dicaprylyl carbonate sold under the name “Cetiol CC” by the company Cognis, ethoxylated or propoxylated fatty esters and ethers; silicone oils (cyclomethicone, polydimethysiloxanes or PDMS) or fluorinated oils, polyalkylenes, trialkyl trimellitates such as tridecyl trimellitate.
As waxy compounds, we may mention carnauba wax, beeswax, hydrogenated castor oil, polyethylene waxes and polymethylene waxes such as that sold under the name Cirebelle 303 by the company SASOL.
Among the organic solvents, we may mention the lower alcohols and polyols. The latter can be selected from glycols and glycol ethers such as ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol.
As hydrophilic thickeners, we may mention the carboxyvinylic polymers such as the Carbopols (Carbomers) and the Pemulens (acrylate/C10-C30-alkylacrylate copolymer); polyacrylamides, for example the crosslinked copolymers sold under the names Sepigel 305 (CTFA name: polyacrylamide/C13-14 isoparaffin/Laureth 7) or Simulgel 600 (CTFA name: acrylamide/sodium acryloyldimethyltaurate copolymer/isohexadecane/polysorbate 80) by the company Seppic; the polymers and copolymers of 2-acrylamido-2-methylpropanesulfonic acid, optionally crosslinked and/or neutralized, such as poly(2-acrylamido-2-methylpropanesulfonic acid) marketed by the company Hoechst under the trade name “Hostacerin AMPS” (CTFA name: ammonium polyacryloyldimethyl taurate or SIMULGEL 800 marketed by the company SEPPIC (CTFA name: sodium polyacryolyldimethyl taurate/polysorbate 80/sorbitan oleate); the copolymers of 2-acrylamido-2-methylpropanesulfonic acid and hydroxyethyl acrylate such as SIMULGEL NS and SEPINOV EMT 10 marketed by the company SEPPIC; cellulose derivatives such as hydroxyethylcellulose; polysaccharides and notably gums such as xanthan gum; water-soluble or water-dispersible silicone derivatives such as the acrylic silicones, polyether silicones and cationic silicones and mixtures thereof.
As lipophilic thickeners, we may mention synthetic polymers such as the poly C10-C30 alkyl acrylates sold under the name “INTELIMER IPA 13-1” and “INTELIMER IPA 13-6” by the company Landec or modified clays such as hectorite and derivatives thereof, such as the products marketed under the names Bentone.
Of course, a person skilled in the art will take care to select the optional additional compound or compounds mentioned above and/or the amounts thereof in such a way that the advantageous properties intrinsically attaching to the compositions used according to the invention are not, or substantially not, altered by the addition or additions envisaged.
The compositions used for photoprotection or care of the skin according to the invention, and the compositions containing compound A or the set of compounds A, can be prepared according to techniques that are well known by a person skilled in the art. They can in particular be in the form of simple or complex emulsion (O/W, W/O, O/W/O or W/O/W) such as a cream, a milk or a gel-cream; in the form of an aqueous gel; in the form of a lotion. They can optionally be packaged as an aerosol and can be in the form of mousse or spray.
Preferably, the compositions used according to the invention are in the form of an oil-in-water or water-in oil emulsion.
The methods of emulsification that can be used are of the blade or propeller, rotor-stator and HHP type.
It is also possible, by HHP (between 50 and 800b), to obtain stable dispersions with droplet sizes down to 100 nm.
The emulsions generally contain at least one emulsifier selected from amphoteric, anionic, cationic or nonionic emulsifiers, used alone or mixed. The emulsifiers are selected appropriately, depending on the emulsion to be obtained (W/O or O/W).
As emulsifying surfactants usable for preparing W/O emulsions, we may mention for example the alkyl esters or ethers of sorbitan, of glycerol or of sugars; the silicone surfactants such as the dimethicone copolyols, for instance the mixture of cyclomethicone and dimethicone copolyol sold under the name “DC 5225 C” by the company Dow Corning, and the alkyl-dimethicone copolyols such as the laurylmethicone copolyol sold under the name “Dow Corning 5200 Formulation Aid” by the company Dow Corning; the cetyl dimethicone copolyol such as the product sold under the name Abil EM 90R by the company Goldschmidt and the mixture of cetyl dimethicone copolyol, polyglycerol isostearate (4 moles) and hexyl laurate sold under the name ABIL WE O9 by the company Goldschmidt. One or more co-emulsifiers can also be added, which can, advantageously, be selected from the group comprising alkylated polyol esters.
As alkylated polyol esters, we may notably mention the polyethylene glycol esters such as PEG-30 Dipolyhydroxystearate such as the product marketed under the name Arlacel P135 by the company ICI.
As esters of glycerol and/or of sorbitan, we may mention for example polyglycerol isostearate, such as the product marketed under the name Isolan GI 34 by the company Goldschmidt; sorbitan isostearate, such as the product marketed under the name Arlacel 987 by the company ICI; sorbitan isostearate and glycerol, such as the product marketed under the name Arlacel 986 by the company ICI, and mixtures thereof.
For O/W emulsions, we may mention for example as emulsifiers, the nonionic emulsifiers such as alkoxylated (more particularly polyethoxylated) esters of fatty acids and of glycerol; the alkoxylated esters of fatty acids and of sorbitan; the alkoxylated (ethoxylated and/or propoxylated) esters of fatty acids such as the mixture PEG-100 Stearate/Glyceryl Stearate marketed for example by the company ICI under the name Arlacel 165; the alkoxylated (ethoxylated and/or propoxylated) ethers of fatty alcohols; the esters of sugars such as sucrose stearate; the ethers of fatty alcohol and of sugar, notably the alkylpolyglucosides (APG) such as the decylglucoside and laurylglucoside marketed for example by the company Henkel under the respective names Plantaren 2000 and Plantaren 1200, cetostearylglucoside optionally mixed with cetostearyl alcohol, marketed for example under the name Montanov 68 by the company Seppic, under the name Tegocare CG90 by the company Goldschmidt and under the name Emulgade KE3302 by the company Henkel, as well as arachidyl glucoside, for example in the form of the mixture of arachidic and behenic alcohols and of arachidyl glucoside marketed under the name Montanov 202 by the company Seppic. According to a particular embodiment of the invention, the mixture of alkylpolyglucoside as defined above with the corresponding fatty alcohol can be in the form of a self-emulsifying composition, as described for example in document WO-A-92/06778.
In the case of an emulsion, the aqueous phase of the latter can comprise a nonionic vesicular dispersion prepared by known methods (Bangham, Standish and Watkins. J. Mol. Biol. 13, 238 (1965), FR 2 315 991 and FR 2 416 008).
The cosmetic compositions used according to the invention can for example be used as a product for care and/or sun protection for the face and/or the body, with a liquid to semi-liquid consistency, such as milks, more or less oily creams, gel-creams, pastes. They can optionally be packaged as an aerosol and can be in the form of mousse or spray.
The compositions according to the invention in the form of vaporizable fluid lotions according to the invention are applied on the skin or on the scalp in the form of fine particles by means of pressurizing devices. The devices according to the invention are well known by a person skilled in the art and comprise non-aerosol pumps or “atomizers”, aerosol containers comprising a propellant as well as aerosol pumps using compressed air as propellant. The latter are described in U.S. Pat. No. 4,077,441 and U.S. Pat. No. 4,850,517 (forming an integral part of the contents of the description).
The compositions packaged as aerosol according to the invention generally contain conventional propellants, for example hydrofluorinated compounds, dichlorodifluoromethane, difluoroethane, dimethyl ether, isobutane, n-butane, propane, trichlorofluoromethane. They are preferably present in amounts in the range from 15 to 50 wt. % relative to the total weight of the composition.
The compositions used according to the invention can also further comprise additional cosmetic and dermatological active ingredients.
Among the active ingredients, we may mention:
Of course, a person skilled in the art will take care to select the optional additional compound or compounds mentioned above and/or the amounts thereof in such a way that the advantageous properties intrinsically attaching to the compositions according to the invention are not, or substantially not, altered by the addition or additions envisaged.
A person skilled in the art will select said active ingredient or ingredients in relation to the desired effect on the skin.
The composition can further comprise at least one ingredient such as of fillers with a blurring effect or agents promoting the natural coloration of the skin, intended to complete the biological effect of these active ingredients or supply an immediate visual antiaging effect.
For the care and/or makeup of greasy skin, a person skilled in the art will preferably select at least one active ingredient selected from desquamating agents, sebo-regulating or antiseborrheic agents, astringents.
The compositions used according to the invention can further comprise at least one additional ingredient intended for completing the biological effect of these active ingredients or for supplying an immediate visual effect; we may notably mention matting agents, fillers with a blurring effect, fluorescent agents, agents promoting the naturally pinkish coloration of the skin and abrasive or exfoliating fillers.
To complement and/or optimize the effects conferred on keratinous substances by the cosmetic and/or dermatological active ingredients mentioned above, it may be advantageous to incorporate other additional ingredients in the compositions of the invention.
In particular, these additional ingredients can confer an immediate visual effect which will be relayed by the biological effect of the active ingredients mentioned above. They can also, via a mechanical action (e.g.: abrasive fillers), amplify the effect of the biological active substances mentioned above.
“Matting agent” means agents intended to make the skin visibly more matt, less shiny.
The matting effect of the agent and/or of the composition containing it can notably be evaluated by means of a gonioreflectometer, by measuring the ratio R of specular reflection to diffuse reflection. A value of R less than or equal to 2 generally signifies a matting effect.
The matting agent can notably be selected from a rice starch or a maize starch, INCI name: ZEA MAYS (CORN) STARCH such as in particular the product sold under the trade name “FARMAL CS 3650 PLUS 036500” by National Starch, kaolinite, talc, a pumpkin seed extract, cellulose microbeads, vegetable fibers, synthetic fibers, in particular of polyamides, microspheres of expanded acrylic copolymers, powders of polyamides, silica powders, polytetrafluoroethylene powders, silicone resin powders, powders of acrylic polymers, wax powders, polyethylene powders, powders of elastomeric crosslinked organopolysiloxane coated with silicone resin, talc/titanium dioxide/alumina/silica composite powders, powders of amorphous mixed silicates, particles of silicate and notably of mixed silicate, and mixtures thereof.
As examples of matting agents, we may notably mention:
These fillers can be any material capable of modifying wrinkles by its intrinsic physical properties and masking them. These fillers can notably modify wrinkles by a lifting effect, a camouflage effect, or a blurring effect.
The following compounds can be given as examples of filler:
The fillers having an effect on the signs of aging are notably selected from porous silica microparticles, hollow hemispherical particles of silicones, silicone resin powders, powders of acrylic copolymers, powders of polyethylenes, powders of crosslinked elastomeric organopolysiloxanes coated with silicone resin, talc/titanium dioxide/alumina/silica composite powders, precipitated calcium carbonate, carbonate of magnesium hydrocarbonate, barium sulfate, hydroxyapatite, calcium silicate, cerium dioxide and microcapsules of glass or of ceramic, fibers of silk, of cotton, and mixtures thereof.
The filler can be a “soft focus” filler.
“Soft-focus” filler means a filler which in addition gives transparency to the complexion and a blurred effect. Preferably, the “soft-focus” fillers have an average particle size less than or equal to 15 microns. These particles can be of any shape and in particular can be spherical or non-spherical. More preferably, these fillers are non-spherical.
The “soft-focus” fillers can be selected from powders of silica and silicates, notably of alumina, powders of the polymethyl methacrylate (PMMA) type, talc, silica/TiO2 or silica/zinc oxide composites, polyethylene powders, starch powders, powders of polyamides, powders of styrene/acrylic copolymers, silicone elastomers, and mixtures thereof.
In particular, we may mention talc with a number-average size less than or equal to 3 microns, for example talc with a number-average size of 1.8 micron and notably that sold under the trade name Talc P3® by the company Nippon Talc, powder of Nylon® 12, notably that sold under the name Orgasol 2002 Extra D Nat Cos® by the company Atochem, particles of silica surface-treated with a mineral wax 1 to 2% (INCI name: hydrated silica (and) paraffin) such as those marketed by the company Degussa, amorphous silica microspheres, such as those sold under the name Sunsphere for example of reference H-53® by the company Asahi Glass, and silica microbeads such as those sold under the name SB-700® or SB-150® by the company Miyoshi, this list not being exhaustive.
The concentration of these fillers having an effect on the signs of aging in the compositions according to the invention can be between 0.1 and 40%, or even between 0.1 and 20 wt. % relative to the total weight of the composition.
The compositions used according to the invention can further comprise an agent for promoting the naturally pinkish coloration of the skin. We may notably mention:
As examples of self-tanning agents, we may notably mention:
dihydroxyacetone (DHA) (used to complement a compound C for photoprotection (or filter) or care, of the skin),
erythrulose, and
combination with a catalytic system formed from:
salts and oxides of manganese and/or of zinc, and
alkali and/or alkaline-earth hydrogen carbonates.
The self-tanning agents are generally selected from mono- or polycarbonylated compounds, for example isatin, alloxan, ninhydrin, glyceraldehyde, mesotartaric aldehyde, glutaraldehyde, erythrulose, derivatives of pyrazoline-4,5-diones as described in patent application FR 2 466 492 and WO 97/35842, dihydroxyacetone (DHA), derivatives of 4,4-dihydroxypyrazolin-5-ones as described in patent application EP 903 342. DHA will preferably be used.
DHA can be used in free form and/or encapsulated for example in lipid vesicles such as liposomes, notably described in application WO 97/25970.
In general, the self-tanning agent is present in an amount in the range from 0.01 to 20 wt. %, and preferably in an amount between 0.1 and 10% of the total weight of the composition.
It is also possible to use other dyes that make it possible to modify the color produced by the self-tanning agent.
These dyes can be selected from synthetic or natural direct dyes.
These dyes can be selected for example from red or orange dyes of the fluorane type such as those described in patent application FR2840806. We may mention for example the following dyes:
These dyes can also be selected from anthraquinones, caramel, carmine, carbon black, blue azulenes, methoxalene, trioxalene, guajazulene, chamuzulene, rose bengal, cosine 10B, cyanosine, daphinine.
These dyes can also be selected from indole derivatives such as monohydroxyindoles as described in patent FR2651126 (i.e.: 4-, 5-, 6- or 7-hydroxyindole) or dihydroxyindoles as described in patent EP-B-0425324 (i.e.: 5,6-dihydroxyindole, 2-methyl-5,6-dihydroxyindole, 3-methyl-5,6-dihydroxyindole, 2,3-dimethyl-5,6-dihydroxyindole);
As exfoliating agents usable in rinsed compositions according to the invention, we may mention for example exfoliating particles of mineral, vegetable or organic origin. Thus, it is possible to use for example polyethylene beads or powder, nylon powder, polyvinyl chloride powder, pumice stone, ground apricot stones or walnut shells, sawdust, glass beads, alumina, and mixtures thereof. We may also mention Exfogreen® from Solabia (bamboo extract), extracts of strawberry achenes (strawberry achenes from Greentech), powdered peach stone, powdered apricot stone, and finally in the area of vegetable powders with abrasive effect, we may mention powdered cranberry stones.
As abrasive fillers or exfoliating agents that are preferred according to the invention, we may mention powdered peach stones, powdered apricot stones, powdered cranberry stones, extracts of strawberry achenes, bamboo extracts.
The invention also relates to a cosmetic kit, comprising at least:
The kit according to the invention can thus be composed of a two-compartment system. It can also correspond to a kit comprising the first composition in a first pharmaceutical form (for example a cream containing the compound or set of compounds A) and the second composition in a second pharmaceutical form (for example a roll-on system, a spray, etc.).
A cosmetic kit of this kind can be useful when components of the first and of the second composition display instability (whether physical or chemical) when they are mixed, or when we wish to prevent the compound or set of compounds A and compound C interacting before they are applied on the skin. By formulating the compositions in this way, we can notably greatly improve the stability of DHA, for example.
Thus, according to a particular embodiment, the cosmetic kit comprises:
The following examples are supplied as a nonlimiting illustration of the invention.
A film of polyAPTES is formed in a Petri dish by evaporation of a solution, by putting about 6 mL of the formulation described in Table 1 below in the Petri dish. After drying and formation of a film in the Petri dish, a few drops of the formulation in Table 2 are then deposited.
In a few minutes, a brown coloration appears where the few drops of the formulation in Table 2 were deposited. The coloration continues to intensify and reaches its maximum in about 1 hour.
The inventors applied formulations side by side (in the form of spots) on a user's arm, according to the following conditions:
a—application of the DHA formulation according to Table 2
b—application of the APTES formulation in Table 1; drying for 10 minutes at room temperature; then application of the DHA formulation in Table 2 on the area covered with APTES
c—application of the APTES formulation in Table 1; then application of the DHA formulation in Table 2 on the area covered with APTES, without intermediate drying
d—application of an extemporaneous mixture of the formulations in Tables 1 and 2.
After about 30 minutes, a brown coloration is seen to appear, which is much more pronounced in the case of application according to conditions b, c and d, compared to condition a. In other words, application of DHA on the skin together with APTES makes it possible to obtain a quicker increase in coloration than when only DHA is applied. The results obtained after one hour are shown in
After several hours, notably after 3 hours, the coloration is very intense when DHA has been applied with APTES, whereas it is only moderate in the case of application of DHA alone. It is also observed that the treated area has become insoluble.
Although the three application conditions b, c and d gave more satisfactory results than with application of DHA alone, the inventors observed a greater increase in coloration and intensity of coloration according to condition c (application of APTES then application of DHA, without intermediate drying).
The required properties of permanence and durability of the cosmetic effect can be improved by making the deposit insoluble by applying a molecule bearing a function capable of reacting with a free amine on the PolyAPTES film obtained from an alkoxysilane with a primary amine function.
The procedure described in example 1 above is employed in its entirety. Then the insolubility of the deposits following application of a DHA solution on the polyAPTES film is demonstrated by applying a sufficient amount of water in the Petri dish. After a few hours the deposit of polyAPTES has dissolved except where a drop of DHA solution was deposited. In this place, the deposit remains insoluble and floats in the Petri dish.
The APTES formulation in Table 1 is applied on an area of the skin. Then a 1% solution of hydroxycitronellal in ethanol is applied. Surprisingly, the treated area displays fluorescence under UV. The same effect was observed after application of nonalal.
The formulation containing an alkoxysilane with free amine function is that from Table 1 above.
The formulation containing an alkoxysilane with free amine function is that in Table 1 above.
The formulation containing an alkoxysilane with free amine function is that in Table 1 above.
The formulation containing an alkoxysilane with free amine function is that in Table 1 above.
The formulation containing an alkoxysilane with free amine function is that in Table 1 above.
| Number | Date | Country | Kind |
|---|---|---|---|
| 0959261 | Dec 2009 | FR | national |
| 0959262 | Dec 2009 | FR | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP10/69803 | 12/15/2010 | WO | 00 | 10/24/2012 |
| Number | Date | Country | |
|---|---|---|---|
| 61296561 | Jan 2010 | US | |
| 61296563 | Jan 2010 | US |
