COSMETIC TREATMENT METHOD INVOLVING A COMPOUND CAPABLE OF CONDENSING IN SITU

Abstract

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.

Description

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:

• • it is possible to deposit, on the surface of the skin, ingredients that modify the appearance of the skin immediately (pigments, dyes) but which, having little or no affinity for the skin, are not tenacious and are removed at the first washing.
  • as an alternative, it is possible to deposit products on the skin that will react with the constituents of the skin and modify it. In this case, the property conferred is tenacious and disappears gradually by the natural phenomenon of desquamation, but conversely, the ingredient deposited must diffuse into the various compartments of the skin to finally reach the reactive sites (proteins, skin lipids) and appearance of the property is then delayed and may take several hours.
    An illustration of this problem is encountered in the case of persons who wish to correct cutaneous dyschromias and use, for this purpose, cosmetic or dermatological compositions that confer uniformity, radiance and/or a healthy appearance.
    For these purposes, it is possible to use covering products which, although concealing skin imperfections, have the major drawback of masking the natural appearance of the skin (mask sensation) and are not tenacious, as the pigments are washed away at the first washing.
    It is also known to use products containing dihydroxyacetone (or DHA) which, by conferring a tanned appearance (or in other words conferring a “healthy appearance”), make it possible to conceal skin imperfections. However, the mechanism of action of DHA on the skin is relatively slow. Consequently, the effect of coloration of the skin cannot be seen until 4 hours after application. Accordingly, development of this method is limited as most people wish to apply the product in the morning and have a visible result within the hour. A coloring effect that takes 4 hours to develop can pose problems for those who do not want the people around them to see that their skin is colored thanks to the use of cosmetic products.

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:

• • acceleration of the kinetics of action of the compound of cosmetic interest,
  • improvement in the durability of the cosmetic effect of the ingredient,
  • appearance of an unexpected cosmetic property on the skin.

The present invention therefore relates to a method for the cosmetic treatment of the skin, comprising 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 F_A after condensation; and
  • a compound C of cosmetic interest comprising a reactive function F_C that is able to form a covalent bond by reaction with the function F_A.

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 F_A 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 F_A after condensation, for capturing, on or in the skin, a compound C of cosmetic or dermatological interest comprising a reactive function F_C that is able to form a covalent bond by reaction with the function F_A.

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:

• • of a compound or set of compounds A capable of condensing in situ and having at least one free reactive function F_A after condensation; and
  • of a compound C of cosmetic interest comprising a reactive function F_C that is able to form a covalent bond by reaction with the function F_A,
    the material resulting from the condensation of A being soluble in water, and 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 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 F_A after condensation, said material being soluble in water, comprising application, on said material, of a compound C of cosmetic interest comprising a reactive function F_C that is able to form a chemical bond, which can be covalent or ionic, by reaction with the function F_A, 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:

• • of a compound or set of compounds A capable of condensing in situ and having at least one free reactive function F_A after condensation; and
  • of a compound C of cosmetic interest comprising a reactive function F_C that is able to form a covalent or ionic bond by reaction with the function F_A,
    the material resulting from the condensation of A being soluble in water, and 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 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 F_A after condensation, said material being soluble in water, C being a compound of cosmetic interest comprising a reactive function F_C that is able to form a covalent or ionic bond by reaction with the function F_A.

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 F_A, or a function leading to the formation of a function F_A 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 F_A after condensation. According to a particular embodiment, the function or functions F_A 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

• • 1st case: A1 comprises a capturing function (compound F_A-A1); not A2
    condensation product:

• • 2nd case: A1 and A2 comprise a capturing function (identical or different)
    (compound F_A-A1 and compound F_A-A1)
    condensation product:

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:

• • application, on the skin, of a compound A capable of condensing in situ and having at least one free reactive function F_A after condensation; and
  • application of a compound C of cosmetic interest comprising a reactive function F_C that is able to form a covalent bond by reaction with the function F_A.

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 F_A 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 F_A.

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:

• • R₄ represents a halogen, a group OR′ or R′₁;
  • R₅ represents a halogen, a group OR″ or R′₂;
  • R₆ represents a halogen, a group OR′″ or R′₃;
  • and R₁, R₂, R₃, R′, R″, R′″, R′₁, R′₂, R′₃ represent, independently of one another, a saturated or unsaturated, linear or branched hydrocarbon group, optionally bearing additional chemical groups such as acid or amine groups, and R₁, R₂, R′, R″ and R′″ can further denote hydrogen, and
    at least two of the groups R₄, R₅ and R₆ are different from the groups R′₁, R′₂ and R′₃. Preferably, R₁, R₂, R′, R″ and R′″, R′₁, R′₂ and R′₃ represent a C₁ to C₁₂ alkyl group, a C₆ to C₁₄ aryl group, a (C₁-C₈)alkyl-(C₆-C₁₄)aryl group, and a (C₆-C₁₄)aryl-(C₁-C₈)alkyl group; and R₃ is preferably a C₁ to C₁₂ alkyl, C₆ to C₁₄ aryl, (C₁-C₈)alkyl-(C₆-C₁₄)aryl and (C₆-C₁₄)aryl-(C₁-C₈)alkyl group.

The organosiloxanes that are preferred in the compositions of the present invention can be represented by the formula:

in which:

• • R₁, R₂, R₃, R₅ and R₆ are defined as above;
  • R′₄ represents a halogen (fluorine, bromine, chlorine or iodine) or a group OR₁₁;
  • R₇ represents a halogen, a group OR₁₀ or R″₁;
  • R₉ represents a halogen, a group OR₈, R″₂ or R₃NR₁R₂;
  • R″₁, R″₂, R₈, R₁₀ and R₁₁ represent a saturated or unsaturated, linear or branched hydrocarbon group, optionally bearing additional chemical groups such as basic solubilizing groups;
  • R₁₁, R₁₀ and R₈ can moreover represent hydrogen.
    Preferably R″₁, R″₂, R₈ or R₁₀ and R₁₁ represent a C₁ to C₁₂ alkyl group, a C₆ to C₁₄ aryl group, a (C₁-C₈)alkyl-(C₆-C₁₄)aryl group, and a (C₆-C₁₄)aryl-(C₁-C₈)alkyl group.
    At least one of the groups R₆, R₇ and R₉ denotes a halogen or a group OR′″, OR₁₀ or OR₈.

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 F_C 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 F_C 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 F_A 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 F_C of compound C are typically electron-accepting groups and thus can be selected from:

• • epoxides,
  • aziridines,
  • vinyl and activated vinyl functions, in particular acrylonitrile, acrylic and methacrylic ester functions,
  • crotonic acids and esters, cinnamic acids and esters, styrene and derivatives thereof, butadiene,
  • vinyl ethers, vinyl ketones, maleic esters, vinyl sulfones, maleimides,
  • aminals, hemiaminals,
  • alpha-hydroxyketones, alpha-haloketones,
  • lactones, thiolactones,
  • thiocyanates,
  • imines,
  • imides, in particular succinimide and glutimide,
  • esters of N-hydroxysuccinimide,
  • imidates,
  • thiosulfates,
  • oxazins and oxazolines,
  • oxaziniums and oxazoliniums,
  • alkyl or aralkyl halides of formula RX, with X═I, Br, Cl,
  • halides of an unsaturated, carbon-containing ring or heterocycle, notably chlorotriazines, chloropyrimidines, chloroquinoxalines and chlorobenzotriazoles,
  • sulfonyl halides RSO₂X with X═Cl or F, R being a C₁ to C₃₀ alkyl.

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 (F_A) 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 F_C 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:

• • compounds C having more than one reactive function (for example, a dialdehyde);
  • compounds C which, once they have reacted with the material resulting from the condensation of A, are transformed, and whose product of transformation can react further with the material (for example, an anhydride, a part of which is coupled to the free function of A and the other, comprising a carboxylic acid function, can also react with the free function of A, for example an amine function);
  • compounds C which, once they have reacted with the material resulting from the condensation of A, are transformed and can react further with another molecule C, which may or may not have reacted with the material resulting from the condensation of A (for example DHA);
  • compounds C which, once they have reacted with the material resulting from the condensation of A, are capable of reacting with a compound D which will react between molecules C or between molecules C and A.

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:

• • to modify its color. Then typically compounds A and C are used which, in addition to the requirements described above, give a chromophore. Or else a compound A that is colored, or a set of compounds A that is colored, is used. Or else a compound A and/or a compound C are used which, although colorless, gradually become colored. It is also possible to use compounds A and/or C that have a bleaching, decolorizing or depigmenting effect.
  • to modify its brightness. Then 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 reacts with the material resulting from the reaction of A to give a heterogeneous deposit which, by the effect of diffusion of light, will decrease the brightness of the skin.
  • to modify its smoothness and/or its feel. Then typically compounds A and C are used, which in addition to the requirements described above, give a material that is soft to the touch or a material that captures or retains water, such as a hygroscopic compound.
  • to modify its physicochemical surface properties. 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. Or alternatively, A and C are used which, in addition to the requirements described above, give a material that forms a barrier to the passage of certain molecules.
  • to retain active molecules.
    • either the molecules C are active once fixed on the material resulting from the reaction of A. There may then be a prolonged effect of the activity of the active molecule. Thus, filters can be used for conferring long-lasting photoprotection.
  • or the active molecules are deactivated by fixation but can be released over time. This may also offer the benefit of prolonged activity. In this case, biological active ingredients or perfumes can be used.

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:

• • Compounds A and C are incorporated in products such as care products, makeup or special products.
  • Compounds A and C can be applied once or twice, optionally with prior, intermediate, or subsequent applications of third compounds.
  • When compounds A and C are applied once, the kinetics of reaction and of penetration and the functions are such that C does not prevent reaction of A with itself. In particular, the reaction of C on the reactive function of A is slower than the penetration of A and/or slower than the reaction of A on itself.
  • The applications of these compounds are integrated in care or makeup routines. For example, the application of compound A is integrated in a skin preparation routine, and the application of compound C is integrated in a foundation.

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:

• • the functions of compound A that permit capture are preferably nucleophilic functions, in particular amines. Now, these functions contribute to the water solubility of compound A but also of the material resulting from the reaction of compound A;
  • the reactivity of compound A is preferably selected to be moderate, so that compound A can penetrate into the skin more easily.

Thus, in a particular embodiment of the invention, compounds A and compound C are selected so that:

• • compound C can react with the material resulting from the reaction of A
  • application of compound C reduces the water solubility of the material resulting from the reaction of A.

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 PP_A+C, which corresponds to the weight loss of the material expressed as a percentage; a value PP_x=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 PP_A is thus measured.
f) the value PP_A+C is compared with the value PP_A.

According to this method of selection, compounds A and C are used which make it possible to obtain a value of PP_A+C lower than the value of PP_A, 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: PP_A+C=PP_A−n, or n=PP_A−PP_A+C, it being understood that PP_A−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, PP_A+C is less than 15% and PP_A 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:

• • A is placed in the same conditions as those used at the time of application on the skin;
  • analytical methods, such as NMR, IR, etc., are used for determining the degree of reaction of A in these conditions. From this, we deduce the ratio, relative to the set of entities A, of entities A that have reacted: A_m;
    • preferably according to the invention, the ratio: A_m/A (where m1, 2, 3) is above 50%, or more preferably above 75%;
    • in the case when the method involves an action on A before or during the application (for example mixing at the time of use), analytical determination is carried out 5 min after this action (for example, mixing is carried out at the time of use and then the analysis is performed 5 min later).
      Properties that can be Conferred on the Skin by Compound C and/or Compound A

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 hydrophobized polymers of acrylamido-2-methylpropanesulfonic acid (AMPS) that can be used according to the invention can comprise both a hydrophilic moiety and a hydrophobic moiety (amphiphilic polymers) having at least one fatty chain.
    The fatty chain present in the polymers of the invention preferably has from 7 to 30 carbon atoms and more preferably from 7 to 22 carbon atoms.
    The amphiphilic polymers according to the invention generally have a weight-average molecular weight in the range from 50 000 to 10 000 000, more preferably from 100 000 to 8 000 000 and even more preferably from 100 000 to 7 000 000.
    The amphiphilic AMPS polymers according to the invention can be crosslinked or noncrosslinked.
    The crosslinking agents can be selected in particular from methylene-bis-acrylamide, allyl methacrylate and trimethylolpropane triacrylate (TMPTA). The degree of crosslinking varies preferably from 0.01 to 10 mol. % and more particularly from 0.2 to 2 mol. % relative to the polymer.
    The amphiphilic AMPS polymers according to the invention can notably be selected from random amphiphilic AMPS polymers modified by reaction with an n-monoalkylamine or a C₆-C₂₂ di-n-alkylamine such as those described in patent application WO00/31154. These polymers can also contain other hydrophilic monomers with an ethylenic unsaturation selected for example from acrylic acid, methacrylic acid or their alkyl substituted derivatives or their esters obtained with mono- or polyalkylene glycols, acrylamide, methacrylamide, vinylpyrrolidone, itaconic acid or maleic acid or mixtures thereof.
    The preferred AMPS polymers of the invention are selected from amphiphilic AMPS polymers and at least one monomer with an ethylenic unsaturation having at least one hydrophobic moiety having from 7 to 30 carbon atoms and more preferably from 7 to 22 carbon atoms and even more preferably from 12 to 22 carbon atoms.
    This hydrophobic moiety can be a saturated or unsaturated linear alkyl radical (for example n-octyl, n-decyl, n-hexadecyl, n-dodecyl, oleyl), branched (for example isostearic) or cyclic (for example cyclododecane or adamantane).
    These same polymers can additionally contain one or more hydrophilic comonomers with an ethylenic unsaturation such as acrylic acid, methacrylic acid or their alkyl substituted derivatives or their esters obtained with mono- or polyalkylene glycols, acrylamide, methacrylamide, vinylpyrrolidone, itaconic acid or maleic acid.
    These same polymers can additionally contain one or more hydrophobic comonomers with an ethylenic unsaturation, comprising for example:
  • a C₇-C₁₈ fluorinated or alkyl-fluorinated radical (for example the group of formula —(CH₂)₂—(CF₂)₉—CF₃);
  • a cholesteryl radical or a radical derived from cholesterol (for example cholesteryl hexanoate);
  • a polycyclic aromatic group such as naphthalene or pyrene;
  • a silicone or alkylsilicone or alkylfluorosilicone radical.
    These copolymers are notably described in patent applications (CLARIANT): EP 1 069 142, WO 02/44224, WO02/44225, WO02/44227, WO02/44229, WO02/44230, WO02/44231, WO02/44267, WO02/44268, WO02/44269, WO02/44270, WO02/44271, WO02/43677, WO02/43686, WO02/43687, WO02/43688 and WO02/43689.

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:

• • the crosslinked or noncrosslinked, neutralized or unneutralized copolymers, having from 15 to 60 wt. % of AMPS units and from 40 to 85 wt. % of (C₈-C₁₆)alkyl(meth)acrylamide units or (C₈-C₁₆)alkyl(meth)acrylate units relative to the polymer, such as those described in application EP-A-750 899;
  • the terpolymers having from 10 to 90 mol. % of acrylamide units, from 0.1 to 10 mol. % of AMPS units and from 5 to 80 mol. % of n-(C₆-C₁₈)alkylacrylamide units, relative to the polymer, such as those described in U.S. Pat. No. 5,089,578.
    As amphiphilic polymers, we may also mention the copolymers of fully neutralized AMPS and of n-dodecyl, n-hexadecyl and/or n-octadecyl methacrylate, as well as the noncrosslinked and crosslinked copolymers of AMPS and of n-dodecylmethacrylamide.

We may mention more particularly the crosslinked or noncrosslinked amphiphilic copolymers consisting of:

• • (a) 2-acrylamido-2-methylpropanesulfonic acid (AMPS) units of the following formula (2):

in which X+ is a proton, an alkali metal cation, an alkaline-earth cation or the ammonium ion;

• • (b) and units of the following formula (3):

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

• • the esters of (meth)acrylic acid and of polyethoxylated C₁₀-C₁₈ fatty alcohol with 8 OE such as the product GENAPOL C-080 sold by the company CLARIANT;
  • the esters of (meth)acrylic acid and of polyethoxylated C₁₁ fatty oxoalcohol with 8 OE such as the product GENAPOL UD-080 sold by the company CLARIANT;
  • the esters of (meth)acrylic acid and of polyethoxylated C₁₂-C₁₄ fatty alcohol with 7 OE such as the product GENAPOL LA-070 sold by the company CLARIANT;
  • the esters of (meth)acrylic acid and of polyethoxylated C₁₂-C₁₄ fatty alcohol with 11 OE such as the product GENAPOL LA-110 sold by the company CLARIANT;
  • the esters of (meth)acrylic acid and of polyethoxylated C₁₆-C₁₈ fatty alcohol with 8 OE such as the product GENAPOL T-080 sold by the company CLARIANT;
  • the esters of (meth)acrylic acid and of polyethoxylated C₁₆-C₁₈ fatty alcohol with 15 OE such as the product GENAPOL T-150 sold by the company CLARIANT;
  • the esters of (meth)acrylic acid and of polyethoxylated C₁₆-C₁₈ fatty alcohol with 11 OE such as the product GENAPOL T-110 sold by the company CLARIANT;
  • the esters of (meth)acrylic acid and of polyethoxylated C₁₆-C₁₈ fatty alcohol with 20 OE such as the product GENAPOL T-200 sold by the company CLARIANT;
  • the esters of (meth)acrylic acid and of polyethoxylated C₁₆-C₁₈ fatty alcohol with 25 OE such as the product GENAPOL T-250 sold by the company CLARIANT; and
  • the esters of (meth)acrylic acid and of polyethoxylated C₁₈-C₂₂ fatty alcohol with 25 OE and/or of polyethoxylated C₁₆-C₁₈ fatty isoalcohol with 25 OE.
    More particularly, the following will be selected:
    (i) those that are noncrosslinked for which p=0, n=7 or 25, R₂₇ denotes methyl and R₂₉ represents a mixture of C₁₂-C₁₄ or C₁₆-C₁₈ alkyls,
    (ii) those that are crosslinked for which p=0, n=8 or 25, R₂₇ denotes methyl and R₂₉ represents a mixture of C₁₆-C₁₈ alkyls.
    These polymers are described and synthesized in application EP1069142. These particular amphiphilic polymers can be obtained according to conventional methods of radical polymerization in the presence of one or more initiators, for example, azobisisobutyronitrile (AIBN), azobisdimethylvaleronitrile, 2,2-azo-bis-[2-amidinopropane]hydrochloride (ABAH), organic peroxides such as dilauryl peroxide, benzoyl peroxide and tert-butyl hydroperoxide, mineral peroxidized compounds such as potassium or ammonium persulfate, or hydrogen peroxide H₂O₂, optionally in the presence of reducing agents.
    These amphiphilic polymers can notably be obtained by radical polymerization in tert-butanol medium, in which they precipitate. By using polymerization by precipitation in tert-butanol, it is possible to obtain a particle size distribution of the polymer that is particularly favorable for its uses.
    The reaction can be carried out at a temperature between 0 and 150° C., preferably between 10 and 100° C., either at atmospheric pressure, or under reduced pressure. It can also be carried out under inert atmosphere, and preferably under nitrogen. The polymers according to the invention are preferably neutralized partially or fully by a mineral or organic base such as those mentioned above.
    The molar concentration percentage of the units of formula (2) and of the units of formula (3) in the amphiphilic polymers according to the invention varies depending on the desired cosmetic application, the nature of the emulsion (oil-in-water or water-in-oil) and the required rheological properties of the formulation. It can vary between 0.1 and 99.9 mol. %.
    The amphiphilic AMPS polymers according to the invention of low hydrophobicity will be more suitable for thickening and/or stabilization of oil-in-water emulsions. The molar proportion of units of formula (3) will preferably vary from 0.1 to 50%, more particularly from 1 to 25% and even more particularly from 3 to 10%.
    The amphiphilic AMPS polymers according to the invention that are more hydrophobic will be more suitable for thickening and/or stabilization of water-in-oil emulsions. The molar proportion of units of formula (3) will preferably vary from 50.1 to 99.9%, more particularly from 60 to 95% and even more particularly from 65 to 90%.
    The distribution of the monomers in the polymers of the invention can be, for example, alternating, block (including multiblock) or any whatever.
    As a nonlimiting guide, we may mention the following commercial references: Aristoflex HMS, Aristoflex LNC, Aristoflex SNC and Aristoflex HMB marketed by Clariant.

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 radicals R₅, which may be identical or different, denote a monovalent hydrocarbon radical selected from alkyl, aryl, aralkyl groups not containing more than 10 carbon atoms and preferably selected from the C₁-C₄ lower alkyls such as methyl, ethyl, butyl or else selected from phenyl and benzyl and even more preferably all denote methyl; some of the radicals R₅ can also contain one plus one ethylcyclohexylene monoxide group and have a low proportion in the polysiloxane chain;
  • u has a value 5 to 59, preferably 10 to 50 and more preferably 12 to 25;
  • v has a value 3 to 12, preferably 4 to 10 and more preferably 5 to 8;
  • E denotes a group —C_xH_2x—(OC₂H₄)_y—(OC₃H₆)_z—OR₆ where:
  • x has a value 1 to 8, preferably from 2 to 4 and more preferably 3;
  • y>0 and z≧0; y and z being selected in such a way that the total molecular weight of radical E varies from 200 to 10000 g/mol and more preferably from 350 to 3000; preferably, the number z is equal to zero.
  • R₆ denotes a hydrogen atom, a linear or branched C₁-C₈ alkyl radical (preferably C₁-C₄ such as methyl) or a C₂-C₈ acyl radical (preferably C₂-C₄ such as acetyl).
    In formula E, the oxyethylene and oxypropylene units can be distributed in the polyether chain E randomly and/or as blocks.

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:

• • R is selected from H, —CH₃, —C₂H₅ or —C₃H₇,
  • X is selected from:
  • alkyl oxides of the —OR′ type where R′ is a saturated or unsaturated, linear or branched hydrocarbon radical, having from 1 to 22 carbon atoms.
    Compound (A) can be methyl methacrylate, ethyl methacrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl acrylate and isobornyl acrylate and 2-hexylethyl acrylate.
    The hydrophilic nonionic polymer block is preferably selected from poly(ethylene oxide) (PEO) and polyvinylpyrrolidone (PVP).

The block copolymer is preferably selected from the following block copolymers:

• • polymethylmethacrylate/polyoxyethylene
  • polybutylmethacrylate/polyoxyethylene

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)

• • polysaccharides selected from:
    A) cellulose derivatives
    The derivatives preferred are the hydroxyethylcelluloses of molecular weight between 50000 and 2 000 000, carboxymethylcelluloses such as Blanose LF7 from Aqualon, hydroxypropylcelluloses, hydrophobized C₁₀-C₃₀ cellulose derivatives such as Natrosol 330+ from Hercules and Polysurf 67 from Aqualon;
    B) xanthan gums such as Keltrol T from CP Kelco and guar gum such as Jaguar HP 105 from Rhodia;
    C) alginates, which may be esterified, such as Kelcoloid O from CP Kelco (degree of esterification 80-85%);
    D) polysaccharide derivatives that have been oxidized and made ketonic, such as oxidized insulin;
    E) derivatives of fucose such as the polyfucose marketed under the name Fucogel by Solabia;
    F) derivatives of fructose such as Fructan from Sochibo/Bioland;
    G) derivatives of rhamnose such as Rhamnosoft from Solabia;
    H) derivatives of pullulan such as pullulan PI-20 from Hayashibara; as well as modified polysaccharides such as guars that have been made cationic, such as Jaguar C13S and C 132.
  • PEO-POP-PEO triblock derivatives such as poloxamers, soluble in water (clear solution at 1% in water at room temperature) and having a molecular weight (MW) above 8000. As examples, we may mention Poloxamer 338 (PEO-POP-PEO: 128/54/128), Poloxamer 407 (PEO-POP-PEO: 98/67/98), Poloxamer 188 (PEO-POP-PEO: 75/30/75) and Poloxamer 238 (PEO-POP-PEO: 97/39/97).
  • derivatives of polyamino acids such as polyglutamic acid such as the Bio PGA solution from Ishumaru Pharcos, polyaspartic acid such as AquaDew SPA-30 from Ajinomoto, polyleucine and polylysine such as the polylysine and Epsilon polylysine from Chisso Corporation.
  • derivatives of galacturonic acid such as Dextran from Fluka.
  • copolymers of maleic anhydride or succinic anhydride such as Licocare PP207 from Clariant and Wacker GF20 from Wacker Chimie.
  • methyl vinyl ether/ethyl monomaleate copolymers such as Gantrez ES225 from ISP.
  • derivatives of poly(alkyloxazoline):
    In the method according to the invention it is possible to use, as compound C, a conditioning polymer which is a polymer of oxazoline of formula (I):

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.

• • acrylic derivatives of phosphorylcholine
    These polymers are described in application EP1764078.

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:

• • the poly-2-(methacryloyloxyethyl)phosphorylcholine at 40% in a water/butanediol mixture (5% of butanediol) sold under the name LIPIDURE HM by the company Nippon Oils and Fats; the CTFA name of this product is: polyphosphorylcholine glycol acrylate (and) butylene glycol;
  • the copolymer of 2-(methacryloyloxyethyl) phosphorylcholine/butyl methacrylate (90/10) at 5% in solution in water sold under the name LIPIDURE PMB by the company Nippon Oils and Fats; the CTFA name of this product is: POLYQUATERNIUM-51;
  • the copolymer of 2-(methacryloyloxyethyl)phosphorylcholine/2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride at 5% in solution in water, sold under the name LIPIDURE-C by the company Nippon Oils and Fats;
  • the terpolymer of 2-(methacryloyloxyethyl) phosphorylcholine/butyl methacrylate/sodium methacrylate at 5% in solution in water, sold under the name LIPIDURE-A by the company Nippon Oils and Fats; and
  • the copolymers of 2-(methacryloyloxyethyl) phosphorylcholine/stearyl methacrylate sold under the names LIPIDURE-S, LIPIDURE-NR, LIPIDURE-NA by the company Nippon Oils and Fats; the CTFA name of these products is: polyquatemium-61.
  • derivatives of polyvinyl alcohol
    Polyvinyl acetate is a vinyl polymer manufactured by radical polymerization of the monomer vinyl acetate then hydrolyzed, in this case at 88%, to obtain polyvinyl alcohol (PVA); the polymer of interest to us in this study has the following unit:

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 F_A after condensation, for capture on the skin and sustained release of a compound C of cosmetic or dermatological interest comprising a reactive function F_C that is able to form a covalent bond by reaction with the function F_A. 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 F_A after condensation, and of a compound C of cosmetic or dermatological interest comprising a reactive function F_C that is able to form a covalent bond by reaction with the function F_A, 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.

• • hydrating agents or humectants
    As humectants or hydrating agents, we may notably mention glycerol and derivatives thereof, urea and derivatives thereof notably Hydrovance® marketed by National Starch, lactic acids, hyaluronic acid, AHA, BHA, sodium pidolate, xylitol, serine, sodium lactate, ectoin and derivatives thereof, chitosan and derivatives thereof, collagen, plankton, an extract of Imperata cylindrica marketed under the name Moist 24® by the company Sederma, homopolymers of acrylic acid such as Lipidure-HM® from NOF Corporation, beta-glucan and in particular the sodium carboxymethyl beta-glucan from Mibelle-AG-Biochemistry; a mixture of passionflower, apricot, maize, and rice bran oils marketed by Nestlé under the name NutraLipids®; a C-glycoside derivative such as those described in application WO 02/051828 and in particular C-β-D-xylopyranoside-2-hydroxypropane in the form of a solution at 30 wt. % of active substance in a water/propylene glycol mixture (60/40 by weight) such as the product manufactured by CHIMEX under the trade name “MEXORYL SBB®”; a musk rose oil marketed by Nestlé; a zinc-enriched extract of microalga Prophyridium cruentum marketed by Vincience under the name Algualane Zinc®; beads of collagen and of chondroitin sulfate of marine origin (Ateocollagen) marketed by the company Engelhard Lyon under the name marine filling beads; beads of hyaluronic acid such as those marketed by the company Engelhard Lyon.
  • desquamating agents
    “Desquamating agent” means any compound capable of acting:
  • either directly on desquamation by promoting exfoliation, such as the β-hydroxy acids (BHA), in particular salicylic acid and derivatives thereof (including n-octanoyl-5-salicylic acid, otherwise called capryloyl salicylic acid); α-hydroxy acids (AHA), such as glycolic, citric, lactic, tartaric, malic and mandelic acids; 8-hexadecene-1,16-dicarboxylic acid or 9-octadecenedioic acid; urea and derivatives thereof; gentisic acid and derivatives thereof; oligofucoses; cinnamic acid; extract of Saphora japonica; resveratrol and certain derivatives of jasmonic acid;
  • or on the enzymes involved in desquamation or degradation of corneodesmosomes, the glycosidases, stratum corneum chymotryptic enzyme (SCCE) or other proteases (trypsin, chymotrypsin-like). We may mention the aminosulfonic compounds and in particular 4-(2-hydroxyethyl)piperazine-1-propanesulfonic acid (HEPES); 2-oxothiazolidine-4-carboxylic acid (procysteine) and derivatives thereof; the derivatives of alpha amino acids of the glycine type (as described in EP-0 852 949, as well as the methyl glycine sodium diacetate marketed by BASF under the trade name TRILON M); honey; derivatives of sugar such as O-octanoyl-6-D-maltose and N-acetyl glucosamine.

As other desquamating agents usable in the composition according to the invention, we may mention:

• • oligofructoses, EDTA and derivatives thereof, Laminaria extracts, o-linoleyl-6D-glucose, (3-hydroxy-2-pentylcyclopentyl) acetic acid, glycerol trilactate, O-octanyl-6′-D-maltose, S-carboxymethyl cysteine, silicon-containing derivatives of salicylate such as those described in patent EP 0 796 861, oligofucases such as those described in patent EP 0 218 200, salts of 5-acyl salicylic acid, active ingredients having effects on transglutaminase as in patent EP 0 899 330,
  • Ficus opuntia indica flower extract such as Exfolactive® from Silab,
  • 8-hexadecene-1,16-dicarboxylic acid,
  • esters of glucose and of vitamin F, and
  • mixtures thereof.
  • agents for improving the barrier function
    As agents for improving the barrier function, we may notably mention arginine, serine, an extract of Thermus thermophilus such as Vénucéane® from Sederma, an extract of rhizome of wild yam (Dioscorea villosa) such as Actigen Y® from Active Organics, extracts of plankton such as omega Plancton® from Secma, yeast extracts such as Relipidium® from Coletica, a chestnut extract such as Recoverine® from Silab, a cedar bud extract such as Gatuline Zen® from Gattefossé, sphingosines such as the salicyloyl sphingosine sold under the name “Phytosphingosine® SLC” by the company Degussa, a mixture of xylitol, xylityl polyglycoside and xylitan such as Aquaxyl® from Seppic, extracts of Solanaceae such as Lipidessence® from Coletica; unsaturated omega 3 oils such as musk rose oils and mixtures thereof.

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.

• • antioxidants
    We may notably mention tocopherol and its esters, in particular tocopherol acetate; ferulic acid; serine; ellagic acid, phloretin, polyphenols, tannins, tannic acid, epoigallocathechine and natural extracts containing it, anthocyans, rosemary extracts, extracts of olive leaves such as those from the company Silab, extracts of green tea, resveratrol and derivatives thereof, ergothineine, N-acetylcysteine, an extract of brown alga Pelvetia canaliculata such as Pelvetiane® from Secma, chlorogenic acid, biotin, chelating agents, such as BHT, BHA, N,N-bis(3,4,5-trimethoxybenzyl)ethylenediamine and its salts; idebenone, vegetable extracts such as Pronalen Bioprotect™ from the company Provital; coenzyme Q10, bioflavonoids, SODs, phytantriol, lignans, melatonin, pidolates, glutathione, caprylyl glycol, phloretin, Totarol™ or extract of Podocarpus totara containing totarol (totara-8,11,13-trienol or 2-phenanthrenol,4b,5,6,7,8,8a,9,10-octahydro-4-b,8,8-trimethyl-1(1-methylethyl)-; a jasmine extract such as that marketed by SILAB under the name Helisun®; hesperitin laurate such as Flavagrum PEG® from the company Engelhard Lyon; an extract of Paeonia suffructicosa root such as that marketed by the company Ichimaru Pharcos under the name Botanpi Liquid B®; a lychee extract such as the extract of lychee pericarp marketed by the company Cognis under the name Litchiderm LS 9704®, an extract of pomegranate fruit (Punica granatum), such as that marketed by the company Draco Natural Products.

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.

• • depigmenting agents
    As depigmenting agents, we may notably mention alpha and beta arbutins, ferulic acid, lucinol and derivatives thereof, kojic acid, resorcinol and derivatives thereof, tranexamic acid and derivatives thereof, gentisic acid, homogentisate, methyl gentisate or homogentisate, dioic acid, D calcium pantetheine sulfonate, lipoic acid, ellagic acid, vitamin B3, linoleic acid and derivatives thereof, ceramides and homologs thereof, derivatives of plants such as chamomile, bearberry, the aloe family (vera, ferox, barbadensis), of mulberry, of skullcap; a water of kiwi fruit (Actinidia chinensis) marketed by Gattefosse, an extract of Paeonia suffructicosa root such as that marketed by the company Ichimaru Pharcos under the name Botanpi Liquid B®, an extract of brown sugar (Saccharum officinarum), such as the molasses extract marketed by the company Taiyo Kagaku under the name Molasses Liquid, but this is not an exhaustive list.
  • dermorelaxing or dermodecontracting agents
    We may mention as examples manganese gluconate and other salts, adenosine, alverine citrate and salts thereof, glycine, an extract of Iris pallida, a hexapeptide (Argériline R from Lipotec) or sapogenins such as Wild yam and the carbonylated amines described in application EP1484052. As examples of sapogenins we may mention those described in patent application WO02/47650, in particular Wild yam, diosgenin extracted notably from Dioscorea opposita or any extract containing naturally, or after treatment, one or more sapogenins (rhizome of wild yam, agave leaf which contains hecogenin and tigogenin, extract of Liliaceae and more particularly Yucca or smilax containing smilagenin and sarsasapogenin, or root of sarsaparilla) or Actigen Y from the company Active Organics; or ginger.

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 agents

“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.

• • agents stimulating the synthesis of dermal and/or epidermal macromolecules and/or preventing their degradation
    Among active ingredients stimulating the macromolecules of the dermis or preventing their degradation, we may mention those that act:
  • either on the synthesis of collagen, such as extracts of Centella asiatica, the asiaticosides and derivatives; ascorbic acid or vitamin C and derivatives thereof; synthetic peptides such as iamin, biopeptide CL or palmitoyl oligopeptide marketed by the company SEDERMA; peptides extracted from plants, such as the soya hydrolyzate marketed by the company COLETICA under the trade name Phytokine®; the rice peptides such as Nutripeptide® from SILAB, methylsilanol mannuronate such as Algisium C® marketed by Exsymol; plant hormones such as auxins and lignans; folic acid; and an extract of Medicago sativa (alfalfa) such as 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®; and arginine;
  • or on inhibition of the degradation of collagen, in particular agents acting on inhibition of metalloproteinases (MMP) such as more particularly MMP 1, 2, 3, 9. We may mention: retinoids and derivatives, extracts of Medicago sativa such as Vitanol® from Silab, an extract of Aphanizomenon flos-aquae (Cyanophyceae) marketed under the name Lanablue® by Atrium Biotechnologies, oligopeptides and lipopeptides, lipoamino acids, the malt extract marketed by the company COLETICA under the trade name Collalift®; extracts of bilberry or of rosemary; lycopene; isoflavones, their derivatives or vegetable extracts containing them, in particular soya extracts (marketed for example by the company ICHIMARU PHARCOS under the trade name Flavosterone SB®), of red clover, of flax, of kakkon; a lychee extract such as the extract of lychee pericarp marketed by the company Cognis under the name Litchiderm LS 9704®; the dipalmitoyl hydroxyproline marketed by Seppic under the name SEPILIFT DPHP®, Baccharis genistelloide or Baccharine marketed by SILAB, a moringa extract such as Arganyl LS 9781® from Cognis; the sage extract described in application FR-A-2812544 of the family Labiatae (Salvia officinalis from the company Flacksmann), rhododendron extract, blueberry extract, an extract of Vaccinium myrtillus such as those described in application FR-A-2814950;
  • or on the synthesis of molecules belonging to the class of elastins (elastin and fibrillin), such as: retinol and derivatives, in particular retinol palmitate; the extract of Saccharomyces cerevisiae marketed by the company LSN under the trade name Cytovitin®; and the extract of alga Macrocystis pyrifera marketed by the company SECMA under the trade name Kelpadelie®; a peptide extract of hazelnut such as that marketed by the company Solabia under the name Nuteline C®;
  • or on the inhibition of elastin degradation such as the peptide extract of seeds of Pisum sativum marketed by the company LSN under the name Parelastyl®; the heparinoids; and the N-acylaminoamide compounds described in application WO 01/94381 such as {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;
  • or on the synthesis of glycosaminoglycans, such as the product of milk fermentation by Lactobacillus vulgaris, marketed by the company BROOKS under the trade name Biomin Yogourth®; 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 Laminïne® from Secma; essence of Mamaku from Lucas Meyer, an extract of cress (Odraline® from Silab);

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.

• • agents stimulating the proliferation of fibroblasts or of keratinocytes and/or the differentiation of keratinocytes
    The agents stimulating fibroblast proliferation usable in the composition according to the invention can be selected for example from plant proteins or polypeptides, extracted notably from 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; and plant hormones such as gibberellins and cytokinins; a peptide extract of hazelnut such as that marketed by the company Solabia under the name Nuteline C®.

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 promoting maturation of the cornified envelope
    Agents that influence the maturation of the cornified envelope, which changes with age and induces a decrease in activity of transglutaminases, can be used in the compositions of the invention. We may mention for example urea and derivatives thereof and in particular Hydrovance® from National Starch and the other active ingredients mentioned in the L'OREAL application FR2877220 (unpublished).
  • inhibitors of nitric-oxide synthases
    The agent having an inhibitory action on NOS can be selected from the PCOs (procyanidolic oligomers); plant extracts of the species Vitis vinifera notably marketed by the company Euromed under the name “Leucocyanidines de raisins extra”, or by the company Indena under the name Leucoselect®, or finally by the company Hansen under the name “Extrait de marc de raisin”; plant extracts of the species Olea europaea preferably obtained from olive leaves and notably marketed by the company VINYALS in the form of dry extract, or by the company Biologia & Technologia under the trade name Eurol® BT; extracts of a plant of the species Ginkgo biloba, preferably a dry aqueous extract of this plant sold by the company Beaufour under the trade name “Ginkgo biloba extrait standard” and mixtures thereof.
  • antagonists of the peripheral benzodiazepine receptors (PBRs)
    We may mention for example 1-(2-chlorophenyl)-N-(1-methylpropyl)-3-isoquinoline carboxamide; the compounds described in applications WO03/030937, WO03/068753, derivatives of pyridazino[4,5-b]indole-1-acetamide of general formula (VII) as described in document WO00/44384.
  • agents increasing sebaceous gland activity
    We may mention for example methyl dehydrojasmonate, hecogenin, hedione, O-linoleyl-6D-glucose and mixtures thereof.
  • agents stimulating the energy metabolism of the cells
    The active ingredient stimulating the energy metabolism of the cells can be selected for example from biotin, an extract of Saccharomyces cerevisiae such as Phosphovital® from Sederma, the mixture of sodium, manganese, zinc and magnesium salts of pyrrolidone carboxylic acid such as Physiogenyl® from Solabia, a mixture of zinc, copper and magnesium gluconate such as Sepitonic M3® from Seppic and mixtures thereof; a beta-glucan derived from Saccharomyces cerevisiae such as that marketed by the company Mibelle AG Biochemistry.

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:

Cinnamic Derivatives:

Ethylhexyl Methoxycinnamate sold notably under the trade name PARSOL MCX by DSM NUTRITIONAL PRODUCTS

Isopropyl Methoxycinnamate

Isoamyl Methoxycinnamate sold under the trade name NEO HELIOPAN E 1000 by Symrise

DEA Methoxycinnamate,

Diisopropyl Methylcinnamate,

Glyceryl Ethylhexanoate Dimethoxycinnamate

Derivatives of Dibenzoylmethane:

Butyl Methoxydibenzoylmethane sold notably under the trade name PARSOL 1789 by DSM, Isopropyl Dibenzoylmethane.

Derivatives of Para-Aminobenzoic Acid:

PABA,

Ethyl PABA,

Ethyl Dihydroxypropyl PABA,

Ethylhexyl Dimethyl PABA sold notably under the name “ESCALOL 507” by ISP,

Glyceryl PABA,

PEG-25 PABA sold under the name “UVINUL P25” by BASF.

Salicylic Derivatives:

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.

Derivatives of Benzophenone:

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-5

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,

Benzophenone-12

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.

Derivatives of Benzylidene Camphor:

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.

Derivatives of Phenyl Benzimidazole:

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.

Derivatives of Phenyl Benzotriazole:

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.

Derivatives of Triazine:

• • Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine sold under the trade name “TINOSORB S” by CIBA GEIGY,
  • Ethylhexyl Triazone sold notably under the trade name “UVINUL T150” by BASF,
  • Diethylhexyl Butamido Triazone sold under the trade name “UVASORB HEB” by SIGMA 3V,
  • 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,
  • the symmetrical triazine filters described in U.S. Pat. No. 6,225,467, application WO2004/085412 (see compounds 6 and 9) or the document “Symmetrical Triazine Derivatives” IP.COM Journal, IP.COM INC WEST HENRIETTA, NY, US (Sep. 20, 2004) notably 2,4,6-tris-(biphenyl)-1,3,5-triazines (in particular 2,4,6-tris(biphenyl-4-yl-1,3,5-triazine and 2,4,6-tris(terphenyl)-1,3,5-triazine which is mentioned in patent applications WO06/03 5 000, WO06/034982, WO06/034991, WO06/03 5007, WO2006/034992, WO2006/034985.

Anthranilic Derivatives:

Menthyl anthranilate sold under the trade name “NEO HELIOPAN MA” by SYMRISE.

Derivatives of Imidazolines:

Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate.

Derivatives of Benzalmalonate:

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

Derivatives of Benzoxazole:

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

Ethylhexyl Methoxycinnamate,

Ethylhexyl Salicylate,

Homosalate,

Butyl Methoxydibenzoylmethane,

Octocrylene,

Phenylbenzimidazole Sulfonic Acid,

Benzophenone-3,

Benzophenone-4,

Benzophenone-5,

n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)-benzoate,
4-Methylbenzylidene camphor,

Terephthalylidene Dicamphor Sulfonic Acid,

Disodium Phenyl Dibenzimidazole Tetra-sulfonate,

Methylene bis-Benzotriazolyl Tetramethylbutylphenol

Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine

Ethylhexyl triazone,

Diethylhexyl Butamido 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

Drometrizole Trisiloxane

Polysilicone-15

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:

• • of silica such as the product “SUNVEIL” from the company IKEDA,
  • of silica and of iron oxide such as the product “SUNVEIL F” from the company IKEDA,
  • of silica and of alumina such as the products “MICROTITANIUM DIOXIDE MT 500 SA” and “MICROTITANIUM DIOXIDE MT 100 SA” from the company TAYCA, “TIOVEIL” from the company TIOXIDE,
  • of alumina such as the products “TIPAQUE TTO-55 (B)” and “TIPAQUE TTO-55 (A)” from the company ISHIHARA, and “UVT 14/4” from the company KEMIRA,
  • of alumina and of aluminum stearate such as the products “MICROTITANIUM DIOXIDE MT 100 T, MT 100 TX, MT 100 Z, MT-01” from the company TAYCA, the products “Solaveil CT-10 W” and “Solaveil CT 100” from the company UNIQEMA and the product “Eusolex T-AVO” from the company MERCK,
  • of silica, of alumina and of alginic acid such as the product “MT-100 AQ” from the company TAYCA,
  • of alumina and of aluminum laurate such as the product “MICROTITANIUM DIOXIDE MT 100 S” from the company TAYCA,
  • of iron oxide and of iron stearate such as the product “MICROTITANIUM DIOXIDE MT 100 F” from the company TAYCA,
  • of zinc oxide and of zinc stearate such as the product “BR 351” from the company TAYCA,
  • of silica and of alumina and treated with a silicone such as the products “MICROTITANIUM DIOXIDE MT 600 SAS”, “MICROTITANIUM DIOXIDE MT 500 SAS” or “MICROTITANIUM DIOXIDE MT 100 SAS” from the company TAYCA,
  • of silica, of alumina, of aluminum stearate and treated with a silicone such as the product “STT-30-DS” from the company TITAN KOGYO,
  • of silica and treated with a silicone such as the product “UV-TITAN X 195” from the company KEMIRA,
  • of alumina and treated with a silicone such as the products “TIPAQUE TTO-55 (S)” from the company ISHIHARA, or “UV TITAN M 262” from the company KEMIRA,
  • of triethanolamine such as the product “STT-65-S” from the company TITAN KOGYO,
  • of stearic acid such as the product “TIPAQUE TTO-55 (C)” from the company ISHIHARA,
  • of sodium hexametaphosphate such as the product “MICROTITANIUM DIOXIDE MT 150 W” from the company TAYCA,
  • TiO₂ treated with octyltrimethylsilane sold under the trade name “T 805” by the company DEGUSSA SILICES,
  • TiO₂ treated with a polydimethylsiloxane sold under the trade name “70250 Cardre UF TiO₂SI₃” by the company CARDRE,
  • anatase/rutile TiO₂ treated with a polydimethylhydrogenosiloxane sold under the trade name “MICRO TITANIUM DIOXIDE USP GRADE HYDROPHOBIC” by the company COLOR TECHNIQUES.

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:

• • those marketed under the name “Z-cote” by the company Sunsmart;
  • those marketed under the name “Nanox” by the company Elementis;
  • those marketed under the name “Nanogard WCD 2025” by the company Nanophase Technologies.

The coated zinc oxide pigments are for example:

• • those marketed under the name “Oxide zinc CS-5” by the company Toshibi (ZnO coated with polymethylhydrogensiloxane);
  • those marketed under the name “Nanogard Zinc Oxide FN” by the company Nanophase Technologies (40% dispersion in Finsolv TN, benzoate of C₁₂-C₁₅ alcohols);
  • those marketed under the name “DAITOPERSION ZN-30” and “DAITOPERSION Zn-50” by the company Daito (dispersions in cyclopolymethylsiloxane/ethoxylated polydimethylsiloxane, containing 30% or 50% of zinc nano-oxides coated with silica and polymethylhydrogensiloxane);
  • those marketed under the name “NFD Ultrafine ZnO” by the company Daikin (ZnO coated with perfluoroalkyl phosphate and perfluoroalkylethyl-based copolymer in dispersion in cyclopentasiloxane);
  • those marketed under the name “SPD-Z1” by the company Shin-Etsu (ZnO coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane);
  • those marketed under the name “Escalol Z100” by the company ISP (ZnO treated with alumina and dispersed in ethylhexyl methoxycinnamate/PVP-hexadecene copolymer/methicone) mixture;
  • those marketed under the name “Fuji ZnO-SMS-10” by the company Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane);
  • those marketed under the name “Nanox Gel TN” by the company Elementis (ZnO dispersed at 55% in benzoate of C₁₂-C₁₅ alcohols with polycondensate of hydroxystearic acid).

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

Amaryllidaceae

Anacardiaceae

Annonaceae: ylang ylang
Apiaceae (for example umbelliferae): dill, angelica, coriander, samphire, carrot, parsley

Araceae

Aristolochiaceae

Asteraceae: yarrow, artemisia, chamomile, helichrysum

Betulaceae

Brassicaceae

Burseraceae: incense

Caryophyllaceae

Canellaceae

Caesalpiniaceae: copaifera (copahu)

Chenopodiaceae

Cistaceae: rockrose

Cyperaceae

Dipterocarpaceae

Ericaceae: wintergreen

Euphorbiaceae

Fabaceae

Geraniaceae: geranium

Guttiferae

Hamamelidaceae

Hernandiaceae

Hypericaceae: St John's wort

Iridaceae

Juglandaceae

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

Malvaceae

Meliaceae

Monimiaceae

Moraceae: hemp, hop

Myricaceae

Myristicaceae: nutmeg
Myrtaceae: eucalyptus, tea tree, niaouli, cajeput, backousia, clove, myrtle

Oleaceae

Piperaceae: pepper

Pittosporaceae

Poaceae: citronella, lemongrass, vetiver

Polygonaceae

Ranunculaceae

Rosaceae: roses

Rubiaceae

Rutaceae: all the citrus plants

Salicaceae

Santalaceae: sandalwood

Saxifragaceae

Schisandraceae

Styracaceae: benzoin
Thymelaeaceae: agar wood

Tiliaceae

Valerianaceae: valerian, nard
Verbenaceae: lantana, verbena

Violaceae

Zingiberaceae: galanga, curcuma, cardamom, ginger

Zygophyllaceae

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 F_A that is free after condensation, and a function F_C 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 F_A 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,

• • compounds A and C are selected so that the presence of C does not prevent the condensation of A; or
  • compounds A and C and/or the conditions of use are selected so that the condensation of A is quicker than the reaction of C; or
  • compound A can condense whereas compound C cannot react. After a certain time, the reaction of C is initiated by a further action or automatically, for example by change of pH or of temperature or by application of a light source.

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.

Pharmaceutical Forms

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.

Formulation for Coloring, in Particular for a Self-Tanning Effect

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:

• • tetrabromofluorescein or eosin known by the CTFA name: CI 45380 or Red 21
  • phloxine B known by the CTFA name: CI 45410 or Red 27
  • diiodofluorescein known by the CTFA name: CI 45425 or Orange 10;
  • dibromofluorescein known by the CTFA name: CI 45370 or Orange 5;
  • the sodium salt of tetrabromofluorescein known by the CTFA name: CI 45380 (Na salt) or Red 22;
  • the sodium salt of phloxine B known by the CTFA name: CI 45410 (Na salt) or Red 28;
  • the sodium salt of diiodofluorescein known by the CTFA name: CI 45425 (Na salt) or Orange 11;
  • erythrosine known by the CTFA name: CI 45430 or Acid Red 51;
  • phloxine known by the CTFA name: CI 45405 or Acid Red 98.

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.

Compositions Containing a Photoprotective Agent (or Filter), Care Composition

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/C_13-14 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:

• • vitamins (A, C, E, K, PP etc.) and the derivatives or precursors thereof, alone or mixed,
  • antiglycation agents;
  • soothing agents,
  • inhibitors of nitric-oxide synthase;
  • agents stimulating the synthesis of dermal or epidermal macromolecules and/or preventing their degradation;
  • agents stimulating fibroblast proliferation;
  • agents stimulating keratinocyte proliferation;
  • muscle relaxants;
  • lifting agents,
  • matting agents,
  • keratolytic agents,
  • desquamating agents;
  • hydrating agents for example polyols such as glycerin, butylene glycol, propylene glycol;
  • anti-inflammatories;
  • agents acting on the energy metabolism of the cells,
  • insect repellents;
  • antagonists of substances P or of CRGP;
  • agents against hair loss and/or for hair regrowth;
  • antiwrinkle agents.

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 Agents

“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:

• • rice starch or maize starch, in particular an aluminum starch octenyl succinate marketed under the name Dry Flo® by the company National Starch,
  • kaolinite;
  • silicas;
  • talc;
  • a pumpkin seed extract such as is marketed under the name Curbilene® by the company Indena;
  • cellulose microbeads as described in patent application EP 1 562 562;
  • fibers, such as fibers of silk, of cotton, of wool, of flax, of cellulose extracted notably from wood, from vegetables or from algae, of polyamide (Nylon®), of modified cellulose, of poly-p-phenylene terephtamide, of acrylic, of polyolefin, of glass, of silica, of aramid, of carbon, of Teflon®, of insoluble collagen, of polyesters, of polyvinyl chloride or of vinylidene, of polyvinyl alcohol, of polyacrylonitrile, of chitosan, of polyurethane, of polyethylene phthalate, fibers formed from a polymer blend, absorbable synthetic fibers, and mixtures thereof described in patent application EP 1 151 742;
  • microspheres of expanded acrylic copolymers such as those marketed by the company EXPANCEL under the names EXPANCEL 551®,
  • fillers with an optical effect as described in patent application FR 2 869 796, in particular:
  • powders of polyamides (Nylon®), for example particles of Nylon 12 of the Orgasol type from Arkema with average size of 10 microns and refractive index 1.54,
  • silica powders, for example Silica beads SB150 from Miyoshi with average size of 5 microns and refractive index 1.45,
  • polytetrafluoroethylene powders, such as the PTFE ceridust 9205F from Clariant with average size of 8 microns and refractive index 1.36,
  • silicone resin powders such as Silicon resin Tospearl 145A from GE Silicone with average size of 4.5 microns and refractive index 1.41,
  • powders of acrylic copolymers, notably of polymethyl (meth)acrylate, such as the particles PMMA Jurymer MBI from Nihon Junyoki with average size of 8 microns and refractive index 1.49, or the particles Micropearl M1008 and F 80 ED® from the company Matsumoto Yushi-Seiyaku,
  • wax powders such as the particles Paraffin wax microease 114S of micropowders with average size of 7 microns and refractive index 1.54,
  • polyethylene powders, notably comprising at least one ethylene/acrylic acid copolymer, and in particular consisting of ethylene/acrylic acid copolymers such as the particles Flobeads EA 209 from Sumitomo (with average size of 10 microns and refractive index 1.48),
  • powders of elastomeric crosslinked organopolysiloxane coated with silicone resin, notably of silsesquioxane resin, as described for example in U.S. Pat. No. 5,538,793. Elastomer powders of this kind are sold under the names “KSP-100”, “KSP-101”, “KSP-102”, “KSP-103”, “KSP-104”, “KSP-105” by the company SHIN ETSU, and
  • talc/titanium dioxide/alumina/silica composite powders such as those sold under the name Coverleaf® AR-80 by the company Catalyst & chemicals,
  • mixtures thereof,
  • absorbent compounds and/or adsorbing sebum as described in patent application FR 2 869 796. We may notably mention:
  • silica powders, for example the porous silica microspheres sold under the name “SILICA BEADS SB-700” marketed by the company MYOSHI, “SUNSPHERE® H51”, “SUNSPHERE® H33”, “SUNSPHERE® H53” marketed by the company ASAHI GLASS; the amorphous silica microspheres coated with polydimethylsiloxane sold under the name “SA SUNSPHERE® H-33” and “SA SUNSPHERE® H-53” marketed by the company ASAHI GLASS;
  • powders of amorphous mixed silicates, notably of aluminum and of magnesium, for example marketed under the name “NEUSILIN UFL2” by the company Sumitomo;
  • powders of polyamides (nylon®), for example “ORGASOL® 4000” marketed by the company Arkema, and
  • powders of acrylic polymers, notably of polymethyl methacrylate, for example “COVABEAD® LH85” marketed by the company WACKHERR; of polymethyl methacrylate/ethylene glycol dimethacrylate, for example “DOW CORNING 5640 MICROSPONGE® SKIN OIL ADSORBER” marketed by the company DOW CORNING, or “GANZPEARL® GMP-0820” marketed by the company GANZ CHEMICAL; of allyl polymethacrylate/ethylene glycol dimethacrylate, for example “POLY-PORES L200” or “POLY-PORE® E200” marketed by the company AMCOL; of ethylene glycol dimethacrylate/lauryl methacrylate copolymer, for example “POLYTRAP® 6603” marketed by the company DOW CORNING;
  • particles of silicate, such as alumina silicate;
  • particles of mixed silicates, such as:
  • particles of aluminum silicate and magnesium silicate, such as the hydrated saponite or silicate of magnesium and of aluminum with a sodium sulfate marketed under the trade name Sumecton® by the company Kunimine;
  • the complex magnesium silicate, hydroxyethylcellulose, black cumin oil, cucurbit oil and phospholipids or Matipure® from Lucas Meyer, and
  • mixtures thereof.
    As preferred matting agents, according to the invention it is possible to use a pumpkin seed extract, a rice starch or maize starch, kaolinite, silicas, talc, powders of polyamides, powders of polyethylenes, powders of acrylic copolymers, microspheres of expanded acrylic copolymers, microbeads of silicone resins, particles of mixed silicate and mixtures thereof.
    Fillers with a Blurring Effect

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:

• • porous silica microparticles, for example Silica Beads® SB 150 and SB 700 from Myochi with average size of 5 μm and SUNSPHERES® series H from Asahi Glass such as H33, H51 with size of 3.5 and 5 μm respectively.
  • hollow hemispherical particles of silicone resins such as NLK 500®, NLK 5060 and NLK 510® from Takemoto Oil and Fat, notably described in EP-A-1579849,
  • silicone resin powders for example SILICON Resin Tospearl® 145 A DE GE silicone with average size of 4.5 μm.
  • powders of acrylic copolymers, notably of polymethyl (meth)acrylate, for example the PMMA particles Jurimer MBI® from Nihon Junyoki with average size of 8 μm, the hollow spheres of PMMA sold under the name COVABEAD® LH 85 by the company Wackherr and the microspheres of expanded vinylidene/acrylonitrile/methylene methacrylates sold under the name Expancel®.
  • powders of waxes such as the particles Paraffin wax microloase® 114S from Micropowders with average size of 7 μm.
  • powders of polyethylenes notably comprising at least one ethylene/acrylic acid copolymer, for example FLOBEADS® EA 209 E from Sumimoto with average size of 10 μm.
  • powders of elastomeric crosslinked organopolysiloxanes coated with silicone resin, notably of silsesquioxane, under the name KSP 100®, KSP 101®, KSP 102®, KSP 103®, KSP 104® and KSP 105® by the company Shin Etsu.
  • composite powders of talc/titanium dioxide/alumina/silica for example Coverleaf AR 80® from the company Catalyst & Chemical.
  • talc, mica, kaolin, lauryl glycine, starch powders crosslinked by the anhydride octeanyl succinate, boron nitride, polytetrafluoroethylene powders, precipitated calcium carbonate, the carbonate of magnesium hydrocarbonate, barium sulfate, hydroxyapatite, calcium silicate, cerium dioxide and microcapsules of glass or of ceramic.
  • synthetic or natural, mineral or organic hydrophilic or hydrophobic fibers such as fibers of silk, of cotton, of wool, of flax, of cellulose extracted notably from wood, from vegetables or from algae, of polyamide (Nylon®), of modified cellulose, of poly-p-phenylene terephtamide, in acrylic, of polyolefin, of glass, of silica, of aramid, of carbon, of polytetrafluoroethylene (Teflon®), of insoluble collagen, of polyesters, of polyvinyl chloride or of vinylidene, of polyvinyl alcohol, of polyacrylonitrile, of chitosan, of polyurethane, of polyethylene phthalate, fibers formed of a polymer blend, absorbable synthetic fibers, and mixtures thereof described in patent application EP 1 151 742.
  • spherical elastomeric crosslinked silicones such as Trefil E-505C® or E-506 C® from Dow Corning.
  • abrasive fillers which by a mechanical effect provide a smoothing of the cutaneous microrelief, such as abrasive silica, for example Abrasif SP® from Semanez or powders of nuts or of shells (apricot, walnut for example from Cosmetochem).

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.

Agents Promoting the Naturally Pinkish Coloration of the Skin:

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:

• • a self-tanning agent, i.e. an agent which, applied on the skin, notably on the face, makes it possible to obtain a tanned effect with an appearance more or less similar to what can result of prolonged exposure to the sun (natural tan) or under a UV lamp;
  • an additional coloring agent, i.e. any compound having a particular affinity for the skin so that it can endow the skin with a coloration that is durable, non-covering (i.e. not having a tendency to opacify the skin) and is not removed with water or by means of a solvent, and withstands both rubbing and washing with a solution containing surfactants. This durable coloration therefore differs from the superficial and momentary coloration supplied for example by a makeup pigment; and mixtures thereof.

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:

• • tetrabromofluorescein or eosin known by the CTFA name: CI 45380 or Red 21
  • phloxine B known by the CTFA name: CI 45410 or Red 27
  • diiodofluorescein known by the CTFA name CI 45425 or Orange 10
  • dibromofluorescein known by the CTFA name: CI 45370 or Orange 5
  • the sodium salt of tetrabromofluorescein known by the CTFA name: CI 45380 (Na salt) or Red 22
  • the sodium salt of phloxine B known by the CTFA name: CI 45410 (Na salt) or Red 28
  • the sodium salt of diiodofluorescein known by the CTFA name: CI 45425 (Na salt) or Orange 11;
  • erythrosine known by the CTFA name: CI 45430 or Acid Red 51.
  • phloxine known by the CTFA name: CI 45405 or Acid Red 98.

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);

Abrasive Fillers or Exfoliating Agents

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:

• • a first composition comprising, in a physiologically acceptable medium, at least one compound or set of compounds A as described above;
  • a second composition comprising, in a physiologically acceptable medium, at least one compound C as described above.

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:

• • a first composition comprising a compound A or set of compounds A as defined above, function F_A being a primary amine function (compound A being more particularly APTES); and
  • a second composition comprising DHA.

The following examples are supplied as a nonlimiting illustration of the invention.

EXAMPLES

Example 1

Demonstration of the Improvement of the Properties of Durability of the Formulas

Test Principle:

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.

Example 2

Formulations Comprising an Alkoxysilane with Free Amine Function (A) and DHA (C)—Demonstration of Improved Color Increase and Color Intensity

TABLE 1
Formulation containing an alkoxysilane with free amine function
Type        Concentration (%)
LACTIC ACID 1.5
APTES       10
WATER       88.5

TABLE 2
Formulation containing DHA:
Type                Concentration
DHA                 7
DISODIUM EDTA       0.1
PRESERVATIVE        0.7
PRESERVATIVE        0.2
GLYCERIN            2
PROPYLENE GLYCOL    2
PEG-60 HYDROGENATED 0.35
CASTOR OIL
WATER               87.65

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 FIG. 1.

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).

Example 3

Demonstration that the Deposit is Made Insoluble

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.

Example 4

Obtaining a Fluorescent Effect

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.

Example 5

Formulations of an Alkoxysilane (A) and a Perfuming Compound (C)

The formulation containing an alkoxysilane with free amine function is that from Table 1 above.

TABLE 3
Formulation containing cinnamic aldehyde
Type                Concentration (%)
CINNAMIC ALDEHYDE   0.5
DISODIUM EDTA       0.1
PRESERVATIVE        0.7
PRESERVATIVE        0.2
GLYCERIN            2
PROPYLENE GLYCOL    2
PEG-60 HYDROGENATED 0.35
CASTOR OIL
WATER               94.15

Example 6

Formulations Containing an Alkoxysilane (A) and a UV Filtering Compound (C)

The formulation containing an alkoxysilane with free amine function is that in Table 1 above.

TABLE 4
Formulation containing Mexoryl SX:
Type                Concentration (%)
MEXORYL SX          20
DISODIUM EDTA       0.1
PRESERVATIVE        0.7
PRESERVATIVE        0.2
GLYCERIN            2
PROPYLENE GLYCOL    2
PEG-60 HYDROGENATED 0.35
CASTOR OIL
WATER               74.65

Example 7

Formulations Containing an Alkoxysilane (A) and an Antidandruff Agent (C)

The formulation containing an alkoxysilane with free amine function is that in Table 1 above.

TABLE 5
Formulation containing ZnPt:
Type                Concentration (%)
ZINC PYRITHIONE     2
DISODIUM EDTA       0.1
PRESERVATIVE        0.7
PRESERVATIVE        0.2
GLYCERIN            2
PROPYLENE GLYCOL    2
PEG-60 HYDROGENATED 0.35
CASTOR OIL
WATER               92.65

Example 8

Formulations Containing an Alkoxysilane (A) and a Skin Care Active Ingredient (C)

The formulation containing an alkoxysilane with free amine function is that in Table 1 above.

TABLE 6
Formulation containing vitamin C
Type                Concentration (%)
VITAMIN C           2
DISODIUM EDTA       0.1
PRESERVATIVE        0.7
PRESERVATIVE        0.2
GLYCERIN            2
PROPYLENE GLYCOL    2
PEG-60 HYDROGENATED 0.35
CASTOR OIL
WATER               92.65

Example 9

Formulations Containing an Alkoxysilane (A) and a Conditioning Polymer (C)

The formulation containing an alkoxysilane with free amine function is that in Table 1 above.

TABLE 7
Formulation containing a copolymer of maleic anhydride:
Type                             Concentration (%)
Polypropylene maleic anhydride - 2
LICOCARE from CLARIANT
DISODIUM EDTA                    0.1
PRESERVATIVE                     0.7
PRESERVATIVE                     0.2
GLYCERIN                         2
PROPYLENE GLYCOL                 2
PEG-60 HYDROGENATED              0.35
CASTOR OIL
WATER                            92.65

Claims

1. A method for treating skin, the method comprising:

(I) applying a compound A, which is capable of condensing in situ to form a condensed material comprising a free reactive function FA, on an area of the skin; and

(II) applying a compound C comprising a reactive function FC, which forms a covalent bond by reaction with the function FA, to area of skin.

2. The method of claim 1, wherein the condensed material is soluble in water, and compound C is selected so that reaction of the compound C on the condensed material decreases the solubility of the condensed material in water.

3. The method of claim 1, wherein the compound A comprises an organic silicon compound comprising 1 to 3 silicon atoms and at least two hydroxyl or hydrolyzable groups.

4. The method of claim 1, wherein the function FA is an amine.

5. The method of claim 1, wherein compound A has a formula: wherein:

R4 is a halogen, an OR′ group, or an R′1 group;

R5 is a halogen, an OR″ group, or an R′2 group;

R6 is a halogen, an OR′″ group, or an R′3 group; and

R1, R2, R3, R′, R″, R′″, R′2, and R′3, are each independently a saturated or unsaturated, linear or branched hydrocarbon group, optionally comprising an acid group, an amine group, or a combination thereof, wherein R1, R2, R′, R″, and R′″ can further denote hydrogen, and at least two of the groups R4, R5, and R6 are different from groups R′1, R′2, and R′3.

6. The method of claim 1, wherein the compound A is γ-aminopropyl triethoxysilane (APTES) or a derivative thereof of APTES.

7. The method of claim 1, wherein the compound A comprises a first compound A1 which is γ-aminopropyl triethoxysilane (APTES) or a derivative of APTES, and a second compound A2, which is methyl-triethoxysilane (MTES).

8. The method of claim 1, wherein compound C is a compound that modifies a physicochemical surface property of the skin, and

wherein the applying (I) and (II) results in a cosmetic conditioning of said area of the skin.

9. The method of claim 8, wherein compound C comprises a conditioning polymer.

10. The method of claim 1, wherein the applying (I) and (II) results in a cosmetic modification of a biological activity of said area of the skin.

11. The method of claim 1, the applying (I) and (II) results in a coloring of said area of the skin.

12. The method of claim 1, comprising, in the following order:

applying the compound A to said area of the skin;

optionally rinsing said area of the skin; and

applying the compound C to said area of the skin.

13. A cosmetic kit comprising:

a first composition comprising, in a physiologically acceptable medium, a compound A, which is capable of condensing in situ on an area of skin to form a condensed material comprising a free reactive function FA; and

a second composition comprising, in a physiologically acceptable medium, a compound C comprising a reactive function FC, which forms a covalent bond by reaction with the function FA.

14. The method of claim 1, wherein the function FA is a primary amine.

15. The method of claim 1, wherein the function FC is a halogen atom, a carbonyl, a carboxylic acid, an ester, an amine, or a hydroxyl function.

16. The method of claim 1, wherein the function FC is a carbonyl function.

17. The method of claim 4, wherein the function FC is an aldehyde function, which is capable of reacting with an amine.

18. The method of claim 4, wherein the function FC is an ketone function, which is capable of reacting with an amine.