EP2819636A1

EP2819636A1 - Use of porphyrin-type catalytic oxidation compounds as an anti-dandruff agent

Info

Publication number: EP2819636A1
Application number: EP13710501.1A
Authority: EP
Inventors: Henri Samain
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2012-02-29
Filing date: 2013-02-22
Publication date: 2015-01-07
Also published as: CN104135989A; CN104135989B; FR2987259A1; US20150064120A1; JP2015508806A; US9326931B2; FR2987259B1; WO2013128101A1

Abstract

The present invention relates to the cosmetic use of catalytic oxidation compounds, selected from among porphyrins, as anti-dandruff agents.

Description

USE AS ANTIPELLICULAR AGENT OF CATALYTIC COMPOUNDS OF PORPHYRIN TYPE OXIDATION

The present invention relates to the cosmetic use of particular catalytic oxidation compounds as anti-dandruff agent, in particular in the cosmetic treatment of dandruff conditions related to the excessive proliferation of yeasts of the genus Malassezia on the scalp. The invention also relates to a cosmetic treatment method for eliminating and / or reducing dandruff, in particular that caused by yeasts of the genus Malassezia, using said compounds.

Dandruff problems affect up to 50% of the world's population. They affect men as well as women and are perceived as having a very negative psychosocial impact. The appearance of dandruff is embarrassing both from the aesthetic point of view and the inconvenience it causes (especially itching), so that many people confronted with this problem to varying degrees wish to get rid of it effectively and permanently.

Dandruff is an excessive and visible desquamation of the scalp, resulting from the rapid multiplication of epidermal cells and their abnormal maturation. This phenomenon can be caused by overly aggressive hair treatments, extreme weather conditions, nervousness, diet, fatigue, pollution.

The dandruff states are most often the result of a disorder of the scalp microflora, and more particularly of the excessive colonization of a fungus which belongs to the yeast family of the genus Malassezia and which is naturally present on the scalp. .

Many anti-dandruff treatments have been developed with the main goal of eradicating Malassezia yeasts from the scalp. Thus, the activity of today's anti-dandruff active agents, such as zinc pyrithione, piroctone olamine or selenium disulfide, relies mainly on their fungicidal properties. However, these anti-dandruff agents are not totally satisfactory in terms of effectiveness (immediate effectiveness, or duration of the effect), and / or in terms of impact on the environment. The present invention aims to provide non-irritating anti-dandruff agents for the skin and scalp, as effective as known anti-dandruff agents, while having a more favorable impact in terms of the environment (low bioaccumulation and good biodegradability in particular). The invention also aims to propose active agents to restore the ecoflora of the scalp and in particular to prevent excessive colonization of the scalp by Malassezia sp.

The Applicant has now found, surprisingly, that the use of at least one particular catalytic oxidation compound makes it possible to effectively treat the dandruff conditions, in particular those associated with the proliferation of yeasts of the Malassezia genus, and to remedy the disadvantages. of the prior art. It has been observed that by employing the compounds according to the invention, it is possible to eliminate and / or reduce the number of yeasts of the genus Malassezia, the number of dandruff, as well as the itching and redness on the scalp. The subject of the present invention is therefore the cosmetic use of at least one catalytic oxidation compound chosen from the porphyrins of formula (I) described hereinafter, or from a cosmetic composition comprising it, as anti-dandruff agent. In the present invention, the term "keratinous material" is understood to mean the skin (face, body, scalp), the hair, the eyelashes, the eyebrows and the nails.

For the purposes of the present invention, the term "catalytic oxidation compound" chosen from porphyrins is intended to mean porphyrin compounds having catalytic oxidation properties.

The catalytic porphyrin oxidation compounds used according to the invention differ from the porphyrin compounds which do not exhibit catalytic oxidation properties by at least one of the three tests as described below. Test 1: Oxidation of 2,2,6,6-tetramethylpiperidine (TEMP)

In this test, the compound 2,2,6,6-tetramethylpiperidine (TEMP) marketed by Sigma Aldrich acts as a probe that reveals the catalytic activity of a porphyrin compound as an oxidation catalyst. The oxidizing agent used during this test is dissolved oxygen.

A solution comprising a phosphate buffer (pH 7.4), 50 mM 2,2,6,6-tetramethylpiperidine compound (TEMP), and a porphyrin compound at 0.5 μΜ is prepared. The solution is saturated with oxygen. The solution is placed in the light of day. After 1 hour, an electron paramagnetic resonance spectrometry (EPR) of the oxidized form of the compound 2,2,6,6-tetramethylpiperidine (TEMP) which corresponds to the compound (2,2,6,6-tetramethylpiperidin-1 - yl) oxyl called TEMPO.

According to the scientific publication Lion et al., 1976; Moan and Wold, 1979, the presence of the compound in the TEMPO form is indicative of oxidation produced by oxygen on the 2,2,6,6-tetramethylpiperidine compound and thus the catalytic effect of the porphyrin compound.

TEMP + O ₂ -> TEMPO

More precisely, the spectrum shows three equivalent intensity peaks characteristic of the presence of the nitroxide radical in the oxidized TEMPO form.

With a porphyrin compound according to the invention, the appearance of the TEMPO compound is observed after 1 hour of contacting.

On the other hand, the presence of a porphyrin which is not included in the invention, such as, for example, cupric chlorophyllin, does not lead to the formation of the TEMPO compound. Test 2: Oxidation of DMPO

In this test, the compound 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) acts as a probe that reveals the catalytic activity of a porphyrin compound as an oxidation catalyst. The oxidizing agent used during this test is dissolved oxygen.

An aqueous solution, pH = 7, comprising 100 mM DMPO and a porphyrin compound at 100 μΜ is prepared. The solution is saturated with oxygen. The solution is placed in the light of day.

After 1 hour, an electron paramagnetic resonance spectrometry (EPR) of the oxidized form of the compound 5,5-dimethyl-1-pyrroline-N-oxide called DMPO-OH is carried out. The presence of the DMPO-OH form is significant for the oxidation of the 5,5-dimethyl-1-pyrroline-N-oxide compound and, therefore, for the catalytic activity of the porphyrin compound.

More precisely, the EPR spectrum is characterized by a constant (constant coupling hyperfine in English) of a ^N = a ^H = 14.6 G.

Test 3: Activation of hydrogen peroxide

1 mM of a porphyrin compound is placed in 10 volumes hydrogen peroxide, spontaneous pH. The solution is placed in daylight. Then, the rate of hydrogen peroxide is measured.

It is considered that the porphyrin compound is catalytic oxidation if it reduces the amount of oxygenated water by a factor of at least 2 (5 volumes or less in the end).

The catalytic porphyrin oxidation compounds according to the invention correspond to at least one of the three tests mentioned above.

The catalytic oxidation compounds according to the present invention may be cationic, anionic or nonionic.

Preferably, the catalytic porphyrin oxidation compounds are chosen from symmetrical porphyrin compounds.

The term "porphyrin symmetric compounds" means porphyrin compounds which, on the one hand, the radicals located in the meso position are identical (to each other) and, on the other hand, the radicals located in the beta-pyrrole position are also identical (between them).

In other words, according to the nomenclature described below, the fact that the radicals in the meso position are identical means that the radicals located in the alpha position are identical. Moreover, the fact that the radicals located in the beta-pyrrole position are identical means that the radicals situated on the one hand in positions 1, 3, 5 and 7 are identical, and, on the other hand, that the radicals located in position 2, 4, 6 and 8 are identical.

The nomenclature of the porphyrin compound is recalled below.

Preferably, the catalytic oxidation porphyrin compounds are chosen from cationic porphyrin compounds, that is to say porphyrin compounds whose groups in the meso or beta-pyrrole position are cationic.

The catalytic oxidation compounds according to the invention correspond to the following formula (I):

in which :

- R2, R3, R5, R6, Re, R9, R11 and R12, identical or different, represent a hydrogen atom; a linear or branched C1-C30 alkyl radical which can be interrupted by one or more groups with heteroatom (s) and / or which can be substituted; a linear or branched C2-C30 alkenyl radical which can be interrupted by one or more groups with heteroatom (s) and / or which can be substituted; a linear or branched C2-C30 alkynyl radical which can be interrupted by one or more groups with heteroatom (s) and / or which can be substituted;

R ₂ and R ₃ , R ₅ and R ₆ , R ₅ and R ₉ and / or R and R 12 may also respectively form with the carbon atoms carrying them an optionally substituted aryl ring, preferably phenyl;

R 1, R ₄ , R ₇ and R 10, which may be identical or different, represent a cationic group such as an optionally substituted pyridinium group; an anionic group such as a phenyl radical substituted with a group SO 3 M '- with M' denoting a hydrogen atom or a cation, for example derived from a metal or an amine or an ammonium cation; a linear or branched C8-C30 alkyl radical which can be interrupted by one or more groups with heteroatom (s) and / or may be substituted; a reactive group, which may be chosen from siloxanes, esters and compounds containing one or more thiol groups; as defined for example in the article Synthesis of "Porphyrin-Linker-Thiol" Molecules with Diverse Linkers for Studies of Molecular-Based Information Storage, by Daniel T. Gryko, Christian Clausen, Kristian Roth, Narasaiah Dontha, David F. Bocian, Werner G. Kuhr, Jonathan S. Lindsey, in the article published in the scientific publication J. Org Chem 2000, 65, 7345-7355;

M is a metal, or a metal ion, chosen from transition metals and alkaline earth metals.

In the context of the definitions of the groups R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 9, R 10, R 11 and R 12, the term "substituted" is understood to mean substituted by one or more radicals chosen from the radicals i) hydroxy, ii) C ₁ -C ₄ alkoxy, iii) acylamino, iv) a halogen atom, preferably chlorine; v) amino optionally substituted with one or two identical or different C 1 -C 10 alkyl radicals, said alkyl radicals being able to form, with the nitrogen atom which bears them, a heterocycle comprising from 5 to 7 ring members, possibly comprising another heteroatom different or different from nitrogen; v) a 5- or 6-membered heterocycle, comprising one or more heteroatoms such as oxygen, optionally substituted nitrogen, optionally carrying at least one cationic charge.

Within the scope of the definitions of the groups R 1, R 2, R 3, R 4, R 5, 6, R 7, R 9, R 9, R 10, R 11 and R 12, "interrupted by one or more groups with heteroatom (s)", is meant to be interrupted by one or more groups selected from an oxygen atom, sulfur; an imino group; an imino group substituted with a linear or branched C1-C10 alkyl radical, optionally bearing one or more linear or branched C1-C10 hydroxyl or alkoxy groups; an imino group substituted with two identical or different C1-C10 alkyl radicals, linear or branched, optionally carrying one or more hydroxyl or alkoxy groups, C1-C10, linear or branched; a carbonyl group; a 5- or 6-membered heterocycle, comprising one or more heteroatoms such as oxygen, optionally substituted nitrogen, possibly carrying at least one cationic charge. In this formula (I), the metal M is connected to the nitrogen atoms forming the pyrrole rings via covalent bonds.

M is a metal, or a metal ion, selected from transition metals and alkaline earth metals, preferably transition metals.

Alkaline earth metal is understood to mean the metals of the MA column of the periodic table of elements, in particular magnesium (Mg) and calcium (Ca). By transition metal is meant metals of columns IB, IIB, IIIB, IVB, VB, VIB, VIIB, and three columns VIII of the Periodic Table of Elements. Preferably, the transition metals are chosen from those of column IB, in particular copper, of column MB, in particular zinc (Zn), column VIIB, in particular manganese (Mn), columns VIII, especially the iron (Fe) and cobalt (Co).

Preferably, the metal M is chosen from zinc, manganese, iron, cobalt, magnesium and calcium, and more preferably the metal M is zinc.

According to one embodiment, R ₂ and R ₃ , R ₅ and R ₆ , R ₅ and R ₆ , R and R ₁₂ may form, respectively, with the carbon atoms carrying them an optionally substituted aryl ring, preferably phenyl.

According to another embodiment, R ₂ , R ₃ , R 5, R 6, R ₅ , R 9, R 11 and R 12 may represent a hydrogen atom. Preferably, R 1, R ₄ , R ₇ and R 10, which may be identical or different, represent an optionally substituted pyridinium group; a phenyl group substituted with a sulfonate group SO3M'-; a linear or branched C8-C30 alkyl radical which may be interrupted by one or more heteroatoms and / or may be substituted.

According to one embodiment, R 1, R, R ₇ and R 10 represent an optionally substituted pyridinium group.

According to another embodiment, R 1, R ₄ , R ₇ and R ₁₀ represent a phenyl group substituted with a group SO 3 M '.

According to another embodiment, R 1, R ₄ , R ₇ and R 10 represent a linear or branched C ₈ -C 30, especially C ₈ -C 18, alkyl radical which can be interrupted by one or more groups with heteroatom (s) and / or may be substituted. In particular, R 1, R, R ₇ and R 10 represent an alkyl radical Cs, Ci ₂ or Cis.

Preferentially, R 1, R ₄ , R ₇ and R 10 represent a pyridinium group, in particular an unsubstituted group.

According to a particular embodiment, M is selected from transition metals and R ₂ , R ₃ , R ₅ , R 6, R ₅ , R ₉ , R ₁ and R ₂ represent a hydrogen atom.

Even more preferentially, M is chosen from transition metals, in particular zinc (Zn), R ₂ , R ₃ , R 5, R 6, Re, R 9, Rn and Ri ₂ represent a hydrogen atom, and Ri, R ₄ , R ₇ and R 10 represent an optionally substituted pyridinium group.

Preferably, the compound of formula (I) used in the context of the present invention is the following compound:

The catalytic oxidation compound, alone or as a mixture, may be present in the cosmetic composition in a content ranging from 0.0001 to 1% by weight, preferably in a content ranging from 0.001 to 0.5% by weight, and more particularly in a content ranging from 0.01 to 0.1% by weight, relative to the total weight of the cosmetic composition.

It is of course possible to use a mixture of catalytic oxidation compounds of formula (I). Thus, the cosmetic composition may comprise two or more different oxidation catalytic porphyrin compounds as defined in formula (I)

In particular, the cosmetic composition may comprise two or more different oxidation catalytic porphyrin compounds (I) chosen from:

the cationic catalytic porphyrin oxidation compounds,

the porphyrin compounds catalytic oxidation anionic and

nonionic catalytic porphyrin oxidation compounds containing one or more fatty chains;

- and their mixtures.

By fatty chain is meant a hydrocarbon chain comprising at least 8 carbon atoms, especially 8 to 30 carbon atoms, more particularly 8 to 18 carbon atoms.

According to a first embodiment, the cosmetic composition may comprise one or more cationic catalytic oxidation porphyrin compounds of formula (I) and one or more anionic catalytic oxidation porphyrin compounds of formula (I).

In particular, the cosmetic composition may comprise a cationic oxidation catalytic porphyrin compound of formula (I) in which R 1, R, R ₇ and R ₁₀ represent an optionally substituted pyridinium group and an anionic catalytic porphyrin oxidation compound of formula (I) wherein R 1, R _4, R ₇ and R represent a phenyl group substituted by a group SOsIvl ^"

According to a second embodiment, the cosmetic composition may comprise one or more canonical catalytic oxidation porphyrin compounds of formula (I) and one or more nonionic catalytic oxidation porphyrin compounds comprising one or more fatty chains of formula

(I) -

In particular, the cosmetic composition may comprise a cationic oxidation catalytic porphyrin compound of formula (I) in which R 1, R ₄ , R ₇ and R 10 represent an optionally substituted pyridinium group and a nonionic catalytic porphyrin oxidation compound. of formula (I) in which R 1, R ₄ , R ₇ and R 10 represent a C 8 -C 30 alkyl radical, in particular C 6 -C 18, in particular C 8, C 12 and C 18.

According to a third embodiment, the cosmetic composition may comprise one or more anionic catalytic porphyrin oxidation compounds of formula (I) and one or more nonionic catalytic porphyrin oxidation compounds containing one or more fatty chains of formula ( I).

In particular, the cosmetic composition may comprise an anionic catalytic porphyrin oxidation compound of formula (I) in which R 1, R ₄ , R ₇ and R ₁₀ represent a phenyl group substituted with a SO 3 M '^"group and a catalytic porphyrin compound. nonionic oxidation of formula (I) in which R 1, R ₄ , R ₇ and R 10 represent a C 8 -C 30, especially C 8 -C 18, especially C ₈ , C ₁₂ and C 18 alkyl radical;

The compounds of formula (I) according to the invention can be prepared easily by the person skilled in the art on the basis of his general knowledge.

The cosmetic compositions that may be used in the context of the invention generally comprise a cosmetically acceptable medium, that is to say a medium that is compatible with keratin materials such as the skin of the face or body, the hair, the eyelashes, eyebrows and nails.

The compounds according to the invention are generally used in topical application. In particular, they can be used as anti-dandruff agents in a cosmetic composition that can be in any galenic form normally used for topical application.

The cosmetic composition used according to the invention may be a composition that can be rinsed or not rinsed. Said composition, in particular a hair composition, is preferably a shampoo, a cream, a mousse (aerosol or not), a paste, a gel, an emulsion, a lotion or a stick. Preferably, the cosmetic composition tick is a shampoo, a gel or a lotion.

The cosmetic composition may be anhydrous or may preferably comprise an aqueous or hydro-organic medium; it may therefore comprise water and / or one or more organic solvents which may be chosen from linear or branched C 1 -C 6 monoalcohols such as ethanol, isopropanol, tert-butanol or n-butanol. butanol; polyols such as glycerol, propylene glycol, hexylene glycol (or 2-methyl-2,4-pentanediol), and polyethylene glycols; polyol ethers such as dipropylene glycol monomethyl ether; and their mixtures.

Preferably, the cosmetic composition comprises an amount of organic solvents ranging from 0.05% to 60%, preferably from 0.5% to 50%, and more preferably from 1% to 40% by weight, relative to the total weight of the cosmetic composition.

The cosmetic composition may also advantageously comprise at least one additional constituent, customary in cosmetics, such as, in particular, thickeners; surfactants selected from anionic, cationic, nonionic, amphoteric and / or zwitterionic surfactants; conditioning agents; silicones; fall arrest agents; other antidandruff agents; vitamins; waxes, sunscreens, inorganic or organic pigments, colored or unstained; dyes; pearlescent and opacifying agents, sequestering agents, plasticizing agents, perfumes; conservatives. Of course, those skilled in the art will take care to choose this or these optional additional compounds and / or their quantity in such a way that the advantageous properties of the composition according to the invention are not, or not substantially, impaired by the addition envisaged. .

In particular, the cosmetic composition may comprise one or more oxidizing agents, chosen for example from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, and enzymes such as than peroxidases and oxidoreductases with two or four electrons.

In particular, the cosmetic composition may comprise one or more polymers, in particular those described in the article "Novel Porphyrin - Inorganic Hydrogels for Photoactive Intraocular Lens Biomaterials", Journal of Physical Chemistry B (2007), 11 (1). ), 527-534.

Preferably, the cosmetic composition does not comprise (0%) sequestering agents, in particular sequestering agents capable of capturing the metal of the oxidation catalytic compounds of formula (I).

Preferably, the cosmetic composition comprises one or more sequestering agents in a low content, in particular in a content of less than 1% by weight, more particularly less than 0.01% by weight relative to the weight. total of the composition.

Preferably, the cosmetic composition may comprise one or more particles having a cationic or anionic surface charge. In particular, the cosmetic composition may comprise one or more particles having a surface ionic charge opposite to that of the catalytic oxidation compounds according to the invention. More particularly, the cosmetic composition may comprise one or more particles having a surface ionic charge opposite to that of the catalytic oxidation porphyrin compounds according to the invention. Thus the cosmetic composition may comprise one or more cationic porphyrin compounds as defined above and one or more particles having an anionic surface charge. In the same way, the cosmetic composition may comprise one or more anionic porphyrin compounds as defined above and one or more particles having a cationic surface charge. The particles can be mineral or organic. Among the mineral particles, there may be mentioned clays, silicates, silica, kaolin, hydroxyapatite or particles formed by alkaline earth metals, transition metals, rare earth metals and alloys of these metals. . In particular, the particles may be silica and alumina.

According to one embodiment, the cosmetic composition may be aqueous. By "aqueous" is meant a composition whose free water content is greater than 10% by weight, preferably greater than 30% by weight, better still greater than 50% by weight, or even greater than 70% by weight, relative to to the total weight of the composition.

According to another embodiment, the cosmetic composition can be anhydrous. By "anhydrous" is meant a composition whose content of free or added water is less than 10% by weight, especially 3% by weight, and preferably whose added water content is less than 1% by weight relative to the total weight of the composition. Preferably, the anhydrous cosmetic composition does not contain water. In particular, the cosmetic composition can be anhydrous in the case where the catalytic oxidation compounds comprise in their structure one or more fatty chains. The cosmetic composition may be rinsed or not after having been applied to the keratin materials (hair and / or scalp).

According to a variant of the invention, prior to the application of the cosmetic composition according to the invention to keratin materials, it is possible to apply a cosmetic composition making it possible to prepare the surface of said keratin materials; such a "preparation" composition may make it possible to improve the retention of the catalytic oxidation compound porphyrin, phthalocyanine and / or porphyrazine, in particular during rinsing and washing. In particular, the composition of pre- paration improves the retention of the porphyrin compound, especially rinsing and washing.

Preferably, the step of preparing the surface of the keratin materials consists in applying to said surface a cosmetic composition comprising, in a cosmetically acceptable medium, one or more reducing compounds.

According to another variant of the invention, after the application of the cosmetic composition according to the invention to keratin materials, it is possible to apply a cosmetic composition which makes it possible to maintain the resistance of the catalytic oxidation compounds on the surface of said materials. keratin. Preferably, a cosmetic composition comprising, in a cosmetically acceptable medium, one or more polymers is applied to said keratinous materials; this composition can make it possible to effectively retain the catalytic oxidation compounds at the surface of the keratin material.

Moreover, after the application of the cosmetic composition according to the invention, it is possible to apply to the surface of keratin materials a composition comprising one or more active agents chosen from antibacterials, antifungals and / or powders.

It is also possible to apply, before or after the application of the composition according to the invention, a cosmetic composition comprising one or more oxidizing agents. Alternatively, it is also possible to apply a cosmetic composition comprising, in a cosmetically acceptable medium, one or more compounds capable of releasing one or more oxidizing agents. By way of example, said cosmetic composition may contain a mixture comprising glucoseoxidase and glucose.

The subject of the invention is also a cosmetic treatment method intended to eliminate and / or reduce dandruff, in particular that caused by yeasts of the genus Malassezia, characterized in that it comprises the application, on the hair and / or the scalp, at least one catalytic oxidation compound selected from porphyrins, phthalocyanines, porphyrazines and mixtures thereof, or a cosmetic composition comprising them.

The application of the catalytic oxidation compound (s), or of the composition (s) comprising them, may or may not be followed by a rinsing step with water.

Preferably, this cosmetic treatment process is repeated at least twice a week. According to one embodiment, the cosmetic treatment method may comprise the following steps:

a cosmetic composition comprising, in a cosmetically acceptable medium, one or more compounds which are used in a cosmetic medium, is applied to the keratin materials; cationic catalytic oxidation phyrines as defined above,

a cosmetic composition comprising, in a cosmetically acceptable medium, one or more anionic catalytic porphyrin oxidation compound as defined above, is applied to said keratin materials. According to this embodiment, the cosmetic composition comprising the anionic oxidation catalytic porphyrin compound can be applied immediately or not after the cosmetic composition comprising the cationic catalytic porphyrin cationic oxidation compound (or conversely). According to another embodiment, the cosmetic treatment process may comprise the following steps:

a cosmetic composition comprising, in a cosmetically acceptable medium, one or more cationic catalytic porphyrin cationic oxidation compounds as defined above, and a cosmetic composition comprising, in a cosmetically-modified medium, on said keratin materials, is applied to the keratin materials; acceptable, one or more nonionic catalytic porphyrin oxidation compounds comprising one or more fatty chains as defined above.

According to this embodiment, the cosmetic composition comprising the nonionic catalytic porphyrin oxidation compound having one or more fatty chains may be applied immediately or not after the cosmetic composition comprising the cationic catalytic porphyrin cationic oxidation compound (or conversely). According to another embodiment, the cosmetic treatment process may comprise the following steps:

a cosmetic composition comprising, in a cosmetically acceptable medium, one or more anionic oxidation catalytic porphyrin compounds as defined above, and on a keratinous material, a cosmetic composition comprising, in a cosmetically-modified medium, a cosmetic composition is applied to the keratin materials. acceptable, one or more catalytic porphyrin compounds of nonionic oxidation comprising one or more fatty chains as defined above.

According to this embodiment, the cosmetic composition comprising the nonionic catalytic porphyrin oxidation compound having one or more fatty chains may be applied immediately or not after the cosmetic composition comprising the anionic catalytic porphyrin oxidation compound (or conversely). The invention is illustrated in more detail in the following examples. Example 1

Tested compound

This porphyrin compound positively responds in particular to tests 1 and 2 as described above.

The inhibitory activity of this compound against Malassezia furfur was evaluated in the following manner.

The test is performed using a micromethode developed in a microplate. The principle of the test is based on the contacting of decreasing concentrations of compound with an identical seed inoculum in a culture medium conducive to its growth.

The test compound is thus brought into contact with an inoculum of the microorganism, in a culture medium conducive to its growth (Sabouraud medium with 10% olive oil).

After incubation for 24 to 48 hours, at 32.5 ° C., the optical density (620 nm) is measured and the results are expressed as a percentage of calculated growth relative to a growth control (not including a test compound). .

Dilutions of the compound are made in agar 1/1000; each concentration is tested 3 times.

It is found that at a concentration of 0.001% by weight of tested compound, eradication of the microorganisms Malassezia furfur (decrease by a factor greater than 10,000) is obtained.

Claims

1. Cosmetic use of at least one catalytic oxidation compound chosen from compounds of formula (I), alone or as a mixture, or from a cosmetic composition comprising it, as anti-dandruff agent:

in which :

R ₂ and R ₃ , R ₅ and R ₆ , Re and R ₉ and / or R and R 12 may also form respectively with the carbon atoms carrying them an optionally substituted aryl ring;

R 1, R ₄ , R ₇ and R ₁₀ , which may be identical or different, represent a cationic group such as an optionally substituted pyridinium group; an anionic group such as a phenyl radical substituted with a group S0 ₃ M 'with M' denoting a hydrogen atom or a cation for example derived from a metal or an amine or an ammonium cation; an alkyl radical containing 8 to C _30, linear or branched trusted, can be interrupted by one or more groups with heteroatom (s) and / or may be substituted; a reactive group, which may be chosen from siloxanes, esters and compounds containing one or more thiol groups;

M is a metal, or a metal ion, chosen from transition metals and alkaline earth metals;

2. Use according to claim 1, wherein the metal M is selected from zinc, manganese, iron, cobalt, magnesium and calcium, and more preferably is zinc.

3. Use according to one of the preceding claims, wherein Ri, R ₄ , R ₇ and Rio represent a pyridinium group, in particular unsubstituted.

4. Use according to one of the preceding claims, wherein M is selected from transition metals, including zinc (Zn), R2, R3, R5, R6, Rs, R _9, R11 and R12 represent a hydrogen atom, hydrogen, and R 1, R ₄ , R ₇ and R 10 represent an optionally substituted pyridinium group.

5. Use according to one of the preceding claims, wherein the catalytic oxidation compound is of formula:

6. Use according to one of the preceding claims, wherein the catalytic oxidation compound (s) are present in the cosmetic composition in a content ranging from 0.0001 to 1% by weight, preferably from 0.001 to 0.5% by weight. by weight, and more particularly from 0.01 to 0.1% by weight, relative to the total weight of the cosmetic composition.

7. Use according to one of the preceding claims, wherein the cosmetic composition comprises two or more different catalytic oxidation porphyrin compounds chosen from:

the cationic catalytic porphyrin oxidation compounds,

the porphyrin compounds catalytic oxidation anionic and

the nonionic catalytic porphyrin oxidation compounds comprising one or more fatty chains,

- and their mixtures.

8. Use according to one of the preceding claims, wherein the cosmetic composition is anhydrous or comprises water and / or one or more solvents. organic.

9. Use according to one of the preceding claims, wherein the cosmetic composition comprises at least one additional component selected from thickeners; surfactants selected from anionic, cationic, nonionic, amphoteric and / or zwitterionic surfactants; conditioning agents; silicones; fall arrest agents; other antidandruff agents; vitamins; waxes, sunscreens, inorganic or organic pigments, colored or unstained; dyes; pearlescent and opacifying agents, sequestering agents, plasticizing agents, perfumes; conservatives; oxidizing agents; polymers; particles having a cationic or anionic surface charge. 0. Cosmetic treatment process intended to eliminate and / or reduce the films, in particular those caused by the yeasts of the genus Malassezia, characterized in that it comprises the application, on the hair and / or the scalp, of one or more catalytic oxidation compounds chosen from compounds of formula (I), or a cosmetic composition comprising them. 1 1. Process according to Claim 10, in which, prior to the application of the compound (s) of formula (I) on the keratin materials, a cosmetic composition is applied to prepare the surface of said keratin materials, comprising one or more reducing compounds. 12. Method according to one of claims 10 to 1 1, wherein, after the application of the compound (s) of formula (I) on keratin materials, applying a cosmetic composition to maintain the strength of the catalyst compounds of oxidation on the surface of said keratin materials; in particular comprising one or more polymers.