FR3159745A1 - Composition comprising a thiopyridinone compound, niacinamide and gluconolactone - Google Patents

Abstract

Composition comprising a thiopyridinone compound, niacinamide and gluconolactone The present invention relates to a composition, preferably cosmetic, comprising: - at least one thiopyridinone compound chosen from the compounds of formula (I), the tautomers of formula (I'), their salts, their solvates such as their hydrates, their optical isomers, their racemates and their mixtures; - at least niacinamide or one of its derivatives; - at least gluconolactone; - a surfactant system comprising (i) at least one N-acyl-amino surfactant and (ii) at least one amphoteric surfactant; and - at least one non-associative crosslinked copolymer of acrylic acid and/or methacrylic acid, or one of their esters. Figure for abstract: none

Description

Composition comprising a thiopyridinone compound, niacinamide and gluconolactone

The present invention relates to a composition, preferably cosmetic, for the care of keratin materials, in particular skin care.

At various times in their lives, some people experience the appearance of darker and/or more colorful spots on their skin, particularly on their face and hands, which give their skin a heterogeneous appearance. These spots are due in particular to a high concentration of melanin in the keratinocytes located on the surface of the skin.

The use of harmless and effective topical depigmenting substances is particularly desirable for the purpose of reducing pigment spots.

For example, arbutin, niacinamide, and kojic acid are known as skin depigmenting agents.

Furthermore, WO2012/080075 and WO2017/102349 disclose a novel depigmenting or whitening agent which is a thiopyridinone compound. This thiopyridinone compound exhibits particularly effective depigmenting or whitening properties by reducing the production of melanin.

However, it has been discovered that thiopyridinone compounds tend to destabilize in a composition over time, particularly when the composition including this compound is maintained for a relatively long period under an elevated temperature.

Thus, an objective of the present invention is to provide a composition including a thiopyridinone compound with increased stability over time, particularly when the composition is maintained for a relatively long period under an elevated temperature.

Another objective is to provide a rinse-off composition, typically a skin cleansing composition, particularly for facial and/or body skin, including a thiopyridinone compound which makes it possible to reduce pigment spots.

The present invention meets these expectations.

The composition according to the invention is a stable cleansing composition, typically a face and body cleansing gel, containing a thiopyridinone compound. It helps reduce pigment spots.

Thus, the subject of the present invention is a composition, preferably cosmetic, comprising:

- at least one thiopyridinone compound chosen from the compounds of formula (I) below, the tautomers of formula (I') below, their salts, their solvates such as their hydrates, their optical isomers, their racemates and their mixtures:

in which,

- R ₁ denotes a radical chosen from a) a hydrogen atom, and b) a linear C ₁ -C ₁₀ or branched C ₃ -C ₁₀ saturated alkyl group optionally substituted by one or more groups, which may be the same or different, chosen from i) -OR ₃ , and ii) -SR ₃ , and

- R ₂ denotes a radical chosen from a) a hydrogen atom, b) a linear C ₁ -C ₁₂ or branched C ₃ -C ₁₂ or cyclic C ₃ -C ₈ saturated hydrocarbon group optionally substituted by one or more groups, which may be the same or different, chosen from i) -OR ₃ , ii) -SR ₃ , iii) -C(O)-OR ₃ , and iv) a C ₅ -C ₁₂ aryl group, optionally substituted by one or more hydroxyls and/or by one or more C ₁ -C _{8 alkoxy radicals,} and c) a C ₅ -C ₁₂ aryl group, optionally substituted by one or more hydroxyls and/or by one or more C ₁ -C ₈ alkoxy radicals and

- R ₃ denotes a radical chosen from a) a hydrogen atom, and b) a linear C ₁ -C ₁₀ or branched C ₃ -C ₁₀ saturated alkyl group;

- at least niacinamide or one of its derivatives;

- at least gluconolactone;

- a surfactant system comprising (i) at least one N-acyl-amino surfactant and (ii) at least one amphoteric surfactant; and

- at least one non-associative crosslinked copolymer of acrylic acid and/or methacrylic acid, or one of their esters.

The invention also relates to a method for cleaning the skin, preferably the skin of the face, neck or body, comprising (i) applying a composition according to the invention to the skin, then (ii) rinsing this composition.

By “the skin” is meant the entire skin of the body, and the scalp and preferably, the skin of the face, décolleté, neck, arms and forearms, hands or even more preferably, the skin of the face (in particular the forehead, nose, cheeks, lips, chin), décolleté and neck.

By "intended for topical administration" is meant an application to the surface of the skin in question.

The composition according to the invention is now described in detail below.

Thiopyridinone compound

The composition according to the present invention comprises at least one thiopyridinone compound of formula (I) or (I'), one of their salts, one of their solvates such as their hydrates, one of their optical isomers, one of their racemates and/or their mixtures.

Two distinct thiopyridinone compounds of formula (I) or (I') may be used in combination. Thus, a single thiopyridinone compound of formula (I) or (I') or a combination of different thiopyridinone compounds of formula (I) or (I') may be used.

The thiopyridinone compound(s) are chosen from the compounds of formula (I) below, the tautomers of formula (I') below, their salts, their solvates such as their hydrates, their optical isomers, their racemates and their mixtures:

in which:

R ₁ denotes a radical chosen from:

a) a hydrogen atom, and

b) a saturated linear C ₁ -C ₁₀ or branched C ₃ -C ₁₀ alkyl group optionally substituted by one or more groups, which may be the same or different, chosen from

i) -OR ₃ , and

ii) -SR ₃ , and

R ₂ denotes a radical chosen from:

a) a hydrogen atom,

(b) a linear C ₁ -C ₁₂ or branched C ₃ -C ₁₂ or cyclic C ₃ -C ₈ saturated hydrocarbon group, optionally substituted by one or more groups, which may be the same or different, chosen from

i) -OR ₃ ,

ii) -SR ₃ ,

iii) -C(O)-OR ₃ , and

iv) a C ₅ -C ₁₂ aryl group, optionally substituted by one or more hydroxyls and/or by one or more C ₁ -C ₈ alkoxy radicals and

c) a C ₅ -C ₁₂ aryl group, optionally substituted by one or more hydroxyls and/or by one or more C ₁ -C ₈ alkoxy radicals, and

R ₃ denotes a radical chosen from:

a) a hydrogen atom, and

b) a linear C ₁ -C ₁₀ or branched C ₃ -C ₁₀ saturated alkyl group.

Hereinafter, for the purposes of the present invention and unless otherwise indicated:

- a "saturated, linear C ₁ -C ₁₂ or branched C ₃ -C ₁₂ " hydrocarbon group is equivalent to a "linear (C ₁ -C ₁₂ ) or branched (C ₃ -C ₁₂ ) alkyl group" which corresponds to a saturated, linear C ₁ -C ₁₂ or branched C ₃ -C ₁₂ hydrocarbon group, preferably a linear C ₁ -C ₁₀ or branched C ₃ -C ₁₀ hydrocarbon group, and more preferably a linear C ₁ -C ₆ or branched C ₃ -C ₆ hydrocarbon group; preferably, the linear or branched groups may be chosen from methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl groups; more preferably, the saturated, linear or branched alkyl groups may be chosen from methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, pentyl, hexyl, heptyl and octyl groups, such as methyl, ethyl, n-pentyl, n-nonyl, isobutyl;

- a saturated hydrocarbon group “cyclic in C₃-C₈» is a group mono or bicyclic cycloalkyl containing from 3 to 8 carbon atoms, and in particular is a monocyclic cycloalkyl group of C₅to C₇such as a cyclohexyl group,

- an “alkoxy radical” is an alkyloxy radical for which the alkyl radical is a linear or branched C ₁ -C ₁₆ hydrocarbon radical, and preferably a C ₁ -C ₈ hydrocarbon radical;

- when the alkoxy group is optionally substituted, this implies that the alkyl group is optionally substituted as defined above;

- an “aryl” group represents a carbon-based group, monocyclic or bicyclic, fused or not, comprising from 5 to 12 carbon atoms, preferably from 6 to 10 carbon atoms, and in which at least one cycle is aromatic; preferably, the aryl radical is a phenyl, biphenyl, naphthyl group, more preferably a phenyl group.

Salts of compounds of formula (I), (I'), (II) or (II') as defined below include conventional non-toxic salts of said compounds, such as those formed from an organic or inorganic acid or an organic or inorganic base.

As salts of the compounds of formula (I), (I’), (II) or (II’), mention may be made of:

- the salts obtained by addition of the compound of formula (I) or (II) to:

- a mineral base, such as sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide, magnesium hydroxide, lithium hydroxide, sodium, potassium or calcium carbonate or hydrogen carbonate, for example; or

- an organic base such as a primary, secondary or tertiary alkylamine, for example triethylamine or butylamine. This primary, secondary or tertiary alkylamine may comprise one or more nitrogen and/or oxygen atoms and may thus comprise, for example, one or more alcohol functions. Mention may be made in particular of 2-amino-2-methylpropanol, ethanolamine, triethanolamine, 2-dimethylaminopropanol, 2-amino-2-(hydroxymethyl)-1,3-propanediol and 3-(dimethylamino)propylamine.

Mention may also be made of amino acid salts, for example lysine, arginine, guanidine, glutamic acid and aspartic acid. Advantageously, the salts of the compounds of formula (I) or (II) (when they comprise a carboxy group) may be chosen from alkali or alkaline earth metal salts such as sodium, potassium, calcium or magnesium salts and ammonium salts.

An “organic or inorganic acid salt” is more particularly chosen from salts chosen from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H ₂ SO ₄ , iv) alkylsulfonic acids: Alk-S(O) ₂ OH such as methanesulfonic acid and ethanesulfonic acid; v) arylsulfonic acids: Ar-S(O) ₂ OH such as benzenesulfonic acid and toluenesulfonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid; x) alkoxysulfinic acids: Alk-OS(O)OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii) phosphoric acid H ₃ PO ₄ ; xiii) acetic acid CH ₃ C(O)OH ; xiv) triflic acid CF ₃ SO ₃ H ; and xv) tetrafluoroboric acid HBF ₄ .

Acceptable solvates of the compounds described include conventional solvates such as those formed during the preparation of said compounds due to the presence of solvents. Examples include solvates due to the presence of water or linear or branched alcohols, such as ethanol or isopropanol.

Optical isomers are in particular enantiomers and diastereoisomers.

Compound (I') is the tautomeric form of compound (I) when a tautomeric equilibrium exists according to the following scheme:

According to one embodiment of the present invention, R ₁ represents a hydrogen atom.

According to one embodiment of the present invention, R ₁ of formula (I) and (I') represents a linear (C ₁ -C ₁₀ ) or branched (C ₃ -C ₁₀ ) alkyl group, in particular a linear (C ₁ -C ₆ ) or branched (C ₃ -C ₆ ) alkyl group, such as methyl, ethyl, n-pentyl, n-nonyl, isobutyl, more preferably, ethyl. In particular, said alkyl group of R ₁ is not substituted.

According to one embodiment of the present invention, R ₂ represents a hydrogen atom.

According to one embodiment of the present invention, R ₂ represents a linear (C ₁ -C ₁₀ ) or branched (C ₃ -C _{10 )} alkyl group, in particular a linear (C ₁ -C ₆ ) or branched (C ₃ -C ₆ ) alkyl group, such as methyl, ethyl, n-pentyl, n-nonyl, isobutyl, more preferably methyl or ethyl; said alkyl group of R ₂ not being substituted.

According to one embodiment of the present invention, R ₂ of formula (I) and (I') represents a linear (C ₁ -C ₁₀ ) or branched (C ₃ -C ₁₀ ) alkyl group, in particular a linear (C ₁ -C ₆ ) or branched (C ₃ -C ₆ ) alkyl group, such as methyl, ethyl, n-pentyl, n-nonyl, isobutyl, more preferably methyl or ethyl; said alkyl group being substituted by one or more groups selected from i), ii), iii) and iv) as defined above. Preferably, said alkyl group being substituted by one or two groups selected from i), ii) and iii), more preferably by one or two groups selected from i) and iii), better substituted by a group iii) such as carboxy.

Another variant for the radical R ₂ is that said alkyl group is substituted by a group iv) in particular substituted by a phenyl group.

According to another embodiment of the present invention, R ₂ represents a cycloalkyl group (C ₃ -C ₈ ), preferably a cycloalkyl group (C ₅ -C ₇ ) such as cyclohexyl.

According to another embodiment of the present invention, R ₂ represents a C ₅ -C ₁₂ aryl group optionally substituted by one or more hydroxyls and/or by one or more C ₁ -C ₈ alkoxy radicals, preferably a phenyl group in particular unsubstituted.

According to one embodiment, R ₃ represents a hydrogen atom.

According to another embodiment, R ₃ represents a saturated, linear C ₁ -C ₁₀ or branched C ₃ -C ₁₀ alkyl group; in particular a linear (C ₁ -C ₆ ) or branched (C ₃ -C ₆ ) alkyl group, preferably a (C ₁ -C ₄ ) alkyl group such as the methyl group.

Preferably, the compounds of formula (I) and the tautomer (I') or their salts, their optical isomers, racemates, and/or solvates such as their hydrates and their derivatives, alone or in mixture, have the following meanings:

R ₁ denotes a radical chosen from:

a) a hydrogen atom, and

b) a linear C ₁ -C ₆ or branched C ₃ -C ₆ saturated alkyl group optionally substituted by one or more groups, which may be the same or different, chosen from:

i) -OR ₃ , and

ii) -SR ₃ ,

preferably optionally substituted by one or more groups i);

R ₂ denotes a radical chosen from:

a) a hydrogen atom;

b) a linear saturated hydrocarbon group in C₁-C₁₀or branched in C₃-C₁₀or cyclic in C₃-C₈such than in C₅-C₆optionally substituted by one or more groups, which may be the same or different, chosen from:

i) -OR ₃ ,

ii) -SR ₃ ,

iii) -C(O)-OR ₃ , and

iv) a phenyl group optionally substituted by one or more hydroxyls and/or by one or more C ₁ -C ₄ alkoxy radicals such as methoxy,

preferably substituted by one or more groups selected from i) and iii), preferably iii) such as carboxy; and

R ₃ denotes a radical chosen from:

a) a hydrogen atom, and

b) a linear C ₁ -C ₆ or branched C ₃ -C _{6 saturated alkyl group.}

Preferably, the compounds of formula (I) and the tautomer (I') or their salts, their optical isomers, racemates, and/or their solvates such as their hydrates, alone or in mixture, have the following meanings:

R ₁ denotes a radical chosen from:

a) a hydrogen atom, and

b) a linear C ₁ -C ₄ or branched C ₃ -C ₄ saturated alkyl group optionally substituted by one or more groups, which may be the same or different, selected from i) -OR _3, more preferably unsubstituted;

R ₂ denotes a radical chosen from:

(a) a hydrogen atom; and

b) a linear saturated hydrocarbon group in C₁-C₁₀or branched in C₃-C₁₀or cyclic in C₃-C₈as in C₅-C₆, optionally substituted by one or more groups, which may be the same or different, chosen from:

i) -OR ₃ ,

iii) -C(O)-OR ₃ ,

iv) a C ₅ -C ₁₂ aryl group, optionally substituted by one or more hydroxyls and/or by one or more C ₁ -C ₄ alkoxy radicals; and

R ₃ denotes a radical chosen from:

a) a hydrogen atom, and

b) a linear C ₁ -C ₄ or branched C ₃ -C ₄ saturated alkyl group such as methyl or ethyl.

Preferably, the compounds of formula (I) and the tautomer (I') or their salts, their optical isomers, racemates, and/or solvates such as hydrates and their derivatives, alone or in mixture, have the following meanings:

R ₁ is a hydrogen atom; and

R ₂ denotes a radical chosen from:

a) a hydrogen atom, and

b) a saturated hydrocarbon group, linear C ₁ -C ₅ or branched C ₃ -C ₅ or cyclic C ₃ -C ₈ such that C ₅ -C ₆ may be the same or different, chosen from v) -C(O)-OR ₃ , preferably substituted by a group iii) -C(O)-OR ₃ ; R ₂ is more preferably still a saturated hydrocarbon group, linear C ₁ -C ₄ or branched C ₃ -C ₄ substituted by a group iii) -C(O)-OR ₃ ; and

R ₃ denotes a radical chosen from:

a) a hydrogen atom, and

b) a linear C ₁ -C ₄ or branched C ₃ -C ₄ saturated alkyl group such as methyl or ethyl.

According to another preferred embodiment, the compounds of formula (I) and the tautomer (I') are selected from the compounds of formula (II) below and also their tautomers of formula (II') below, their salts, their solvates and their optical isomers, and their racemates, alone or as a mixture:

(II) (II’)

In formula (II) and (II'), R ₁ and R ₃ have the same meaning as R ₁ and R ₃ for the compounds of formula (I) and (I'), and X denotes an alkylene radical -(CH ₂ ) _n - with n being an integer ranging inclusively from 1 to 10, preferably from 1 to 6, more preferably from 1 to 4, such as 1; preferably, R ₃ represents a hydrogen atom.

Among the compounds of formula (I), the following compounds are preferably used, and their tautomer (I') or their salts, their optical isomers, racemates, and/or solvates such as hydrates and their derivatives, alone or in mixture:

No. Structure Chemical name CAS No. 1 N-ethyl-2-thioxo-1,2-dihydropyridine-3-carboxamide 91859-75-5 2 N-methyl-2-thioxo-1,2-dihydropyridine-3-carboxamide 91859-74-4 3 N-octyl-2-thioxo-1,2-dihydropyridine-3-carboxamide 91859-77-7 4 N-benzyl-2-thioxo-1,2-dihydropyridine-3-carboxamide 91859-79-9 5 N-phenyl-2-thioxo-1,2-dihydropyridine-3-carboxamide 104857-16-1 6 N-cyclohexyl-2-thioxo-1,2-dihydropyridine-3-carboxamide 91859-78-8 7 N-[2-(4-methoxyphenyl)ethyl]-2-thioxo-1,2-dihydropyridine-3-carboxamide 923682-88-6 8 N-(2-methylpropyl)-2-thioxo-1,2-dihydropyridine-3-carboxamide 1100027-79-9 9 N-pentyl-2-thioxo-1,2-dihydropyridine-3-carboxamide 330667-57-7 10 N-nonyl-2-thioxo-1,2-dihydropyridine-3-carboxamide 1031149-44-6 11 N-(2-hydroxyethyl)-2-thioxo-1,2-dihydropyridine-3-carboxamide 12 N,N-diethyl 2-mercaptonicotinamide 13 N-ethyl-N-(2-hydroxyethyl)-2-thioxo-1,2-dihydropyridine-3-carboxamide 14 N-(2,3-dihydroxypropyl)-2-thioxo-1,2-dihydropyridine-3-carboxamide 15 N-(1,3-dihydroxypropan-2-yl)-2-thioxo-1,2-dihydropyridine-3-carboxamide 16 N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]ethyl alaninate 17 N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]phenyl ethyl alaninate 18 N-methyl-N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]ethyl glycinate 19 N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]ethyl glycinate 20 N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]glycine 21 N-methyl-N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]glycine 22 N,N-bis(2-hydroxyethyl)-2-thioxo-1,2-dihydropyridine-3-carboxamide 23 N-(3-methoxypropyl)-2-thioxo-1,2-dihydropyridine-3-carboxamide 24 N-butyl-2-thioxo-1,2-dihydropyridine-3-carboxamide

Among these compounds, the following compounds are more particularly preferred:

No. Structure Chemical name CAS No. 1 N-ethyl-2-thioxo-1,2-dihydropyridine-3-carboxamide 91859-75-5 2 N-methyl-2-thioxo-1,2-dihydropyridine-3-carboxamide 91859-74-4 4 N-benzyl-2-thioxo-1,2-dihydropyridine-3-carboxamide 91859-79-9 6 N-cyclohexyl-2-thioxo-1,2-dihydropyridine-3-carboxamide 91859-78-8 7 N-[2-(4-methoxyphenyl)ethyl]-2-thioxo-1,2-dihydropyridine-3-carboxamide 923682-88-6 9 N-pentyl-2-thioxo-1,2-dihydropyridine-3-carboxamide 330667-57-7 11 N-(2-hydroxyethyl)-2-thioxo-1,2-dihydropyridine-3-carboxamide 12 N,N-diethyl 2-mercaptonicotinamide 14 N-(2,3-dihydroxypropyl)-2-thioxo-1,2-dihydropyridine-3-carboxamide 15 N-(1,3-dihydroxypropan-2-yl)-2-thioxo-1,2-dihydropyridine-3-carboxamide 16 N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]ethyl alaninate 17 N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]phenyl ethyl alaninate 18 N-methyl-N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]ethyl glycinate 19 N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]ethyl glycinate 20 N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]glycine 21 N-methyl-N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]glycine

More preferably, among these compounds, the following compounds are more particularly preferred:

No. Structure Chemical name CAS No. 1 N-ethyl-2-thioxo-1,2-dihydropyridine-3-carboxamide 91859-75-5 9 N-pentyl-2-thioxo-1,2-dihydropyridine-3-carboxamide 330667-57-7 16 N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]ethyl alaninate 18 N-methyl-N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]ethyl glycinate 19 N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]ethyl glycinate 20 N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]glycine 21 N-methyl-N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]glycine

Even more preferably, among these compounds, the following compounds are more particularly preferred:

No. Structure Chemical name CAS No. 18 N-methyl-N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]ethyl glycinate 19 N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]ethyl glycinate 20 N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]glycine 21 N-methyl-N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]glycine

In a most preferred embodiment, the compound according to the present invention is as follows:

20 N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]glycine

All of the above compounds can be obtained by a chemical process known to those skilled in the art, from commercially available reagents.

The thiopyridinone compound may be prepared according to the process described, for example, in EP-A-3390363 or WO 2017/102349, which is incorporated herein by reference.

The thiopyridinone compound may be an active ingredient or compound in cosmetic or dermatological products. The term "active" ingredient or compound as used herein means an ingredient or compound that has an active cosmetic or dermatological property.

Preferably, the amount of the thiopyridinone compound(s) of formula (I) or (I') in the composition according to the present invention is at least 0.01% by weight, preferably at least 0.03% by weight, and more preferably at least 0.04% by weight relative to the total weight of the composition.

Preferably, the amount of the thiopyridinone compound(s) of formula (I) or (I') in the composition according to the present invention is less than 5% by weight, preferably less than 3% by weight, and more preferably less than 1% by weight relative to the total weight of the composition.

Preferably, the amount of the thiopyridinone compound(s) of formula (I) or (I') in the composition according to the present invention is between 0.01% and 1% by weight, preferably between 0.03% and 0.8% by weight, more preferably between 0.04% and 0.3% by weight relative to the total weight of the composition.

Niacinamide or its derivatives

The composition according to the invention comprises niacinamide or one of its derivatives.

For the purposes of the invention, niacinamide has the following structure:

By "niacinamide derivative" is preferably meant a compound in which the amide group of niacinamide is secondary or tertiary, preferably substituted by one or two alkyl groups independently chosen from C1-C4 alkyl groups and/or in which at least one hydrogen atom of the pyridine group is replaced by a C1-C4 alkyl group.

Preferably, the compound selected from niacinamide and its derivatives is niacinamide.

For example, we can cite the product Niacinamide PC® marketed by the company DSM NUTRITIONAL PRODUCTS.

Preferably, the composition comprises from 0.1% to 2.5% by weight of the compound chosen from niacinamide and its derivatives relative to the total weight of the composition, preferably from 0.2% to 2% by weight, preferentially from 0.3% to 1.5%, more preferentially from 0.4% to 1% by weight.

Preferably, the weight ratio of the amount of compound chosen from niacinamide and its derivatives to the amount of thiopyridinone compound, in the composition according to the present invention, is at least equal to 1.6, preferably at least equal to 5, and more preferably at least equal to 8.

Preferably, the weight ratio of the amount of compound chosen from niacinamide and its derivatives to the amount of thiopyridinone compound, in the composition according to the present invention, is between 1.6 and 20, preferably between 5 and 15, and more preferably between 9 and 12.

Gluconolactone

Gluconolactone is a polyhydroxy acid (or PHA).

Preferably, the gluconolactone is delta-gluconolactone (or glucono-delta-lactone), of the following formula:

For example, we can cite the product Glucono-delta-lactone F5010 Personal Care marketed by the company Jungbunzlauer.

Preferably, the composition comprises from 0.1% to 5% by weight of gluconolactone relative to the total weight of the composition, preferably from 0.3% to 2% by weight, preferably from 0.6% to 1.5% by weight, more preferably from 0.9% to 1.1% by weight.

Surfactant system

The composition according to the invention contains a surfactant system which gives the composition its foaming character. Said surfactant system comprises (i) at least one N-acyl-amino surfactant and (ii) at least one amphoteric surfactant.

Preferably, the surfactant system is present in the composition in an amount ranging from 1% to 30% by weight, preferably from 5% to 25% by weight, preferably from 7% to 20% by weight relative to the total weight of the composition.

Foaming surfactants are detergents and differ from emulsifiers in their HLB (Hydrophilic-Lipophilic Balance) value, HLB being the ratio of the hydrophilic to the lipophilic part of the molecule. The term "HLB" is well known to those skilled in the art and is described, for example, in "The HLB system. A time-saving guide to Emulsifier Selection" (published by ICI Americas Inc., 1984). For emulsifiers, the HLB generally ranges from 3 to 8 for the preparation of W/O emulsions and from 8 to 18 for the preparation of O/W emulsions, whereas foaming surfactants generally have an HLB greater than 20.

N-acyl amino surfactant

The N-acyl amino surfactant is preferably chosen from glycine derivatives (glycinates).

The N-acyl amino surfactant is preferably sodium N-cocoyl glycinate, such as that marketed under the name Amilite GCS-12K®, or potassium N-cocoyl glycinate, such as that marketed under the name Amilite GCK 12H® by the company Ajinomoto.

Preferably, the N-acyl amino surfactant is sodium N-cocoyl glycinate.

The N-acyl amino surfactant is preferably present in the composition in an amount ranging from 0.8 to 15% by weight, in particular from 1 to 10% by weight, and more particularly from 1.5 to 5% by weight relative to the total weight of the composition.

Amphoteric surfactant

The amphoteric surfactant is preferably chosen from betaines, alkyl betaines, N-alkylamidobetaines and their derivatives.

Betaines that may be mentioned include alkyl betaines, such as, for example, coco betaine, such as the product sold under the name Dehyton AB-30® by the company Cognis, lauryl betaine, such as the product sold under the name Genagen KB® by the company Clariant, oxyethylenated lauryl betaine (10 EO), such as the product sold under the name Lauryl Ether (10 EO) Betaine® by the company Shin Nihon Rica, or oxyethylenated stearyl betaine (10 EO), such as the product sold under the name Stearyl Ether (10 EO) Betaine® by the company Shin Nihon Rica.

Among the N-alkylamidobetaines and their derivatives, we can cite, for example, cocamidopropyl betaine, such as that marketed under the name Lebon 2000 HG® by the company Sanyo or under the name Empigen BB® by the company Albright & Wilson, or lauramidopropyl betaine, such as that marketed under the name Rewoteric AMB12P® by the company Witco.

Preferably, the amphoteric surfactant is selected from coco betaine, lauryl betaine, oxyethylenated lauryl betaine (10 EO), oxyethylenated stearyl betaine (10 EO), cocamidopropyl betaine and mixtures thereof, and more preferably is selected from lauryl betaine, coco betaine and mixtures thereof and, even more preferably, coco betaine.

The amphoteric surfactant is preferably present in the composition according to the present invention in an amount ranging from 1% to 20% by weight, in particular from 2% to 15% by weight, and more particularly from 3 to 10% by weight relative to the total weight of the composition.

According to a particular embodiment, the weight ratio between the N-acyl amino surfactant and the amphoteric surfactant varies from 1:2 to 2:1 and preferably between 0.5 and 1.7.

Non-associative crosslinked copolymer of acrylic acid and/or methacrylic acid

The composition according to the invention comprises at least one non-associative crosslinked copolymer of acrylic acid and/or methacrylic acid, or one of their esters.

For the purposes of the present invention, the term "non-associative polymer" means that the polymer does not have the behavior of an associative polymer, that is to say a hydrophilic polymer comprising more particularly at least one hydrophilic region and at least one hydrophobic region, which is capable, in an aqueous medium, of associating with each other or with other molecules.

According to a particular embodiment, said non-associative crosslinked copolymer of acrylic acid and/or methacrylic acid is capable of forming a microgel.

According to the present invention, a microgel is a gel in which at least 90%, preferably 95%, more preferably all of the gel is in the form of particles.

According to one embodiment, the crosslinked copolymer may be in the form of a dispersion in water. The number-average size of the copolymer particles in the dispersion is generally between 10 and 500 nm, for example from 20 to 200 nm and again for example from 50 to 150 nm.

The non-associative crosslinked copolymer of acrylic acid and/or methacrylic acid, and optionally one of their esters, acts as a thickening polymer and also contributes to the composition's ability to deposit additional ingredients when present, even after rinsing.

The copolymers are partially or fully crosslinked with at least one standard crosslinking agent. The crosslinking agent may be selected, for example, from polyunsaturated compounds, such as polyethylenically unsaturated compounds. For example, these compounds may be selected from sucrose polyalkenyl ethers, polyol polyalkenyl ethers, diallyl phthalates, divinylbenzene, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane methylenebisacrylamide tri(meth)acrylate, diallyl itaconate, diallyl fumarate, diallyl maleate, zinc (meth)acrylate, castor oil derivatives, and polyol derivatives made from unsaturated carboxylic acids.

For the purposes of the present invention, the non-associative crosslinked copolymer of acrylic acid and/or methacrylic acid means that the copolymer comprises at least one acrylic acid unit or one methacylic acid unit or a mixture thereof. The copolymer may comprise other units such as units formed by an ester of acrylic acid or methacrylic acid, preferably acrylic, comprising less than 6 carbon atoms, i.e. a C1-C4 alkyl acrylate group chosen from methyl acrylate, ethyl acrylate and butyl acrylate, hereinafter referred to as "simple ester".

According to a particular embodiment, a non-associative crosslinked copolymer according to the present invention comprises at least one acrylic acid unit.

According to another embodiment, a non-associative crosslinked copolymer according to the present invention comprises at least one methacrylic acid unit.

According to another embodiment, a non-associative crosslinked copolymer according to the present invention comprises at least one acrylic acid unit and at least one methacrylic acid unit.

Examples include crosslinked copolymers of vinyl neodecanoate and one or other monomers of acrylic acid, methacrylic acid or one of their simple esters crosslinked with an allyl ether of trimethylolpropane or pentaerythritol, such as the product sold under the trade name ACULYN 38® (INCI name: ACRYLATES/VINYL NEODECANOATE CROSSPOLYMER) sold by THE DOW CHEMICAL COMPANY.

Other examples of such non-associative crosslinked copolymers of acrylic acid and/or methacrylic acid include:

(1) homopolymers of acrylic acid crosslinked by a pentaerythritol allyl ether, a sucrose allyl ether or a propylene allyl ether such as carbomer sold under the trade name CARBOPOL® by the company LUBRIZOL,

(2) non-associative crosslinked copolymers of acrylic acid and/or methacrylic acid and its esters. Examples of such non-associative crosslinked copolymers of acrylic acid and/or methacrylic acid and its esters include:

i) Crosslinked copolymers of acrylic acid and/or methacrylic acid comprising less than 6 carbon atoms and more particularly in the form of a 30% aqueous copolymer dispersion sold under the trade name ACULYN 33® by the company DOW CHEMICAL COMPANY and having the INCI name: ACRYLATES COPOLYMER,

ii) Crosslinked copolymers comprising at least one methacrylic acid unit and at least one C1-C4 alkyl acrylate unit. These copolymers are described for example in patent application No. WO 01/76552. As used herein, crosslinked copolymer comprising at least one methacrylic acid unit and at least one C1-C4 alkyl acrylate unit means a crosslinked copolymer comprising at least one methacrylic acid unit and at least one alkyl acrylate unit, wherein the alkyl acrylate unit is selected from C1-C4 alkyl acrylates.

In the crosslinked copolymers described herein, the methacrylic acid unit may be present, for example, in an amount ranging from 20% to 80% by weight, such as from 25 to 70% by weight, and even more preferably from 35 to 60% by weight relative to the total weight of the copolymer.

In the crosslinked copolymer described herein, the alkyl acrylate unit may be present, for example, in an amount ranging from 15% to 80% by weight, better still from 25% to 75% by weight and even better still from 40% to 65% by weight relative to the total weight of the copolymer. The alkyl acrylate unit may be chosen, for example, from methyl acrylate, ethyl acrylate and butyl acrylate. In one embodiment, the alkyl acrylate unit is ethyl acrylate.

For example, crosslinked copolymers comprising at least one methacrylic acid unit and at least one ethyl acrylate unit can be used, for example in the form of a 30% aqueous dispersion manufactured and sold under the name CARBOPOL AQUA SF-1® by the company NOVEON.

Other examples of such non-associative crosslinked copolymers of acrylic acid and/or methacrylic acid include:

(3) associative anionic crosslinked polymers of acrylic acid and/or methacrylic acid and/or their esters and more particularly those consisting of 95 to 60% by weight of acrylic acid (hydrophilic unit), 4 to 40% by weight of C10-C30 alkyl acrylate (hydrophobic unit), and 0 to 6% by weight of crosslinking polymerizable monomer, or alternatively those consisting of 98 to 96% by weight of acrylic acid (hydrophilic unit), 1 to 4% by weight of C10-C30 alkyl acrylate (hydrophobic unit) and 0.1 to 0.6% by weight of crosslinking polymerizable monomer such as those described above.

Among the above polymers, we can cite the products marketed by the company GOODRICH under the trade names PEMULEN TR1®, PEMULEN TR2®, CARBOPOL 1382®, and even more preferably PEMULEN TR1®, and the product marketed by the company S.E.P.P.I.C. under the name COATEX SX®, and bearing the INCI name: ACRYLATES/C10-C30 ALKYL ACRYLATE CROSSPOLYMER.

Mention may also be made of copolymers comprising among their monomers an α,β-monoethylenically unsaturated carboxylic acid and an α,β-monoethylenically unsaturated carboxylic acid ester and an oxyalkylenated fatty alcohol. Preferably, these compounds also comprise, as monomer, an α,β-monoethylenically unsaturated carboxylic acid ester and a C1-C4 alcohol. As an example of this type of compound, mention may be made of ACULYN 22® marketed by THE DOW CHEMICAL COMPANY which is an oxyalkylenated stearyl methacrylate/ethyl acrylate/methacrylic acid terpolymer bearing the INCI name ACRYLATES/STEARETH-20 METHACRYLATE COPOLYMER.

We can also cite crosslinked copolymers of acrylic acid/vinyl isodecanoate such as those sold under the trade name STABYLEN 30 ® (INCI name: ACRYLATES/VINYL ISODECANOATE CROSSPOLYMER) marketed by the company

SIGMA 3V.

Preferably, the non-associative crosslinked copolymer of acrylic acid and/or methacrylic acid, and optionally one of their esters, is chosen from:

- a crosslinked copolymer of acrylic acid and/or methacrylic acid and an ester thereof comprising less than 6 carbon atoms,

- a crosslinked copolymer comprising at least one methacrylic unit and at least one C1-C4 alkyl acrylate unit, for example an ethyl acrylate unit,

- a crosslinked copolymer of vinyl neodecanoate and one or more monomers of acrylic acid, methacrylic acid or one of their simple esters crosslinked by an allyl ether of trimethylolpropane or pentaerythritol, and

- their mixtures.

The non-associative crosslinked copolymer of acrylic acid and/or methacrylic acid, and optionally its esters, is preferably present in the composition according to the present invention in an active material content greater than or equal to 0.3% by weight, more particularly greater than or equal to 0.5% by weight relative to the total weight of the composition, for example in a content ranging from 0.3% to 8% by weight, preferably from 0.5% to 5% by weight, preferably from 0.7% to 3% by weight relative to the total weight of the composition.

Additional surfactant

The composition according to the invention may comprise, in addition to the surfactant system comprising (i) at least one N-acyl-amino surfactant, and (ii) at least one amphoteric surfactant, an additional surfactant.

This additional surfactant can be chosen from anionic, amphoteric (or zwitterionic), non-ionic and cationic surfactants.

Preferably, the additional surfactant is non-ionic, preferably selected from alkylpolyglucosides (APG), oxyalkylenated glycerol esters, oxyalkylenated sugar esters, and mixtures thereof.

As APG, those containing an alkyl group comprising from 6 to 30 carbon atoms, preferably from 8 to 16 carbon atoms, and containing a glucoside group preferably comprising from 1.2 to 3 glucoside units are preferably used. The APGs may be chosen, for example, from decylglucosides (alkyl-C9/C11-polyglucoside (1.4)), such as the product sold under the name Mydol 10® by the company Kao Chemicals or the product sold under the name Plantacare 2000 UP® by the company Cognis; caprylyl/capryl glucoside, such as the product sold under the name Plantacare KE 3711® by the company Cognis; laurylglucoside, such as the product sold under the name Plantacare 1200 UP® by the company Cognis; cocoglucoside, such as the product sold under the name Plantacare 818 UP® by the company Cognis; caprylylglucoside, such as the product sold under the name Plantacare 810 UP® by the company Cognis; and mixtures thereof.

Oxyalkylenated glycerol esters include polyoxyethylenated derivatives of glycerol fatty acid esters and their hydrogenated derivatives.

These oxyalkylenated glycerol esters may be chosen, for example, from esters of glycerol and hydrogenated and oxyethylenated fatty acids such as PEG-200 hydrogenated glyceryl palmate, sold under the name Rewoderm LI-S 80 by the company Goldschmidt; oxyethylenated glycerol cocoates, such as PEG-7 glyceryl cocoate, sold under the name Tegosoft GC by the company Goldschmidt, or PEG-30 glyceryl cocoate sold under the name Rewoderm LI-63 by the company Goldschmidt; and mixtures thereof.

Oxyalkylenated sugar esters include polyethylene glycol ethers of fatty acids and sugars. These oxyalkylenated sugar esters may be selected from oxyethylenated glucose esters, such as PEG-120 methyl glucose dioleate, sold under the name Glucamate DOE 120 by Amerchol.

According to a preferred embodiment of the invention, the additional surfactant is an oxyalkylenated sugar ester which may be chosen in particular from oxyethylenated glucose esters, such as PEG-120 methyl glucose dioleate.

Antioxidant reducing agent

Preferably, the composition according to the invention also comprises at least one antioxidant reducing agent.

Preferably, the antioxidant reducing agent is chosen from sodium thiosulfate, sodium metabisulfite, thioglycolic acid, thiolactic acid, cysteine, cysteamine, homocysteine and mixtures thereof.

Preferably, the antioxidant reducing agent is sodium thiosulfate.

Preferably, the composition comprises from 0.01% to 3% by weight of antioxidant reducing agent relative to the total weight of the composition, preferably from 0.05% to 1% by weight, preferentially from 0.08% to 0.3% by weight.

Vitamin E and its derivatives

Preferably, the composition according to the invention also comprises vitamin E or one of its derivatives.

Vitamin E is a fat-soluble vitamin that comprises eight organic molecules, i.e. four tocopherols (alpha-tocopherol, beta-tocopherol, gamma-tocopherol and delta-tocopherol) and four tocotrienols (α-tocotrienol, β-tocotrienol γ-tocotrienol and δ-tocotrienol).

Preferably, the composition according to the invention comprises a vitamin E derivative, preferably tocopheryl acetate.

Preferably, the composition comprises from 0.01% to 3% by weight of vitamin E or one of its derivatives relative to the total weight of the composition, preferably from 0.05% to 1% by weight, preferentially from 0.08% to 0.5% by weight.

Preferably, the composition according to the invention comprises a mixture of sodium thiosulfate and tocopheryl acetate.

Physiologically acceptable environment

In addition to the compounds indicated above, the composition according to the invention comprises a physiologically acceptable medium.

By "physiologically acceptable medium" is meant a medium which is particularly suitable for the application of a composition of the invention to keratin materials, in particular the skin.

The physiologically acceptable medium is generally adapted to the nature of the support on which the composition is to be applied, as well as to the aspect in which the composition is to be packaged.

The cosmetic compositions of the invention may be in the form of a gel, particularly an aqueous gel, or in the form of an H/W emulsion.

The physiologically acceptable medium may include water and optionally one or more water-miscible solvent(s).

According to a preferred embodiment, the compositions of the invention comprise at least 20% by weight of water, in particular at least 40% by weight of water relative to the total weight of said composition.

Preferably, the composition according to the invention has a water content ranging from 20% to 95% by weight, even better from 40% to 90% by weight relative to the total weight of the composition.

A water suitable for the invention may be a floral water such as cornflower water and/or a mineral water such as VITTEL water, VICHY water or LA ROCHE POSAY water and/or a thermal water.

Among the water-miscible organics (at room temperature, i.e. 25°C), one or more cosmetically acceptable organic solvents may be mentioned, which may be alcohols, in particular monovalent alcohols such as ethanol, isopropyl alcohol, benzyl alcohol and phenylethyl alcohol; diols such as ethylene glycol, propylene glycol, propane-1,3-diol, butylene glycol and pentylene glycol; and ethers such as ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol monomethyl, monoethyl and monobutyl ethers, and butylene glycol monomethyl, monoethyl and monobutyl ethers, and glycerin.

The water-miscible organic solvent(s) may be present in a concentration of 0.01% to 30% by weight, preferably 0.1% to 20% by weight and more preferably 1% to 15% by weight, relative to the total weight of the composition.

The composition according to the invention may also comprise at least one fatty substance such as one or more oil(s).

According to one embodiment, the composition may comprise from 0.1% to 50% by weight of fatty substances, preferably oil(s), and preferably from 0.5% to 40% of fatty substances, preferably oil(s), by weight relative to the total weight of said composition.

Oil is any fatty substance in liquid form at room temperature (20-25°C) and atmospheric pressure. These oils can be of vegetable, mineral or synthetic origin.

• les huiles hydrocarbonées d'origine animale ;
• les huiles hydrocarbonées d’origine végétale ;
• les esters et les éthers de synthèse, notamment d'acides gras, comme les huiles de formules R1COOR2 et R1OR2 dans laquelle R1 représente le reste d’un acide gras comportant de 8 à 29 atomes de carbone, et R2 représente une chaîne hydrocarbonée, ramifiée ou non, contenant de 3 à 30 atomes de carbone ;
• les hydrocarbures linéaires ou ramifiés, d’origine minérale ou synthétique ;
• les alcools gras ayant de 8 à 26 atomes de carbone ;
• les huiles fluorées partiellement hydrocarbonées et/ou siliconées ;
• les huiles de silicone ;
• leurs mélanges.

As oils which can be used in the composition of the invention, we can cite for example:

• hydrocarbon oils of animal origin;
• hydrocarbon oils of vegetable origin;
• synthetic esters and ethers, in particular of fatty acids, such as oils of formulas R1COOR2 and R1OR2 in which R1 represents the residue of a fatty acid containing from 8 to 29 carbon atoms, and R2 represents a hydrocarbon chain, branched or not, containing from 3 to 30 carbon atoms;
• linear or branched hydrocarbons, of mineral or synthetic origin;
• fatty alcohols having 8 to 26 carbon atoms;
• partially hydrocarbon and/or silicone fluorinated oils;
• silicone oils;
• their mixtures.

In the list of oils cited above, hydrocarbon oil means any oil containing mainly carbon and hydrogen atoms, and possibly ester, ether, fluorine, carboxylic acid and/or alcohol groups.

The composition according to the invention may comprise at least one sequestrant.

Preferred sequestrants include salts of ethylenediaminedisuccinic acid, EDTA and its salts, and mixtures thereof.

Ethylenediaminedisuccinic acid is a compound of formula (III):

(III)

Preferably, the salt of ethylenediamine disuccinic acid is selected from alkali metal salts, such as potassium salts and sodium salts, ammonium salts, and amine salts. The alkali metal salts of ethylenediamine disuccinic acid are more particularly preferred.

Preferably, the salt of ethylenediamine disuccinic acid used according to the invention is trisodium ethylenediamine disuccinate.

Such a compound is, for example, that marketed under the name Natrlquest® E30 by the company Innospec Active Chemicals, or that marketed under the name Octaquest E30 ^® by the company Octel Performance Chemicals.

According to a particular embodiment, the salt of ethylenediaminedisuccinic acid can be introduced into the composition dissolved in water, in particular in a content ranging from 25% to 50% by weight, preferably from 35% to 40% by weight in water.

One such compound is, for example, the one marketed under the name Natrlquest® E30 by the company Innospec Active Chemicals, at 37% by weight in water.

Preferably, the composition comprises an EDTA salt, preferably disodium EDTA.

Preferably, the composition comprises trisodium ethylene diamine disuccinate and disodium EDTA.

The composition according to the invention may comprise at least one glycol, preferably caprylyl glycol.

Preferably, the composition according to the invention comprises from 0.1% to 2% by weight, preferably from 0.2% to 1.5% by weight of glycol(s) relative to the total weight of the composition.

In a particular embodiment of the invention, the composition according to the present invention may also comprise at least one pH correction agent (pH corrector).

Two or more pH correction agents can be used in combination. For example, a single type of pH correction agent or a combination of different types of pH correction agents can be used.

As a pH correction agent, at least one acidifying agent and/or at least one basifying agent (alkaline agent) can be used.

The acidifying agent may be a monovalent or polyvalent acid, such as divalent.

Acidifying agents may be, for example, mineral (inorganic) acids such as hydrochloric acid, sulfuric acid, phosphoric acid, or organic acids such as carboxylic acids, e.g. tartaric acid, citric acid and lactic acid, as well as sulfonic acids.

The basifying agent may be a monovalent or polyvalent base, such as divalent.

Basifying agents can be mineral (inorganic) or organic, or hybrid.

The basifying agent can be an organic or mineral base, for example sodium hydroxide.

Preferably, the composition according to the present invention has a pH at least equal to 4.5, preferably at least equal to 5. Preferably, the composition according to the present invention has a pH less than or equal to 7.0, preferably less than or equal to 6.5. Preferably, the composition according to the present invention has a pH ranging from 4.5 to 6.5, and more preferably from 5.4 to 6.0.

The pH of the composition means the pH of the aqueous phase of the composition according to the present invention.

It may be preferable that at least one buffer or buffering agent is also used, such as the pH correcting agent, in combination with the acidifying agent and/or the basifying agent, in order to stabilize the pH of the composition according to the present invention.

Any commonly known buffer can be used as a buffer. For example, salts of acids or bases, preferably salts of weak acids or weak bases, can be used. For example, sodium citrate or sodium lactate can be used as a buffer, if citric acid or lactic acid is used as the acidifying agent.

A cosmetic composition according to the invention may also further comprise any additive usually used in the field concerned, for example chosen from gums, resins, dispersing agents, polymers, antioxidant agents, essential oils, preservatives, perfumes, antiseptic agents, UV filters, cosmetic active ingredients and mixtures thereof.

It is within the routine operations of a person skilled in the art to adjust the nature and quantity of the additives present in the compositions in accordance with the invention, so that the desired cosmetic properties and stability properties thereof are not affected.

The composition according to the invention can be presented in all the galenic forms normally used in the cosmetic field.

It may be in particular in the form of an aqueous, hydroalcoholic, possibly gelled solution, a dispersion of the lotion type, possibly biphasic, an oil-in-water or water-in-oil or multiple emulsion, an aqueous gel, a dispersion of oils in an aqueous phase, in particular using spherules, these spherules being able to be polymeric particles or better, lipid vesicles of ionic and/or non-ionic type, or even in the form of a powder, a serum, a paste or a flexible stick or even a stick. It may be of solid, pasty, or more or less fluid liquid consistency. It may be applied to the skin in the form of an aerosol. It may also be in solid form, and for example in the form of a stick.

The composition according to the invention is typically suitable for topical application. Thus, the composition may comprise all the constituents usually employed in the topical application and administration envisaged.

The composition according to the invention may advantageously be in the form of an emulsion, in particular obtained by dispersion of an aqueous phase in a fatty phase (W/O) or of a fatty phase in an aqueous phase (O/W), of liquid or semi-liquid consistency of the milk type, or of soft, semi-solid or solid consistency of the cream or gel type, or even of multiple emulsion (W/O/W or O/W/O). These compositions are prepared according to the usual methods.

Preferably, the composition according to the invention is in the form of a gel, preferably an aqueous gel, preferably a cleansing gel.

The compositions according to the invention may be applied directly to the skin or, alternatively, to cosmetic supports of the occlusive or non-occlusive type, intended to be applied locally to the skin. As non-limiting examples of cosmetic supports, mention may in particular be made of a patch, a wipe, a roll-on or a pen.

Preferably, the composition is rinsed off after being applied to the skin.

Thus, the invention also relates to a method for cleaning the skin, preferably the skin of the face, neck or body, comprising (i) applying a composition according to the invention to the skin, then (ii) rinsing this composition.

The invention is now illustrated by the following examples. Unless otherwise stated, the quantities are given as a percentage by weight relative to the total weight of the composition (% w/w).

Example 1: Composition according to the invention

The following composition according to the invention was prepared by mixing the different ingredients:

Ingredient Quantity (% w/w) Water Qsp 100 Coco betaine (Amphitol 24B-2 from Kao) 18
(=5.4% ma) Sodium cocoyl glycinate (Amilite GCS-12K from Ajinomoto) 9
(=2.7% ma) Glycerin 7 Acrylates copolymer (30% by weight aqueous dispersion, Carbopol Aqua SF-1 Polymer from Lubrizol) 3
(=0.9% ma) Propanediol 3 PEG-120 methyl glucose dioleate 2.5 Gluconolactone 1 Capryloyl glycine 0.7 Capryloyl glycol 0.7 Niacinamide 0.5 Sodium hydroxide 0.31 Scent Qs Sodium thiosulfate 0.1 Tocopheryl acetate 0.1 Disodium EDTA 0.1 2-mercaptonicotinoyl glycine
(N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]glycine, i.e. compound No. 20 of formula (I)) 0.05 Pentylene glycol 0.01 Ceramide NP Qs Trisodium ethylene diamine disuccinate (Natrlquest® E30 from Innospec Active Chemicals) Qs Citric acid Qs

m.a. = active ingredient

This composition is stored for two months at 4°C or 45°C, then the niacinamide is measured and the presence of niacin is tested.

After two months of storage at 4°C or 45°C, the niacinamide levels are compliant and stable (0.5% measured for each case), and the niacin levels are below the limit of quantification (<10ppm).

Furthermore, the 2-mercaptonicotinoyl glycine dosages obtained after two months at 45°C are in accordance with the theoretical rates (i.e. within the limit of a maximum loss of 10%), and no degradation product is detected.

In conclusion, the composition according to the invention is stable at room temperature, and after two months at 4°C and 45°C.

Example 2: Clinical study of a composition according to the invention

The following composition according to the invention was prepared by mixing the different ingredients:

Ingredient Quantity (% w/w) Water Qsp 100 Red 33 0.00008 Coco betaine (Amphitol 24B-2 from Kao) 18
(=5.4% ma) Sodium cocoyl glycinate (Amilite GCS-12K from Ajinomoto) 9
(=2.7% ma) Glycerin 7 Acrylates copolymer (30% by weight aqueous dispersion, Carbopol Aqua SF-1 Polymer from Lubrizol) 3
(=0.9% ma) Propanediol 3 PEG-120 methyl glucose dioleate 2.5 Gluconolactone 1 Capryloyl glycine 0.7 Capryloyl glycol 0.7 Niacinamide 0.5 Sodium hydroxide 0.31 Scent Qs Sodium thiosulfate 0.1 Tocopheryl acetate 0.1 Disodium EDTA 0.1 2-mercaptonicotinoyl glycine
(N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]glycine, i.e. compound No. 20 of formula (I)) 0.05 Pentylene glycol 0.01 Ceramide NP Qs Trisodium ethylene diamine disuccinate (Natrlquest® E30 from Innospec Active Chemicals) Qs Citric acid Qs

m.a. = active ingredient

This composition has been evaluated for the reduction of pigment spots as follows:

49 Caucasian women aged 40 to 65 years and phototype I to IV took part in the study in South Africa. They presented pigmented spots on the face (actinic lentigo, senile lentigo and/or sunspots) with at least one defined and homogeneous size greater than or equal to 3 mm in diameter.

These women applied the composition twice a day (morning and evening) for 8 weeks, followed by a week of after-effect ( ^9th week without application). The evaluation is made using at T0, T5 weeks, T8 weeks and T9 weeks:

-clinical scoring by a dermatologist, using a 10-point scale (0=RAS to 9=severe);

-clinical scoring by a dermatologist, using the Skin Aging Atlas (Skin Aging Atlas, vol. 2 Asian Type (R. BAZIN, F. FLAMENT).

The results show that after 5 weeks and 8 weeks of application of the composition, with clinical scoring by dermatologist on a 10-point scale, a statistically significant improvement is observed in :

- “the visibility of brown spots” with respectively -23.1% and -36.3% variation; and

- “the contrast of an isolated pigment spot” with respectively -21.6% and -27.1% variation.

Assessment of persistence

a- At time D63, after one week of non-application of the composition (i.e. end of the ^9th week), the results show a statistically significant improvement compared to the initial level in:

- “the visibility of brown spots” with -37.1% variation; and

- “the contrast of an isolated pigment spot” with -27.1% variation.

b- No changes were observed between 63 days (end of the ^9th week) and 56 days (end of the ^8th week).

All of these results show that the effectiveness of the product on the “visibility of dark spots” and on the “contrast of an isolated pigment spot” lasts one week after the last application, and is maintained at a level of effectiveness comparable to that after 56 days of application.

Claims (23)

Composition, preferably cosmetic, comprising:
- at least one thiopyridinone compound chosen from the compounds of formula (I) below, the tautomers of formula (I') below, their salts, their solvates such as their hydrates, their optical isomers, their racemates and their mixtures:

in which:
- R ₁ denotes a radical chosen from a) a hydrogen atom, and b) a linear C ₁ -C ₁₀ or branched C ₃ -C ₁₀ saturated alkyl group optionally substituted by one or more groups, which may be the same or different, chosen from i) -OR ₃ , and ii) -SR ₃ , and
- R ₂ denotes a radical chosen from a) a hydrogen atom, b) a linear C ₁ -C ₁₂ or branched C ₃ -C ₁₂ or cyclic C ₃ -C ₈ saturated hydrocarbon group optionally substituted by one or more groups, which may be the same or different, chosen from i) -OR ₃ , ii) -SR ₃ , iii) -C(O)-OR ₃ , and iv) a C ₅ -C ₁₂ aryl group, optionally substituted by one or more hydroxyls and/or by one or more C ₁ -C _{8 alkoxy radicals,} and c) a C ₅ -C ₁₂ aryl group, optionally substituted by one or more hydroxyls and/or by one or more C ₁ -C ₈ alkoxy radicals and
- R ₃ denotes a radical chosen from a) a hydrogen atom, and b) a linear C ₁ -C ₁₀ or branched C ₃ -C ₁₀ saturated alkyl group;
- at least niacinamide or one of its derivatives;
- at least gluconolactone;
- a surfactant system comprising (i) at least one N-acyl-amino surfactant and (ii) at least one amphoteric surfactant; and
- at least one non-associative crosslinked copolymer of acrylic acid and/or methacrylic acid, or one of their esters. Composition according to claim 1, in which the compounds of formula (I) and the tautomer (I') or their salts, their optical isomers, racemates, and/or solvates such as hydrates and their derivatives, alone or in mixture, have the following meanings:
R ₁ is a hydrogen atom; and
R ₂ denotes a radical chosen from:
a) a hydrogen atom, and
b) a saturated hydrocarbon group, linear C ₁ -C ₅ or branched C ₃ -C ₅ or cyclic C ₃ -C ₈ such that C ₅ -C ₆ may be the same or different, chosen from v) -C(O)-OR ₃ , preferably substituted by a group iii) -C(O)-OR ₃ ; R ₂ is more preferably still a saturated hydrocarbon group, linear C ₁ -C ₄ or branched C ₃ -C ₄ substituted by a group iii) -C(O)-OR ₃ ; and
R ₃ denotes a radical chosen from:
a) a hydrogen atom, and
b) a linear C ₁ -C ₄ or branched C ₃ -C ₄ saturated alkyl group such as methyl or ethyl. Composition according to claim 1 or 2, in which the thiopyridinone compound is chosen from:
Composition according to one of the preceding claims, in which the thiopyridinone compound is the following: 20 N-[(2-thioxo-1,2-dihydropyridin-3-yl)carbonyl]glycine Composition according to one of the preceding claims, wherein the thiopyridinone compound is present in an amount of at least 0.01% by weight, preferably at least 0.03% by weight, and more preferably at least 0.04% by weight relative to the total weight of the composition; and/or in an amount of less than 5% by weight, preferably less than 3% by weight, and more preferably less than 1% by weight relative to the total weight of the composition; and/or in an amount of between 0.01% and 1% by weight, preferably between 0.03% and 0.8% by weight, more preferably between 0.04% and 0.3% by weight relative to the total weight of the composition. Composition according to one of the preceding claims, which comprises from 0.1% to 2.5% by weight of compound chosen from niacinamide and its derivatives relative to the total weight of composition, preferably from 0.2% to 2% by weight, preferentially from 0.3% to 1.5%, more preferentially from 0.4% to 1% by weight. Composition according to one of the preceding claims, in which the weight ratio of the quantity of compound chosen from niacinamide and its derivatives to the quantity of thiopyridinone compound is at least equal to 1.6, preferably at least equal to 5, and more preferably at least equal to 8, preferably between 1.6 and 20, preferably between 5 and 15, and more preferably between 9 and 12. Composition according to one of the preceding claims, which comprises from 0.1% to 5% by weight of gluconolactone relative to the total weight of composition, preferably from 0.3% to 2% by weight, preferentially from 0.6% to 1.5% by weight, more preferentially from 0.9% to 1.1% by weight. Composition according to one of the preceding claims, which comprises the surfactant system in an amount ranging from 1% to 30% by weight, preferably from 5% to 25% by weight, preferably from 7% to 20% by weight relative to the total weight of the composition. Composition according to one of the preceding claims, in which the N-acyl amino surfactant is chosen from sodium N-cocoyl glycinate and potassium N-cocoyl glycinate, preferably the N-acyl amino surfactant is sodium N-cocoyl glycinate. Composition according to one of the preceding claims, in which the N-acyl amino surfactant is present in an amount ranging from 0.8 to 15% by weight, in particular from 1 to 10% by weight, and more particularly from 1.5 to 5% by weight relative to the total weight of the composition. Composition according to one of the preceding claims, in which the amphoteric surfactant is chosen from betaines, alkyl betaines and N-alkylamidobetaines; preferably chosen from coco betaine, lauryl betaine, oxyethylenated lauryl betaine (10 EO), oxyethylenated stearyl betaine (10 EO), cocamidopropyl betaine and lauramidopropyl betaine; preferably chosen from lauryl betaine, coco betaine and mixtures thereof; even more preferably is coco betaine. Composition according to one of the preceding claims, in which the amphoteric surfactant is present in an amount ranging from 1% to 20% by weight, in particular from 2% to 15% by weight, and more particularly from 3 to 10% by weight relative to the total weight of the composition. Composition according to one of the preceding claims, in which the weight ratio between the N-acyl amino surfactant and the amphoteric surfactant varies from 1:2 to 2:1 and preferably between 0.5 and 1.7. Composition according to one of the preceding claims, in which the non-associative crosslinked copolymer of acrylic acid and/or methacrylic acid, and optionally one of their esters, is chosen from:
- a crosslinked copolymer of acrylic acid and/or methacrylic acid and an ester thereof comprising less than 6 carbon atoms,
- a crosslinked copolymer comprising at least one methacrylic unit and at least one C1-C4 alkyl acrylate unit, for example an ethyl acrylate unit,
- a crosslinked copolymer of vinyl neodecanoate and one or more monomers of acrylic acid, methacrylic acid or one of their simple esters crosslinked by an allyl ether of trimethylolpropane or pentaerythritol, and
- their mixtures. Composition according to one of the preceding claims, in which the non-associative crosslinked copolymer of acrylic acid and/or methacrylic acid, and optionally its esters, is present in an active material content greater than or equal to 0.3% by weight, more particularly greater than or equal to 0.5% by weight relative to the total weight of the composition, for example in a content ranging from 0.3% to 8% by weight, preferably from 0.5% to 5% by weight, preferably from 0.7% to 3% by weight relative to the total weight of the composition. Composition according to one of the preceding claims, which comprises, in addition to the surfactant system comprising (i) at least one N-acyl-amino surfactant and (ii) at least one amphoteric surfactant, an additional surfactant; preferably the additional surfactant is non-ionic, preferably chosen from alkylpolyglucosides (APG), oxyalkylenated glycerol esters, oxyalkylenated sugar esters, and mixtures thereof; preferably the additional surfactant is an oxyalkylenated sugar ester which may be chosen in particular from oxyethylenated glucose esters, such as PEG-120 methyl glucose dioleate. Composition according to one of the preceding claims, which also comprises at least one antioxidant reducing agent, preferably chosen from sodium thiosulfate, sodium metabisulfite, thioglycolic acid, thiolactic acid, cysteine, cysteamine, homocysteine and mixtures thereof. Composition according to claim 18, which comprises from 0.01% to 3% by weight of antioxidant reducing agent relative to the total weight of composition, preferably from 0.05% to 1% by weight, preferentially from 0.08% to 0.3% by weight. Composition according to one of the preceding claims, which also comprises vitamin E or tocopheryl acetate. Composition according to claim 20, which comprises from 0.01% to 3% by weight of vitamin E or tocopheryl acetate relative to the total weight of composition, preferably from 0.05% to 1% by weight, preferentially from 0.08% to 0.5% by weight. Composition according to one of the preceding claims, which is in the form of a gel, preferably an aqueous gel, preferably a cleansing gel, or an emulsion, in particular obtained by dispersing an aqueous phase in a fatty phase (W/O) or a fatty phase in an aqueous phase (O/W). A method of cleansing the skin, preferably the skin of the face, neck or body, comprising (i) applying a composition according to one of the preceding claims to the skin, then (ii) rinsing off this composition.