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Title:
BLUE POWDER AND USE THEREOF IN COSMETICS
Document Type and Number:
WIPO Patent Application WO/2018/050504
Kind Code:
A1
Abstract:
The invention relates to a blue coloured, water-insoluble powder comprising the combination of an anthocyanin, a complexed metal chosen from aluminium or zinc or the mixture thereof, and a nitrogen-based compound. The invention also relates to a cosmetic composition comprising the coloured powder and a process for making up keratin materials by applying the coloured powder to the keratin materials.

Inventors:
CHOISY PATRICK (FR)
GUENAULT EMILIE (FR)
Application Number:
PCT/EP2017/072304
Publication Date:
March 22, 2018
Filing Date:
September 06, 2017
Export Citation:
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Assignee:
OREAL (FR)
International Classes:
A61K8/02; A61K8/26; A61K8/27; A61K8/43; A61K8/44; A61K8/49; A61K8/60; A61K8/67; A61K8/88; A61Q1/10
Domestic Patent References:
WO2014029842A12014-02-27
WO2014029842A12014-02-27
Foreign References:
FR2994693A12014-02-28
Other References:
GREGORY T. SIGURDSON ET AL: "Bathochromic and Hyperchromic Effects of Aluminum Salt Complexation by Anthocyanins from Edible Sources for Blue Color Development", JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY, vol. 62, no. 29, 23 July 2014 (2014-07-23), US, pages 6955 - 6965, XP055352726, ISSN: 0021-8561, DOI: 10.1021/jf405145r
BROUILLARD R ET AL: "pH and Solvent Effects on the Copigmentation Reactionof Malvin with Polyphenols Purine and Pyrimidine Derivatives", JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS 2, CHEMICAL SOCIETY. LETCHWORTH, GB, vol. 8, 1 January 1991 (1991-01-01), pages 1235 - 1241, XP009156684, ISSN: 1472-779X
RAYMOND BROUILLARD; ANDRE FOUGEROSSE: "Le mystere de la couleur des fleurs, des fruits ... et du vin!", THE MYSTERY OF THE COLOUR OF FLOWERS, FRUILAND WINE!, 18 February 2008 (2008-02-18), Retrieved from the Internet
JIN-MING KONG ET AL., PHYTOCOMPOSE, vol. 64, 2003, pages 923 - 933
A CASTANEDA-OVANDO ET AL., FOOD COMPOSE, vol. 113, 2009, pages 859 - 871
Attorney, Agent or Firm:
KROMER, Christophe (FR)
Download PDF:
Claims:
CLAIMS

1 . Coloured, water-insoluble powder comprising the combination of an anthocyanin, a complexed metal chosen from aluminium or zinc or the mixture thereof, and a nitrogen- based compound chosen from:

(i) heterocyclic nitrogen-based compounds of formula (IVa):

in which:

the— bonds may signify a single bond or a double bond, it being understood that 2 contiguous bonds cannot be double bonds, the nitrogen-based heterocycles being able to be saturated, unsaturated or aromatic;

X denotes -C(Rs)= or -N= or -N(Re)- ; Y denotes -N= or -N(R7)- or -(R8)N+-, An

Ri denotes an amino radical, a (C1 -C4)alkylamino radical, a (C1 -C4)dialkylamino radical, an oxygen atom (in carbonyl form), a hydrogen atom, or a C1 -C4 alkyl radical, optionally substituted by at least one hydroxyl group, such as methyl;

R2 denotes a hydrogen atom, a hydroxyl radical, a carboxyl (-CO2H) radical, or a C1 -C4 alkyl radical such as methyl;

R3 denotes a hydrogen atom or a C1 -C4 alkyl radical optionally substituted by one or more hydroxyl radicals, such as hydroxymethyl;

R4 denotes a hydrogen atom, an amino radical or an oxygen atom (in carbonyl form);

R5 denotes a hydrogen atom or a C1 -C4 alkyl radical optionally substituted by one or more hydroxyl radicals, such as hydroxymethyl;

R6 denotes a hydrogen atom, a C1 -C4 alkyl radical such as methyl, or a radical of formula (aa):

R7 denotes a hydrogen atom or a C1 -C4 alkyl radical such as methyl;

Rs denotes a C1 -C4 alkyl radical such as methyl; R2 and R3 possibly forming, together with the carbon atoms which bear them, a saturated or unsaturated 4- to 8-membered (hetero)cycle, 1 or more non-adjacent ring members of which may denote a nitrogen atom -N= or an -N(Rg)- radical, with Rg denoting a hydrogen atom or a radical R10 of formula:

in which A is chosen from a hydrogen atom, or a (dd), (ee) or (ff) radical as follows:

O O O

HO-P-O-P-O-P - OH OH OH

(ee)

O O

HO-P-O-P *

OH OH

(ff)

* indicates the point of attachment of the radical A to the oxygen atom of R10

An" denotes a cosmetically acceptable anion,

and the salts thereof

(ii) heterocyclic nitrogen-based compounds of formula (IVb): in which:

the— bonds may signify a single bond or a double bond, it being understood that 2 contiguous bonds cannot be double bonds, the nitrogen-based heterocycles being able to be saturated, unsaturated or aromatic;

Rii denotes an oxygen atom (in carbonyl form) or a -CH2-CH(NH2)-CC>2H radical or a -COOH group;

Ri2 denotes a hydrogen atom or an oxygen atom (in carbonyl form);

Ri3 denotes a hydrogen atom or an -NH-CO-NH2 radical;

Z denotes a nitrogen atom -N= or an-N(Ri4)- radical, in which Ri4 denotes a hydrogen atom or a -CH2-CH(NH2)-C02H radical, or a -CH2- radical;

and the salts thereof

(iii) nitrogen-based compounds of formula (V):

RVR'sNH (V) in which RV and R's represent, independently of one another

- a hydrogen atom;

- a linear, branched and/or cyclic, saturated and/or unsaturated, aromatic or non- aromatic C1-C20 hydrocarbon-based radical, which may contain from 1 to 5 carbon- carbon double bonds and/or which is optionally substituted, optionally interrupted by one or more heteroatoms and/or by one or more groups comprising at least one heteroatom or group comprising at least one heteroatom (preferably chosen from oxygen, sulfur, C=0, C=S, SO, SO2 or combinations thereof);

or else RV = H and R'8 = -C(=NH)-NH2;

and the salts thereof

(iv) amino polymers with the proviso that, when the nitrogen-based compound is an amino acid, then the coloured powder does not contain tannic acid or a gallotannin derivative thereof, or the mixtures thereof.

2. Powder according to the preceding claim, characterized in that the anthocyanin is a compound of formula (I):

in which Ri , R2 and R4 independently denote H, OH, OMe, a sugar unit or an acylated sugar unit, the acyl group of which contains 2 to 15 carbon atoms, it being understood that at least one of the radicals Ri , R2 and R4 denotes a sugar unit or an acylated sugar unit, and R3, R5, R6 and R7 independently denote H, OH or OMe.

3. Powder according to either one of the preceding claims, characterized in that the anthocyanin is derived from plant material chosen from black carrot, elderberry, hibiscus, purple corn, black potato, red cabbage, red onion, purple potato, black grape, cranberry, strawberry, raspberry, aronia, black soybean, blackcurrant, radish, gooseberry, blueberry, cherry, aubergine and black rice.

4. Powder according to any one of the preceding claims, characterized in that the anthocyanin is present in the coloured powder in a content ranging from 0.05% to 50% by weight, relative to the total weight of dry matter of the coloured powder, preferably ranging from 0.3% to 30% by weight, preferentially ranging from 5% to 30% by weight, and more preferentially ranging from 10% to 30% by weight. 5. Powder according to any one of the preceding claims, characterized in that the complexed metal is aluminium.

6. Powder according to any one of Claims 1 to 4, characterized in that the complexed metal is derived from salts chosen from aluminium sulfate, ammonium aluminium sulfate, aluminium acetate, aluminium chloride, aluminium chlorohydrate, zinc acetate, zinc gluconate, zinc chloride, zinc sulfate; and mixtures thereof, and preferably chosen from ammonium aluminium sulfate, aluminium chloride, zinc sulfate, and mixtures thereof.

7. Powder according to any one of the preceding claims, characterized in that the complexed metal is present at a weight ratio of metal ions/anthocyanin ranging from 0.01/1 to 10/1 , preferably ranging from 0.05/1 to 5/1.

8. Powder according to any one of the preceding claims, characterized in that the nitrogen-based compound is a compound of formula (IVa) or (IVb) and is chosen from nicotinamide adenine diphosphate, adenosine triphosphate disodium salt, pyridoxine, adenosine diphosphate, theobromine, adenosine, thymidine, guanine, cytidine, uridine, caffeine, xanthine, nicotinic acid, trigonelline, paraxanthine, adenine, histidine, allantoin, tryptophan and proline.

9. Powder according to one of Claims 1 to 7, characterized in that the nitrogen-based compound of formula (V) is chosen from the compounds of formula (Va): in which:

- Rg represents a hydrogen atom or a linear or branched C1-C6 alkyl radical, optionally substituted by one or more identical or different groups chosen from hydroxyl, hydroxycarbonyl, thiol, (Ci-C4)alkylthio, amido, amino or guanidine radicals, or a phenyl radical, optionally substituted by one or more hydroxyls;

- R'g represents a hydrogen, a C1-C4 alkyl radical, or an unsubstituted benzyl radical, or a C2-C16 acyl radical; R'g preferably represents a hydrogen atom;

- R10 represents a hydrogen or a C1-C4 alkyl radical; R10 preferably represents a hydrogen atom.

10. Powder according to any one of Claims 1 to 7 and 9, characterized in that the nitrogen-based compound is a compound of formula (V) or (Va) and is chosen from guanidine (especially in hydrochloride form), lysine, N-lauroyl lysine or arginine. 1 1 . Powder according to any one of Claims 1 to 7, characterized in that the nitrogen- based compound is an amino polymer chosen from:

- poly((C2-C5)alkyleneimine)s;

- poly(allylamine);

- polyvinylamines and copolymers thereof, especially with vinylamides;

- aminodextran;

- vinylamine/vinyl alcohol copolymers;

- acrylamidopropylamine polymers;

- chitosans.

12. Powder according to any one of Claims 1 to 7 and 1 1 , characterized in that the nitrogen-based compound is polylysine.

13. Powder according to any one of Claims 1 to 7, characterized in that the nitrogen- based compound is chosen from Nicotinamide Adenine Diphosphate, pyridoxine, adenosine triphosphate disodium salt, adenosine diphosphate, theobromine, adenosine, thymidine, guanine, cytidine, uridine, caffeine, xanthine, allantoin, nicotinic acid, trigonelline, paraxanthine, histidine, guanidine (especially in hydrochloride form), lysine, polylysine, N-Lauroyl lysine, arginine, adenine; preferably chosen from pyridoxine, adenosine triphosphate disodium salt, adenosine, caffeine, allantoin, trigonelline, histidine, polylysine, N-Lauroyl lysine, arginine, adenine; more preferentially chosen from pyridoxine, adenosine triphosphate disodium salt, adenosine, allantoin, trigonelline, histidine, polylysine, arginine and adenine.

14. Powder according to any one of Claims 1 to 7, characterized in that the nitrogen- based compound is chosen from pyridoxine, adenosine triphosphate disodium salt, adenosine, allantoin, histidine and adenine.

15. Powder according to any one of Claims 1 to 7, characterized in that the nitrogen- based compound is chosen from adenosine triphosphate disodium salt and histidine.

16. Powder according to any one of Claims 1 to 7, characterized in that the nitrogen- based compound is adenosine triphosphate disodium salt.

17. Powder according to any one of Claims 1 to 7, characterized in that the nitrogen- based compound is present at a weight ratio of nitrogen-based compound/anthocyanin ranging from 1/10 to 10/1 , preferably ranging from 1/3 to 3/1 by weight, preferentially ranging from 1/2 to 2/1 by weight.

18. Powder according to any one of the preceding claims, characterized in that it has a blue colour and a hue angle of between 210° and 325°, and preferably between 250° and 300°.

19. Cosmetic composition comprising, in a physiologically acceptable medium, a coloured powder according to any one of the preceding claims.

20. Cosmetic process for the treatment of keratin materials, comprising the application, to the keratin materials, of a coloured powder according to one of Claims 1 to 18 or of a composition according to Claim 19.

21 . Process according to the preceding claim, characterized in that it is a process for making up keratin materials.

Description:
Blue powder and use thereof in cosmetics

The present invention relates to a coloured powder comprising an anthocyanin, a composition containing the coloured powder and a process for treating keratin materials using the coloured powder.

For several years, there has been an increasing interest in natural compounds of use as coloured material, especially in the field of cosmetics.

The colour range available in natural dyes or in natural pigments is not as broad as that of synthetic dyes or synthetic pigments, and many natural dyes or natural pigments have poor stability during their exposure to light. In particular, there are very few natural blue dyes or natural blue pigments, and they are not sufficiently photostable: their hue fades and thus does not produce a very attractive colour effect. Coloured blue powders obtained from anthocyanins, metal ions derived from Al(lll), Ca(ll), Fe(ll), Mg(ll), Zn(ll), and tannic acid or its gallotannin derivatives, used for making up keratin materials, are known from document WO2014/029842. These coloured powders have good photostability. Nonetheless, the blue colour of these coloured powders is not very vibrant and therefore blue powders are sought which have better chromaticity, in order to be able to obtain better colour effects, especially with the makeup products containing such powders.

The aim of the present invention is thus to make available a blue coloured powder having a good hue angle, good chromaticity and also good photostability.

The inventors have discovered that such a coloured powder is obtained by stabilizing anthocyanins with certain complexed metals and certain nitrogen-based compounds, as defined below.

Aside from the good properties of chromaticity and photostability, the powders according to the invention also have at least one good property from properties of coverage, tinting strength and lightness.

More specifically, the invention relates to a coloured, water-insoluble powder comprising the combination of an anthocyanin, a complexed metal chosen from aluminium or zinc, and a particular nitrogen-based compound as described below.

The invention also relates to a process for preparing the coloured, water-insoluble powder.

The invention also relates to a composition comprising, in a physiologically acceptable medium, a coloured, water-insoluble powder as described previously. The invention also relates to a process for treating keratin materials, comprising the application, to the keratin materials, of a coloured, water-insoluble powder as described above or of a composition containing same.

The process is advantageously carried out on human keratin materials.

The process for treating keratin materials is preferably a process for making up keratin materials, in particular human keratin materials.

Within the meaning of the present invention, keratin materials is intended to mean the skin (especially the skin of the face, the cheeks and the eyelids), the lips, the hair, the nails, the eyelashes and the eyebrows.

Water-insoluble powder is intended to mean a pulverulent material (hence in particulate form) which is not soluble in water or ethanol or mixtures of water/ethanol in any proportions, at a concentration of 0.5% by weight and at room temperature (25°C).

The document "Le mystere de la couleur des fleurs, des fruits ... et du vin!" The mystery of the colour of flowers, fruit..and wine!') by Raymond Brouillard and Andre Fougerosse, dated 18 February 2008 (URL:

http://radium.net.espci.fr/esp/CONF/2008/C08_02/conf02_20 08.htm)

describes that a mixture of blueberry extract, aluminium nitrate and caffeine in water gives a blue-coloured solution. This blue aqueous solution appears clear, without the formation of a precipitate: the formation of water-insoluble coloured particles is not demonstrated in this mixture produced.

The coloured powder according to the invention comprises at least one anthocyanin.

As is known, anthocyanins are anthocyanidin glycosides (Jin-Ming Kong et al., Phytocompose, 64, 923-933 (2003)).

There are more than 500 different anthocyanins in nature. Their main differences relate to the number of hydroxyl groups and methoxy groups, the nature and the number of sugar units present, the aliphatic or aromatic carboxylate groups bonded to the sugars in the molecule, and the position of these bonds (A Castafieda-Ovando et al., Food Compose, 1 13, 859-871 (2009)).

Anthocyanidins are compounds of formula (I) below:

in which the radicals Ri to R7 denote, independently, H, OH or OMe, it being understood that at least one of the radicals Ri to R7 denotes a sugar radical.

The 6 most common anthocyanidins are indicated in Table 1 below, with their name, abbreviation and substituents of formula (I) described above.

Tab e 1 : common anthocyanidins

As indicated above, anthocyanins may contain sugar units chosen from glucose, rhamnose, galactose, xylose, arabinose, rutinose and glucuronic acid. The sugar units may be present in the form of monosaccharide or oligosaccharides, such as, for example, diglucose.

Most anthocyanins in nature are 3-monosaccharides or 3,5-disaccharides such as 3,5- diglucosides and 3,7-diglucosides.

Anthocyanins may also be acylated: the sugar units may be acylated by esterification with a carboxylic acid, especially having 2 to 15 carbon atoms, such as acetic acid, malonic acid, p-coumaric acid, ferulic acid, sinapic acid or caffeic acid.

Advantageously, the anthocyanins present in the coloured, water-insoluble powder according to the invention may be chosen from those of formula (Γ):

in which Ri , R2 and R 4 independently denote H, OH, OMe, a sugar unit or an acylated sugar unit (acyl group having especially from 2 to 15 carbon atoms, such as those derived from acetic acid, malonic acid, p-coumaric acid, sinapic acid, ferulic acid or caffeic acid), it being understood that at least one of the radicals Ri , R2 and R 4 denotes a sugar unit or an acylated sugar unit, and R3, R5, R6 and R 7 independently denote H, OH or OMe.

The anthocyanins may be of natural or synthetic origin.

A certain number of plants are naturally rich in anthocyanins. Mention may be made, by way of example, of black carrot, elderberry, hibiscus, blackcurrant, purple corn, black potato, red cabbage, red onion, purple potato, black grape, cranberry, strawberry, raspberry, aronia, black soybean, radish, gooseberry, blueberry, cherry, aubergine and black rice.

The anthocyanins used according to the present invention may be chosen from anthocyanins, the anthocyanidin-derived units of which are chosen from cyanidin, delphinidin, malvidin, peonidin or petunidin, the sugar(s) present preferably being chosen from galactose, glucose, arabinose, rutinose or diglucose, this (these) sugar(s) possibly being acylated by acetic acid, malonic acid, p-coumaric acid, sinapic acid, ferulic acid or caffeic acid. Thus, the anthocyanins used according to the invention may be chosen from:

cyanidin-3-O-arabinoside, cyanidin-3-O-galactoside, cyanidin-3-O-glucoside, cyanidin- 3,5-O-diglucoside, cyanidin-3-O-rutinoside,

delphinidin-3-O-arabinoside, delphinidin-3-O-galactoside, delphinidin-3-O-glucoside, delphinidin-3-O-glucoside, delphinidin-3-O-rutinoside,

malvidin-3-O-arabinoside, malvidin-3-O-galactoside, malvidin-3-O-glucoside, malvidin- 3,5,-O-diglucoside,

peonidin-3-O-glucoside, peonidin-3-O-glucoside,

petunidin-3-O-arabinoside, petunidin-3-O-galactoside, petunidin-3-O-glucoside, these anthocyanins possibly being acylated by acetic acid, malonic acid, p-coumaric acid, sinapic acid, ferulic acid or caffeic acid. The four predominant anthocyanins present in blackcurrants are cyanidin-3-O-glucoside, cyanidin-3-O-rutinoside, delphinidin-3-O-glucoside and delphinidin-3-O-rutinoside. Black grapes and red cabbage are the two largest sources of anthocyanins in nature. The anthocyanidin units of the anthocyanins present in black grapes are cyanidin, peonidin, malvidin, petunidin and delphinidin; and the organic acids present are acetic, coumaric and caffeic acids. The only sugar present is glucose (F.J. Francis, Colorants, p56, Eagan Press (1999)). One grape anthocyanin, malvidin-3,5,-diglucoside, corresponds to the following formula (II), in which Glu is glucose and Me is the methyl radical.

(ll)

According to one embodiment of the invention, the anthocyanins used may be chosen from cyanidin-3-O-galactoside, cyanidin-3-O-glucoside, cyanidin-3-O-arabinoside, delphinidin-3-O-galactoside, delphinidin-3-O-glucoside, delphinidin-3-O-arabinoside, malvidin-3-O-galactoside, malvidin-3-O-glucoside, malvidin-3-O-arabinoside, peonidin- 3-O-glucoside, petunidin-3-O-galactoside, petunidin-3-O-glucoside, petunidin-3-O- arabinoside. According to another embodiment of the invention, the anthocyanins used may be chosen from cyanidin-3-O-glucoside, peonidin-3-O-glucoside, cyanidin-3,5-0- diglucoside, cyanidin-3-rutinoside.

Seven of the anthocyanins present in red cabbage are described in formula (III) and Table 2 below. The Ri and R2 groups of these seven anthocyanins are indicated in Table

(Hi)

Feruloyl Sinapoyl p-Coumaroyl

The anthocyanins used according to the present invention may be one or more of the cyanidin-3-diglucosides A to G described above in Table 2.

The anthocyanins may be added in the form of plant material or of an extract of plant material.

The plant material may be chosen, for example, from vegetables, fruit or flowers. The plant material may be chosen from red cabbage, red onion, purple potato, grape, cranberry, strawberry, raspberry, aronia, black soybean, blackcurrant, elderberry, hibiscus, radish, gooseberry, blueberry, cherry, aubergine, black carrot and black rice.

In particular, the anthocyanins present in the coloured, water-insoluble powder may be derived from blueberry or a blueberry extract.

Blueberry is intended to mean Vaccinium sp, for example Vaccinium myrtillus, common bilberry, Vaccinium uliginosum, bog blueberry, or also Vaccinium caespitosum, Vaccinium corymbosum, Vaccinium angustifolium, Vaccinium deliciosum, Vaccinium membranaceum, Vaccinium ovalifolium, or Vaccinium myrtilloides. Vaccinium myrtillus is preferably used.

In particular, the anthocyanins present in the coloured, water-insoluble powder may be derived from black rice or a black rice extract.

Rice is intended to mean Oryza sp, for example Oryza sativa, rice originating from the wet tropics of Asia, and Oryza glaberrima, West African rice, which are the two species of cultivated rice, or Oryza sativa L. indica, or Oryza sativa L. japonica, the subspecies of Asian rice. The anthocyanin may be present in the coloured, water-insoluble powder in a content ranging from 0.05% to 50% by weight, relative to the total weight of dry matter of the coloured powder, preferably ranging from 0.3% to 30% by weight, preferentially ranging from 5% to 30% by weight, and more preferentially ranging from 10% to 30% by weight.

Metal ions

The coloured powder according to the invention comprises a complexed metal chosen from aluminium or zinc or the mixture thereof.

The complexed metal is especially formed from metal ions chosen from Al , Zn and mixtures thereof.

These metal ions make it possible to stabilize the anthocyanins by complex formation. The complexed metal is advantageously derived from aluminium or zinc metal ions and in particular from aluminium or zinc salts formed with anions such as gluconate, chloride, sulfate and acetate.

For example, such salts may be chosen from aluminium sulfate, Al2(SC>4)3, containing the (Al 3+ ) ion, ammonium aluminium sulfate, aluminium acetate, aluminium chloride, aluminium chlorohydrate, zinc acetate, zinc gluconate, zinc chloride, zinc sulfate, Zn(S0 4 ) containing the (Zn 2+ ) ion, and mixtures thereof.

The complexed metal is preferably derived from salts chosen from ammonium aluminium sulfate, aluminium chloride, zinc sulfate, and mixtures thereof. The complexed metal may be present in the coloured powder at a weight ratio of metal ions/anthocyanin ranging from 0.01/1 to 10/1 , preferably ranging from 0.05/1 to 5/1.

Nitrogen-based compound: The coloured powder according to the invention comprises a nitrogen-based compound chosen from nitrogen-based heterocyclic compounds of formula (IVa) or of formula (IVb) or nitrogen-based compounds of formula (V) or amino polymers as described below.

The nitrogen-based compound may be a heterocyclic nitrogen-based compound of formula (IVa):

(IVa) in which:

the— bonds may signify a single bond or a double bond, it being understood that 2 contiguous bonds cannot be double bonds, the nitrogen-based heterocycles being able to be saturated, unsaturated or aromatic;

X denotes -C(Rs)= or -N= or -N(Re)- ; Y denotes -N= or -N(R 7 )- or -(R 8 )N + -, An " Ri denotes an amino radical, a (C1 -C4)alkylamino radical, a (C1 -C4)dialkylamino radical, an oxygen atom (in carbonyl form), a hydrogen atom, or a C1 -C4 alkyl radical, optionally substituted by at least one hydroxyl group, such as methyl;

R2 denotes a hydrogen atom, a hydroxyl radical, a carboxyl (-CO2H) radical, or a C1 -C4 alkyl radical such as methyl;

R3 denotes a hydrogen atom or a C1 -C4 alkyl radical optionally substituted by one or more hydroxyl radicals, such as hydroxymethyl;

R 4 denotes a hydrogen atom, an amino radical or an oxygen atom (in carbonyl form);

R5 denotes a hydrogen atom or a C1 -C4 alkyl radical optionally substituted by one or more hydroxyl radicals, such as hydroxymethyl;

R6 denotes a hydrogen atom, a C1 -C4 alkyl radical such as methyl, or a radical of formula (aa):

R7 denotes a hydrogen atom or a C1 -C4 alkyl radical such as methyl;

Rs denotes a C1 -C4 alkyl radical such as methyl;

R2 and R3 possibly forming, together with the carbon atoms which bear them, a saturated or unsaturated 4- to 8-membered (hetero)cycle, 1 or more non-adjacent ring members of which may denote a nitrogen atom -N= or an -N(Rg)- radical, with Rg denoting a hydrogen atom or a radical R10 of formula:

in which A is chosen from a hydrogen atom, or a (dd), (ee) or (ff) radical as follows:

O O

HO-P-O-P—

I I OH OH

(ff)

* indicates the point of attachment of the radical A to the oxygen atom of R10 An " denotes a cosmetically acceptable anion such as a halide anion, such as, for example, a chloride anion;

and the salts thereof.

Preferably, when 2 and R3 form, together with the carbon atoms which bear them, a saturated or unsaturated (hetero)cycle, this heterocycle comprises 5 or 6 ring members, preferably 5 ring members, and one or more non-adjacent ring members denote a nitrogen atom -N= or an -N(Rg)- radical as defined above.

Particularly preferably, R2 and R3 form, together with the carbon atoms which bear them, a 5- or 6-membered, preferably 5-membered, unsaturated heterocycle, two non-adjacent ring members of which denote, on the one hand, a nitrogen atom

-N= and, on the other hand, an -N(Rg)- radical as defined above.

By way of example of compound (IVa), mention may be made of:

Nitrogen-based CAS no. Chemical structure

compound

(a) Nicotinamide 53-84-9

Adenine Diphosphate

(r) Adenine 73-24-5

The compound (IVa) is preferably chosen from nicotinamide adenine diphosphate, adenosine triphosphate disodium salt, adenosine diphosphate, theobromine, adenosine, thymidine, guanine, cytidine, uridine, caffeine, xanthine, nicotinic acid, trigonelline, paraxanthine, and adenine.

The nitrogen-based compound may be a heterocyclic nitrogen-based compound of formula (IVb):

in which:

the— bonds may signify a single bond or a double bond, it being understood that 2 contiguous bonds cannot be double bonds, the nitrogen-based heterocycles being able to be saturated, unsaturated or aromatic;

Rii denotes an oxygen atom (in carbonyl form) or an -CH2-CH(NH2)-CC>2H radical or a -COOH group;

Ri2 denotes a hydrogen atom or an oxygen atom (in carbonyl form);

Ri3 denotes a hydrogen atom or an -NH-CO-NH2 radical;

Z denotes a nitrogen atom -N= or an-N(Ri 4 )- radical, in which Ri 4 denotes a hydrogen atom or a -CH 2 -CH(NH 2 )-C02H radical, or a -CH2- radical;

and the salts thereof.

When the compound (IVa) or (IVb) comprises an anionic group such as a carboxylic acid group, the anionic group may be in salt form, for example in the form of an alkali metal salt or alkaline earth metal salt, such as sodium, potassium, magnesium or calcium salt.

By way of example of compound (IVb), mention may be made of:

Nitrogen-based CAS no. Chemical structure compound

(s) Histidine 71 -00-1

(t) Allantoin 97-59-6 H O

H

The heterocyclic nitrogen-based compound (IVa) or (IVb) is preferably chosen from nicotinamide adenine diphosphate, adenosine triphosphate disodium salt, adenosine diphosphate, theobromine, adenosine, thymidine, guanine, cytidine, uridine, caffeine, xanthine, nicotinic acid, trigonelline, paraxanthine, adenine, histidine, allantoin, tryptophan and proline.

The heterocyclic nitrogen-based compound is preferentially chosen from pyridoxine, adenosine triphosphate disodium salt, adenosine, caffeine, allantoin, trigonelline, histidine and adenine.

The heterocyclic nitrogen-based compound is more preferentially chosen from pyridoxine, adenosine triphosphate disodium salt, adenosine, allantoin, trigonelline, histidine and adenine.

The nitrogen-based compound may be a compound of formula (V): RVR'sNH (V) in which RV and R's represent, independently of one another

- a hydrogen atom;

- a linear, branched and/or cyclic, saturated and/or unsaturated, aromatic or non- aromatic C1-C20 hydrocarbon-based radical, which may contain from 1 to 5 carbon- carbon double bonds and/or which is optionally substituted, optionally interrupted by one or more heteroatoms and/or by one or more groups comprising at least one heteroatom or group comprising at least one heteroatom (preferably chosen from oxygen, sulfur, C=0, C=S, SO, SO2 or combinations thereof) ;

or else RV = H and R' 8 = -C(=NH)-NH2;

and the salts thereof.

Among the groups present as substituents of the heterocyclic hydrocarbon-based groups, mention may be made of the following groups:

carboxylic, in acid or salified form,

sulfonic, in acid or salified form, phosphonic, in acid or salified form,

hydroxyl,

C1-C4 alkoxy,

(Ci-C8)alkoxycarbonyl,

(Ci-C4)alkylsulfonate,

(Ci-C8)alkylphosphonate,

(Ci-C 4 )trialkylsilyl,

(Ci-C4)trialkoxysilanyl,

amino;

(di)(Ci-C4)alkylamino,

(Ci-C4)trialkylammonium,

thiol,

(Ci-C 4 )alkylthio,

aminosulfonyl,

(di-)(Ci-C4)alkylaminosulfonyl,

aminocarbonyl,

(di)(Ci-C4)alkylaminocarbonyl,

(Ci-C4)alkylcarbonylamino,

guanidine

ureido (N(R)2-CO-NR'-) in which the radicals R and R', independently of one another, represent a hydrogen atom, a C1-C4 alkyl radical or a (Ci-C4)alkylsulfonylamino radical;

phenyl, optionally substituted by one or more C1-C2 alkyl or hydroxyl.

Preferably, the groups present as substituents are chosen from:

carboxylic, in acid or salified form,

hydroxyl,

C1-C4 alkoxy,

(Ci-C8)alkoxycarbonyl,

thiol,

(Ci-C 4 )alkylthio,

amino,

(C1-C4) mono- and di-alkylamino,

aminocarbonyl,

(C1-C2) mono- and di-alkylaminocarbonyl,

(Ci-C4)alkylcarbonylamino,

phenyl, optionally substituted by one or more C1-C2 alkyl or hydroxyl.

In particular, the amine(s) of formula (V), which may be identical or different, comprise from one to five primary and/or secondary amine functions; the amine(s) not comprising any N-N bonds. Also, the amine(s) of formula (V) do not comprise more than two adjacent oxygen atoms.

Preferably, the amine(s) are compounds of formula (V), more particularly chosen from the compounds of formulae (Va) to (Vg) below:

o amino acids and general formula (Va):

(Va)

in which formula (Va):

- Rg represents a hydrogen atom or a linear or branched C1-C6 alkyl radical, optionally substituted by one or more identical or different groups chosen from hydroxyl, hydroxycarbonyl, thiol, (Ci-C4)alkylthio, amido, amino or guanidine radicals, or a phenyl radical, optionally substituted by one or more hydroxyls;

- R'g represents a hydrogen, a C1-C4 alkyl radical, or an unsubstituted benzyl radical, or a C2-C16 acyl radical; R'g preferably represents a hydrogen atom;

- R10 represents a hydrogen or a C1-C4 alkyl radical; R10 preferably represents a hydrogen atom; o esters derived f /or derivatives of general formula (Vb): in which formula (Vb):

- Rg represents a hydrogen atom or a linear or branched C1-C6 alkyl radical, optionally substituted by one or more identical or different groups chosen from hydroxyl, hydroxycarbonyl, (Ci-C4)alkoxycarbonyl, thiol, (Ci-C4)alkylthio, amido, amino or guanidine radicals, or a phenyl radical, optionally substituted by one or more hydroxyls,

- R'g represents a hydrogen, a C1-C4 alkyl radical, or an unsubstituted benzyl radical, or a C2-C16 acyl radical;

- R10 represents a hydrogen or a C1-C4 alkyl radical; R10 preferably represents a hydrogen atom;

- R11 represents:

- a linear or branched, saturated or unsaturated C1-C18 hydrocarbon-based radical optionally comprising from 1 to 5 conjugated or unconjugated carbon-carbon double bonds, optionally substituted as indicated previously for Rg, optionally interrupted by one or more heteroatoms and/or by one or more groups comprising at least one heteroatom, preferably chosen from oxygen, sulfur, -NH-, C=0, C=S, SO and SO2 or combinations thereof;

- a benzyl radical optionally substituted by NO2, CI, CN, C1-C4 alkoxy such as methoxy, C1-C4 alkyl such as methyl; preferably an unsubstituted benzyl radical;

- a phenyl radical.

According to a particular variant, Rg and Rn may optionally form a saturated 5- membered carbon-based ring.

Preferably, Rn represents a linear or branched C1-C10 alkyl radical, optionally substituted as indicated above for Rg; a benzyl radical; and even more preferably a linear or branched C1-C4 alkyl radical optionally substituted by at least one hydroxyl group, preferably from 1 to 2 hydroxyl groups; a benzyl radical. o amides and thioesters derived from amino acids and/or derivatives of general formula (Vc): in which formula (Vc):

- Rg represents a hydrogen atom or a linear or branched C1-C6 alkyl radical, optionally substituted by one or more identical or different groups chosen from hydroxyl, (Ci- C4)alkoxycarbonyl, hydroxycarbonyl, thiol, (Ci-C4)alkylthio, amido, amino or guanidine radicals, or a phenyl radical, optionally substituted by one or more hydroxyls,

- Rg represents a hydrogen or a C1-C4 alkyl radical optionally substituted by a hydroxysulfonyl radical;

- R10 represents a hydrogen or a C1-C4 alkyl radical;

- R12 represents:

* a hydrogen atom;

* a C1-C6 alkyl radical, preferably substituted by one or more hydroxyl, thiol, (Ci- C4)alkylthio, amido or amino groups or a phenyl radical, optionally substituted by one or more hydroxyls;

- Y represents a sulfur atom or -NH-.

According to a particular variant, Rg and R12 may optionally form a saturated 5-, 6- or 7-membered carbon-based ring when Y = S.

In the case where Y represents a nitrogen atom and R12 represents an alkyl radical as defined previously and most particularly an amino acid residue and/or the corresponding methyl or ethyl ester thereof chosen from alanine, arginine, asparagine, aspartate, cysteine, glutamate, glutamine, glycine, lysine, methionine, phenylalanine, serine, threonine, tyrosine, valine, leucine or isoleucine, the compound of formula (Vc) represents a dipeptide or an oligopeptide.

o Amino compounds of general formula (Vd):

(Vd)

Ί which formula (Vd):

Ri3, Ri4, i5 and R16 represent, independently of each other:

* a hydrogen atom;

* a linear, branched and/or cyclic, saturated and/or unsaturated C1-C20 hydrocarbon-based radical, which may contain from 1 to 5 optionally aromatic carbon- carbon double bonds, optionally substituted as indicated previously for R9, optionally interrupted by one or more heteroatoms and/or by one or more groups comprising at least one heteroatom, preferably chosen from oxygen, sulfur, CO, C=S, SO and SO2 or combinations thereof, optionally bearing at least one hydroxyl or C1-C2 alkoxy group, said alkyl radicals R13 and R14 or R14 and R15 or R15 and R16 more particularly representing a C1-C10 alkyl radical, optionally substituted as indicated previously for R9; and preferably a linear or branched Ci-Cs alkyl radical optionally substituted by at least one hydroxyl group, preferably from 1 to 2 hydroxyl groups, a hydroxycarbonyl radical, a ureido radical, a (Ci-C4)alkoxycarbonyl radical; an unsubstituted phenyl radical;

W represents an oxygen or sulfur atom or -NH-.

Ri7 represents:

* a hydrogen atom;

* a linear or branched, saturated or unsaturated C1-C18 hydrocarbon-based radical, optionally comprising from 1 to 5 conjugated or unconjugated carbon-carbon double bonds, optionally substituted as indicated previously for R9, optionally interrupted by one or more heteroatoms and/or by one or more groups comprising at least one heteroatom, preferably chosen from oxygen, sulfur, -NH-, CO, C=S, SO and SO2 or combinations thereof; more particularly, R17 represents a hydrogen, a linear or branched C1-C10 alkyl radical, optionally substituted as indicated previously for R9; and preferably a hydrogen, a linear or branched C1-C4 alkyl radical optionally substituted by at least one hydroxyl group, preferably from 1 to 2 hydroxyl groups;

R18 represents:

* a hydrogen atom;

* a linear or branched C-i-Cs alkyl radical, optionally substituted as indicated previously for Rg, optionally interrupted with one or more heteroatoms and/or with one or more groups comprising at least one heteroatom, preferably chosen from oxygen, sulfur, -NH-, CO, C=S, SO and SO2 or combinations thereof, optionally bearing at least one hydroxyl or C1-C2 alkoxy group; the alkyl radical not comprising any nitro, nitroso, peroxo or diazo functions;

- n is an integer between 0 and 5. o amino compounds of general formula (Ve):

(Ve)

in which formula (Ve):

- Ri3, Ri4, i5, 16 and Ris have the same meaning as previously; in addition, the radicals Ri3, Ri4, Ris and R16, independently of one another, may also represent a hydroxyl radical, a (Ci-C4)alkoxycarbonyl radical, a carboxaldehyde radical or a (Ci-Cs)alkoxy;

- m is an integer between 1 and 18;

- Z represents an oxygen atom, an SH or OH group, or a methylene group optionally substituted by a hydroxyl radical;

- when Z represents an oxygen atom, then Ris forms a 5- or 6-membered ring optionally substituted by one or more hydroxy(methyl), preferably from 1 to 4 hydroxy(methyl) groups.

According to another variant of the invention, the amine of formula (Ve) may be a β-amino alcohol originating from the reduction of the acid or ester function to an alcohol of one of the twenty esterified or non-esterified amino acids.

o Amino compounds of general formula (Vf):

(Vf)

in which formula (Vf):

- Ri3, Ri4, Ris, R16 and Ris have the same meaning as previously. In addition, the radicals Ri3, Ri4, Ris and R16, independently of each other, may also represent a hydroxyl radical, a (Ci-C4)alkoxycarbonyl radical, a carboxaldehyde radical, a (Ci-Cs)alkoxy;

- R21 and R22 represent, independently of each other:

* a hydrogen atom;

* a linear, branched and/or cyclic, saturated and/or unsaturated C1-C20 hydrocarbon-based radical, which may contain from 1 to 5 carbon-carbon double bonds, optionally substituted as indicated previously for R9, optionally interrupted by one or more heteroatoms and/or by one or more groups comprising at least one heteroatom, preferably chosen from oxygen, sulfur, -NH, CO, C=S, SO and SO2 or combinations thereof, optionally bearing at least one hydroxyl or C1-C2 alkoxy group, more particularly a C1-C10 alkyl radical, optionally substituted as indicated previously for Rg; and preferably a linear or branched C1-C4 alkyl radical optionally substituted by at least one hydroxyl group, preferably from 1 to 2 hydroxyl groups;

- 1 is an integer between 1 and 10.

o Amino compounds of general formula (Vg):

(Vg)

in which formula (Vg):

- R23 represents:

* an optionally substituted C1-C6 alkyl radical, optionally interrupted by one or more heteroatoms and/or by one or more groups comprising at least one heteroatom, preferably chosen from oxygen, sulfur, -NH-, CO, SO and SO2 or combinations thereof;

* an alkylcarbonyl radical (R-CO-) in which R represents a C1-C4 alkyl radical;

* an alkylsulfonyl radical (RSO2-) in which R represents a C1-C4 alkyl radical;

* a (di)(alkyl)aminosulfonyl radical ((R)2N-S02-) in which the radicals R independently represent a hydrogen or a C1-C4 alkyl radical;

* a (di)(alkyl)aminocarbonyl radical ((R)2N-CO-) in which the radicals R independently represent a hydrogen or a C1-C4 alkyl radical;

* a halogen atom preferably chosen from bromine, chlorine and fluorine;

* a C1-C4 alkoxy group;

* a C2-C4 (poly)hydroxyalkoxy group;

* a hydroxycarbonyl group (HO-CO-);

* an alkoxycarbonyl group (RO-CO-) in which R represents a C1-C4 alkyl radical;

* an alkylcarbonylamino group (RCO-NR'-) in which the radical R represents a C1-C4 alkyl radical and the radical R' represents a hydrogen atom or a C1-C4 alkyl radical;

* an alkylsulfonyl radical (RSO2-) in which the radical R represents a C1-C4 alkyl radical;

- q is an integer between 0 and 2; when q is less than 2, the unsubstituted carbon atom(s) bear(s) a hydrogen atom.

Preferably, the amines of formula (V) of use within the context of the invention are chosen from the compounds of formula (Va) and most particularly arginine, asparagine, cysteine, glutamine, lysine, N-lauroyl lysine, methionine, phenylalanine, serine, threonine, and tyrosine.

According to another variant, the compounds of formula (Va) are preferably:

arginine, lysine or N-lauroyl lysine.

According to another preferred embodiment of the invention, the amines of formula (V) used are of formula (Vb) and more particularly chosen from:

tyrosine methyl or ethyl ester, phenylalanine methyl or ethyl ester, cystine dimethyl ester, leucine methyl ester, valine methyl ester, glutamic acid diethyl ester, 2-amino-3-methyl butanoic acid ethyl ester, serine methyl or ethyl ester, tyrosine methyl ester, 3- aminodihydrofuran-2-one, methyl 2-aminoacetate, ethyl glycinate, alanine methyl or ethyl ester, methyl 2-(phenylamino)acetate, ethyl glutamate, aspartic acid dibutyl ester, 2-aminoisocaproic acid ethyl ester, benzyl glycinate, and threonine methyl ester.

According to another preferred embodiment of the invention, the amines of formula (V) used are of formula (Vc) and more particularly chosen from:

homocysteine thiolactone, leucyl-alanine, aspartame, [N-(2-acetamido)]-2- aminoethanesulfonic acid, alanyl-phenylalanine, glycyl-tyrosine, glycylglycine, glycinamide, leucinamide, 2-aminopropanediamide, valyl-alanine, tyrosyl-alanine, valyl- phenylalanine, sarcosinyl-alanine, leucyl-glycyl-phenylalanine, sarcosyl-phenylalanine, tyrosyl-beta-phenylalanine, glycyl-valine, 2-aminomalonamide, methioninamide, vanilamide, alaninamide, tyrosinamide, aspartic acid monoamide, argininamide, lysinamide, threoninamide, isoleucinamide, phenylalaninamide, leucinamide, asparaginamide, glutamic acid diamide, glutamic acid monoamide, leucinamide, methioninamide, cystine diamide, glycinamide, glutamic acid monoamide methyl ester, cysteinyl-glycine, glutamyl-cysteinyl-glycine.

According to another preferred embodiment of the invention, the amines of formula (V) used are of formula (Vd), in particular chosen from:

2-aminohexanoic acid amide, aminosuccinnic acid, 2-(methylamino)succinic acid, 3- phenyl-beta-alanine, ethyl 3-aminobutyrate, 2-carboxyethylamine, beta-aminoadipic acid, methyl-beta-alaninate, ethyl-beta-alaninate, ethyl 3-amino-3-ureido butyrate, dimethylamino succinate, 4-amino butyric acid, 4-(methylamino)butyric acid, ethyl 4- amino butyrate.

According to another preferred embodiment of the invention, the amines of formula (V) used are of formula (Ve) and in particular are chosen from the following compounds, the enantiomers thereof if they exist, and the hydrates thereof: isopropanolamine, isopropylamine, methylethanolamine, methylglucamine, stearamine, tromethamine, 1 ,3- dimethylpentylamine, octodrine, spermidine, theanine, octamylamine, 2-amino-1 - phenylpropane-1 ,3- diol, 1 ,3-dihydroxy-2-amino-2-methylpropane, 2-amino-2- (hydroxymethyl)propane-1 ,3-diol tris, 2-amino-1 ,3-dihydroxy-2-ethylpropane, 2-amino-

3- methylbutan-1 -ol, 2-amino-2-methylpropan-1 -ol, phenylglycinol, 2-aminopropyl alcohol, 2-hydroxyethylamine, 2-aminohexan-1 -ol, 1 -amino-1 -cyclopentanemethanol, histidinol, 3-(4-hydroxyphenyl)-2-amino-1 -propanol, beta-aminoisobutanol, 2-amino-1 - propanol, 2-amino-1 ,3-propanediol, 2-amino-4-methyl-1 -pentanol, 1 -butanol-2-amino-3- methyl, beta-aminobenzenepropanol, 2-aminopropan-1 -ol, 2-amino-1 -butanol, 2-amino-

4- methylpentan-1 -ol, 3-aminopropanethiol, ethyl 2-amino-4-mercaptobutanoate, 6- hydroxyhexylamine, beta-D-galactopyranosylamine, B-D-glucopyranosylamine, 1 - amino-2,5-anhydro-D-mannitol, 1 -amino-1 -deoxy-D-fructose, D-glucosamine, 1 -amino-

2.3- dihydroxypropane, 3-propanolamine, 3-[(2-hydroxyethyl)amino]propan-1 -ol, di-beta- hydroethylamine, bis(3-hydroxypropyl)amine, N-2'-aminoethyl-N-propanolamine, 4- amino-N-butyl alcohol, methyl 3-amino-3-deoxy-A-D-mannopyranoside, N-butyl-4- hydroxybutylamine, 4-amino-4-(3-hydroxypropyl)-1 ,7-heptanediol, 1 -hexylamine, 1 - octylamine, 1 -nonylamine, 1 -decylamine, laurylamine, 1 -tetradecylamine, 1 - hexadecylamine, 3-amino-2-hydroxypropionic acid, 3-amino-2-hydroxy-4- phenylbutanoic acid, 4-amino-3-hydroxybutyric acid, and mixtures thereof.

According to another preferred embodiment of the invention, the amines of formula (V) used are of formula (Vf) and in particular the amines below, the enantiomers thereof if they exist, and the hydrates thereof: gerontine, N-[3-aminopropyl]-1 ,4-butanediamine,

1 .4- butanediamine, 4-(ethylamino)-N-butylamine, 2-[3-(2-hydroxy-1 ,1 -bis- hydroxymethylethylamino)propylamino]-2-hydroxymethylpropane- 1 ,3-diol, 1 ,3-diamino- 2-hydroxypropane, N,N'-bis(2-aminoethyl)propane-1 ,3-diamine, 3- methylaminopropylamine, 1 ,3-diaminopropane, N,N'-dimethyltrimethylenediamine, 2,2- dimethyltrimethylenediamine, 2,2-dimethyl-1 ,3-diaminopropane, N-(2-hydroxyethyl)-1 ,3- diaminopropane, N-(2-hydroxyethyl)-1 ,3-diaminopropane, cystamine, 1 ,5 diaminopentane, 1 ,6-diaminohexane, lauraminopropylamine, 2-methylheptylamine (2- (N-methyl)heptylamine), ethylenediamine, N,N-bis(2-hydroxyethyl)ethylenediamine, 3- aminoalanine, beta-N-methylaminoalanine, ethyl 3-aminoprolinate, 2,4-diamino-N- butyric acid, N-[3-(trimethoxysilyl)propyl]ethylenediamine, or mixtures thereof.

According to another preferred embodiment of the invention, the amines used are of formula (Vg) and in particular the compounds listed below, the enantiomers thereof if they exist, and the hydrates thereof: (4-)aminosalicylic acid, methyl para-aminobenzoate, benzocaine, aminobenzoic acid, 4-amino-m-anisic acid, 4-amino-3-hydroxybenzoic acid, methyl 3,4-diaminobenzoate, methyl-4-amino-3-methoxybenzenecarboxylic acid, 2- aminoanisole-4-carboxylic acid, 3-amino-4-hydroxybenzoic acid, ethyl 3- aminobenzoate, 1 -amino-3-carboxybenzene, methyl 2-aminobenzoate, ethyl anthranilate, and mixtures thereof. Use may also be made of the following amines, which may or may not be in salt form: lauroylethylenediamine, octopamine, oleamine, palmitamine, 2-(2-aminoethoxy)ethanol, mecamylamine, tranylcypromine, methyl[2-(3-trimethoxysilylpropylamino)ethylamine], bis(triethoxysilylpropyl)amine, N1 -(3-(trimethoxysilyl)propyl)hexane-1 ,6-diamine, diethylenetriaminopropyltrimethoxysilane, N-(3-triethoxysilylpropyl)ethylenediamine, N- (3-trimethoxysilylethyl)ethylenediamine.

The primary or secondary amine(s) are preferably chosen from the compounds of formula (V) and most especially from the compounds of formula (Vb) or (Vc), with, more particularly, Y representing -NH-, (Vd) in which Y more particularly represents an oxygen atom or -NH-, (Ve) with Y most particularly representing an oxygen atom, OH or a methylene group optionally substituted by a hydroxyl radical, (Vf) and (Vg), alone or in a mixture.

The non-heterocyclic nitrogen-based compound is preferably chosen from guanidine (especially in hydrochloride form), lysine, N-lauroyl lysine, and arginine.

The amino compound may also be an amino polymer, in particular chosen from amino- based polymers containing primary amine groups. These are polymers resulting from the polymerization of monomers, the polymer comprising at least 2 primary amine groups -NH 2 .

The amino polymer may especially be chosen from:

poly((C2-C5)alkyleneimine)s, and in particular polyethyleneimines and polypropyleneimines, especially linear or branched poly(ethyleneimine)s (for example that sold under the reference 46,852-3 by Aldrich Chemical);

- poly(allylamine) (for example that sold under the reference 47,913-6 by Aldrich Chemical or by Beckmann-Kenko);

- polyvinylamines and copolymers thereof, in particular with vinylamides; mention may especially be made of vinylamine/vinylformamide copolymers (the vinylamine content possibly ranging from 30% to 90% by weight of the total weight of the polymer), such as those sold under the name Lupamin® 9030 by BASF;

- polyamino acids which have Nhb groups, such as polylysine; for example that sold by JNC Corporation;

- aminodextran, such as that sold by CarboMer Inc;

- vinylamine/vinyl alcohol copolymers, such as those sold by Chemwill;

- acrylamidopropylamine polymers;

- chitosans, such as those sold under the names Zenvivo® Protect and Zenvivo Aqua by Clariant;

- dendrimers containing terminal NH2 functions such as the PAMAM (polyamidoamines) dendrimers sold by Dendritech.

Preferably, the amino polymer is chosen from: - poly(ethyleneimine)s;

- poly(allylamine);

- polylysine;

- vinylamine/vinylformamide copolymers;

- chitosans;

- dendrimers containing terminal NH2 functions such as the PAMAM (polyamidoamines) dendrimers sold by Dendritech.

More preferentially, the amino polymer is a polylysine.

Advantageously, the amino polymer has a weight-average molecular weight ranging from 200 to 1 000 000 g/mol, preferably ranging from 300 to 500 000 g/mol.

Preferably, the amino polymer is water-soluble. The term "water-soluble polymer" means a polymer with a solubility in water, at 25°C, of at least 0.1 g/l.

The nitrogen-based compound is preferably chosen from Nicotinamide Adenine Diphosphate, pyridoxine, adenosine triphosphate disodium salt, adenosine diphosphate, theobromine, adenosine, thymidine, guanine, cytidine, uridine, caffeine, xanthine, allantoin, nicotinic acid, trigonelline, paraxanthine, histidine, guanidine (especially in hydrochloride form), lysine, polylysine, N-Lauroyl lysine, arginine and adenine.

The nitrogen-based compound is preferentially chosen from pyridoxine, adenosine triphosphate disodium salt, adenosine, caffeine, allantoin, trigonelline, histidine, polylysine, N-Lauroyl lysine, arginine and adenine.

The nitrogen-based compound is more preferentially chosen from pyridoxine, adenosine triphosphate disodium salt, adenosine, allantoin, trigonelline, histidine, polylysine, arginine and adenine.

The nitrogen-based compound is more preferentially chosen from pyridoxine, adenosine triphosphate disodium salt, adenosine, allantoin, histidine and adenine.

The nitrogen-based compound is even more preferentially chosen from adenosine triphosphate disodium salt and histidine.

According to a preferred mode of the invention, the nitrogen-based compound is adenosine triphosphate disodium salt. The nitrogen-based compound may be present in the coloured powder at a weight ratio of nitrogen-based compound/anthocyanin ranging from 1/10 to 10/1 , preferably ranging from 1/3 to 3/1 by weight, preferentially ranging from 1/2 to 2/1 by weight. Advantageously, when the coloured powder comprises an amino acid, it does not contain tannic acid or a gallotannin derivative thereof, or the mixtures thereof.

Tannic acid (or hydrolysable gallotannin) is a mixture of polygalloyi glucoses or of polygalloyi quinic acid esters with a number of galloyl units per molecule ranging from 2 to 12, depending on the plant source used to extract the tannic acid.

The chemical formula of commercial tannic acid commonly given is C76H52O46, which corresponds to decagalloyl glucose.

Gallotannin derivatives of tannic acid is intended to mean the polygalloyi glucose compounds and the polygalloyi quinic acid esters described previously which are present in tannic acid.

Commercial tannic acid is usually extracted from tara husk seeds (Caesalpinia spinosa), gall nuts or excrescences thereof which form on the young branches of Quercus infectoria and belonging to the species of Quercus L. (Fam. Fagaceae), or gall nuts of various species of sumac.

The coloured powder according to the invention is blue in colour.

Blue is the hue of the portion of the visible light spectrum located between green and indigo. One method for measuring colour, proposed by the Commission Internationale de I'Eclairage (CIE) (International Commission on Illumination), is the CIE 1976 L * a * b * colour scale, hereinafter denoted CIELAB (CIE technical report, Colorimetry, 2 nd Edition, CIE 15.2 - 1986, revised edition 1996). The CIELAB colour space is obtained by arranging the values L * , a * , b * as rectangular coordinates. The coordinates of an object and the light intensity are measured on a scale ranging from 0 (black) to 100 (absolute white).

The coordinates a * and b * do not have any specific numerical limits. The parameter a * ranges from pure green (negative a * ) to pure red (positive a * ), while the parameter b * ranges from pure blue (negative b * ) to pure yellow (positive b * ).

The hue angle h a b is calculated from the values a * and b * according to the equation: hab = arctang (b * /a * )

and for which h a b ranges from 0° to 90° if b * and a * are both positive, between 90° and 180° if b * is positive and a * is negative, between 180° and 270° if b * and a * are both negative, and between 270° and 360° if b * is negative and a * is positive.

The colour blue within the context of the present invention means that the hue angle h a b is between 210° and 325°, and preferably between 250° and 300°. Preparation process: The coloured powder may be prepared in a first step by mixing in a buffered solution, having a pH of between 4.5 and 5.5, of the anthocyanin (especially in plant extract form), then adding the metal ions in the form of salts, and the nitrogen-based compound, and then the pH of the mixture is adjusted to between 4.5 and 6 (to cause the powder formed to precipitate).

In a second step, the solid phase of the mixture obtained in the first step is isolated, especially by centrifugation or by filtration, then dried, for example by lyophilization, to thereby recover the coloured powder. The composition according to the invention comprising the coloured powder also comprises a physiologically acceptable medium, that is to say a medium compatible with the keratin fibres and/or materials of a living creature, in particular of humans, such as, for example, in a non-limiting manner, the skin, the lips, the nails, the hair, the eyelashes or the eyebrows.

The composition according to the invention may also contain cosmetic additives such as fragrances, preservatives, film-forming polymers, fillers, UV screening agents, thickeners, oils, gums, waxes, surfactants, moisturizers, vitamins, proteins and hydrolysates thereof, ceramides, antioxidants, anti-free-radical agents, organic solvents, inorganic pigments, organic pigments, nacres, dyes, water.

The amounts of these various additives are those conventionally used in the cosmetics field, and may range, for example, from 0.01 % to 30% of the total weight of the composition. In general, the amounts are adjusted as a function of the formulation prepared.

The composition may be anhydrous or contain water.

A cosmetic composition according to the invention may be in the form of a product for making up the hair (in particular a coloured coating for the hair), the eyelashes, the eyebrows, the skin, the lips or the nails.

Other characteristics and advantages of the invention will emerge more clearly from the examples that follow, which are given as non-limiting illustrations. In the text hereinbelow or hereinabove, the proportions are given as weight percentages, unless otherwise indicated.

Examples 1 to 11 : Preparation of powders and colorimetric evaluation

The following 3 solutions were first prepared: Anthocyanin solution 1 : aqueous-alcoholic extract of bilberry fruit (BILBERRY FRUIT PE25% ANTHOCYANOSIDES from NATUREX): 10 g (i.e. 2.5 g of anthocyanin active material in 1 litre of mixture comprising 90% by volume of 0.2 M sodium acetate buffer pH 5 in water and 10% by volume of ethanol.

Solution of amino compound 2: 0.2 M adenosine triphosphate (ATP) disodium salt in 0.1 M sodium acetate buffer

For the other nitrogen-based compounds tested, the solution 2 was prepared at 0.05 M or 0.1 M depending on the solubility so as to obtain a solution of the dissolved compound.

Solution of metal ions 3: Ammonium aluminium sulfate dodecahydrate at 0.2 M in 0.1 M sodium acetate buffer

Powder preparation method:

750 ml of solution 1 containing 10 g of bilberry extract (i.e. 2.5 g AM of anthocyanins) was mixed with 125 ml of solution 2 of ATP.

The mixture was stirred for 15 minutes at 25 °C, then 125 ml of solution 3 of ammonium aluminium sulfate dodecahydrate were added, then left again with stirring for 15 minutes under the same conditions; the pH of the mixture was then adjusted to pH 5.09 by addition of sodium hydroxide.

Thus, the amounts used in the final reaction mixture are as follows:

Bilberry extract: 5 g/l

ATP: 0.025 M

Ammonium aluminium sulfate dodecahydrate: 0.025 M

The mixture was then centrifuged to recover the final solid phase which was washed with water. This solid phase was then frozen at -22°C then lyophilized, or else was dried in an oven under vacuum at 45°C.

A blue coloured powder was thus recovered.

Other powders were prepared by replacing the ATP with another nitrogen-based compound as indicated in the table below.

Evaluation of the colorimetric properties of the powders:

For each powder obtained, the colorimetric properties were evaluated according to the following protocol:

A paste with the following composition was used (% by weight)

- Polybutene (Indopol H 100 from Ineos) 13.25%

- Polybutene (Indopol H 1500 from Ineos) 10%

- Polyethylene wax (Performalene 500-L polyethylene

from New Phase Technologies) 6%

- hydrogenated myristic esters of olive oil fatty acids

(PHYTOWAX OLIVE 14L48 from Sophim) 4.5% - Shea butter 2.8%

- Caprylic, capric, isostearic,

stearic, hydrostearic and adipic glyceryl fatty acid ester

(SOFTISAN 649 from Cremer Oleo) 7.6%

- Petroleum jelly (ULTIMA WHITE PET USP from Calumet Speciality) 15%

- Diisostearyl malate 17.5%

- 2-Octyldodecanol 20%

- Silica Silylate (Aerogel VM-2270 from Dow Corning) 0.8%

- Polyurethane powder

(PLASTIC POWDER D 400 from TOSHIKI PIGMENT) 2%

- Tocopherol acetate 0.5%

- Dibutylpentaerythrityl tetrahydroxycinnamate 0.05%

A first paste was prepared by mixing 5% by weight of the powder to be evaluated and 95% by weight of the paste described above. Mixing was first carried out manually with a spatula, then continued in a mill to obtain a homogeneous paste.

The paste was then spread on an Erichsen contrast card, ref Typ 24/5, 50 μηη thick; the colour of the deposit obtained spread on the white part and on the black part of the contrast card was measured at 3 points for each part of the card on the Minolta CM2600d colorimeter. The mean of 3 measurements made on each part of the card was calculated. Thus, the values Li , ai , bi for the deposit on the white part and Lr, ar, br for the deposit on the black part were obtained.

The following parameters were taken (mean of the 3 measurements taken) from the colorimetric reading on the white part of the contrast card:

Lightness Li

Chromaticity C = ( (ai ) 2 + (bi ) 2 ) 1/2 Hue angle H = arctang (bi / ai )

Coverage was determined by the Contrast Ratio CR = (ΥΊ/Υι)

Y being the component of the Xyz colour space also measured by the colorimeter and corresponding to the percentage reflection.

The higher the CR value, the greater the coverage.

A second paste was prepared containing 10% by weight of the powder to be evaluated and 90% by weight of the paste described above. In this paste, the powder gives what is referred to as a full tone. A third paste was prepared, containing 10% by weight of powder, 7.5% by weight of alumina/silica/trimethylolpropane-treated rutile titanium dioxide (TIPAQUE PF-671 COSMETIC GRADE from ISHIHARA SANGYO) and 82.5% by weight of the paste described above. In this paste, the powder is mixed with the white titanium dioxide pigment, thereby giving what is referred to as a reduced tone of the powder in this paste.

The tinting strength (TS) of the powder was then determined according to the following protocol:

2 g of the second paste were deposited in a small cup (made of galvanized steel and rectangular in shape; length = 25.8 mm, width = 22.8 mm, height = 3.6 mm), then the same operation was carried out with the third paste.

The content of each small cup was read with the colorimeter to measure the colorimetric parameters l_2, a2, b2 of the second paste (full tone) and those of the third paste (L3, a3, b3) (reduced tone).

The tinting strength TS of the powder = [ (l_3 - L2) 2 + (a3 - a2) 2 + (b3 - b2) 2 ] 1/2

The smaller the TS value, the greater the tinting strength.

The photostability of the powder was determined according to the following protocol:

The small cup containing the third paste (reduced tone) was exposed for one hour to irradiation under a LOT Oriel solar simulator (1600 W power). Then, in the body of the irradiated paste, the parameters L3', as', b3' were measured with the colorimeter.

The photostability was determined by calculating the difference ΔΕ between the colour measurements taken before and after irradiation: Photostability = ΔΕ = ((L3'-L3) 2 + (a3'-as) 2 + (b3'-b3) 2 ) ½

The following results were obtained:

(1 ) polylysine sold under the reference P8920 by Aldrich

(2) sold under the reference AMIHOPELL by Ajinomoto

The results obtained show that: All the powders are blue in colour (hue angle between 264 and 287).

The powders have good properties of chromaticity and photostability and also at least one good property from properties of coverage, tinting strength and lightness.

Comparative Example 12:

A powder 1 ' was prepared, similar to the powder 1 described above but with modification of the concentrations of the ingredients used during the preparation, as described below:

Bilberry extract: 8.8 g/l

ATP: 1 1 .2 g/l (i.e. 0.02 M)

Ammonium aluminium sulfate dodecahydrate: 19 g/l (i.e. 0.0419 M)

A powder 1 'a, similar to the powder 1 ' but without using ATP (obtained with the bilberry extract and ammonium aluminium sulfate dodecahydrate) and a powder 1 'b, without using ammonium aluminium sulfate dodecahydrate (obtained with the bilberry extract and ATP), were also prepared.

The colorimetric properties of these powders were measured, and the yield of powder obtained was also noted.

The following results were obtained:

The powder V (ATP) has good chromaticity, good coverage and a good hue angle, and also good photostability.

The powder 1 'a has good tinting strength, a good hue angle and good coverage, but poorer chromaticity and too red a colour (a = 6.5).

The powder 1 'b was obtained with a very low yield and has very poor chromaticity, and also a poorer hue angle and coverage.

The colorimetric properties of the powder 1 ' according to the invention were also compared with those of another powder described in the prior art (example 3 from FR2994693) prepared from bilberry extract, iron sulfate and tannic acid.

The following results were obtained:

The results obtained show that the powder of example 3 of FR2994693 based on bilberry/iron sulfate/tannic acid has poor chromaticity and hence an insufficiently vibrant blue colour.

Examples 13 and 14:

2 powders according to the invention were prepared with different salts using the following final concentrations according to the procedure described above in examples 1 to 1 1 :

Bilberry extract: 8.8 g/l

ATP: 1 1.2 g (i.e. 0.02 M)

salt: AINH4(SC>4)2 dodecahydrate at 0.0419 M (example 1 ') or aluminium chloride at 0.055 M (example 13) or zinc sulfate at 0.052 M (example 16)

The following results were obtained:

The powder 14 (zinc sulfate) is the best performer: it has good hue angle, chromaticity, tinting strength and coverage properties. Nonetheless, it has a redder "a".

The powder 13 (aluminium chloride) has good hue angle, chromaticity, and lightness properties. The yield is higher than that of powder 14.

Examples 15 and 16:

2 powders according to the invention were prepared with black rice extracts using the following final concentrations according to the procedure described above in examples 1 to 1 1 :

Black rice extract: 8.8 g/l

ATP: 1 1 .2 g/l (i.e. 0.02 M)

Ammonium aluminium sulfate dodecahydrate: 19 g/l (i.e. 0.0419 M)

For the powder 15, the black rice extract used is that sold under the name RED RICE RED by Chenguang Biotech group.

For the powder 16, the black rice extract used is that sold under the name BLACK RICE extract by DAXINGANLING LINGONBERRY GROUP.

The colorimetric properties of these powders were measured.

The following results were obtained: Example Extracts C ΔΕ TS CR (%) L H pigment

r Bilberry 23.1 2.9 20.3 59.6 32.1 283

15 Black rice 18.1 3.7 18.2 55.9 32.2 278

16 Black rice 19.7 3.7 19.1 57.2 32.1 281

The powders 15 and 6 have good chromaticity and photostability properties.

Example 17: eyeshadow example

The following eyeshadow composition is prepared:

Magnesium stearate 4%

Talc 30%

Glyceryl triisostearate 5%

Hydrogenated polydecene 5%

Blue powder according to one of examples 1 to 1 1 or 1 ' or 13 to 16 q.s. 100%

The shadow applied to the eyelids has a very attractive blue colour.