Use of hydroxyanthraquinones for the coloration of human keratin fibres

The present invention relates to the use for the dyeing of human keratinous fibers, and in particular live hair, of hydroxyanthraquinones to dyeing processes as well as dyeing compositions based on such compounds.

Hair dye has already been used for the direct dyeing of aminoanthraquinone derivatives described, inter alia, in the French patents of the proprietor no.^s 1422016,1391675,1401163,1379649, 1430091,1574275. Moreover, it has already been proposed to use for hair certain hydroxyanthraquinones described in particular in the French patent holder No. 2106264.

The licensee has discovered that, surprisingly, a particular class of hydroxyanthraquinones was able to directly obtain a coloratin of human hair even at room temperature. These compounds give rise to dyes with good resistance to light, washing, weather, perspiration. Moreover, they make it possible to obtain very varied colorations.

These dyes also have the advantage of being very stable in solution, in the cosmetic media usually used for this type of dyeing.

In addition, these dyes generally have low toxicity and good affinity making them particularly suitable for dyeing human hair.

This type of dye has already been recommended for the dyeing of textile materials especially with etching agents such as transition metal derivatives (chromium dyes), unusable metals in the field of hair dye due to the risk of breakage that they can cause with subsequent treatments such as permanent, but it was never thought to use these compounds in the conditions of dyeing human hair.

The present invention therefore relates to compositions for coloring. human hair made from hydroxyanthraquinones.

It also relates to a staining process using these hydroxyanthraquinones. Other objects of the invention

651 202 will appear on reading the description and examples which follow.

The hydroxyanthraquinones used for the dyeing of human hair in accordance with the present invention are more particularly characterized by the fact that they correspond to the general formula:

<img file="CH651202A5_D0001.tif" />

in which R_ls R₂, R₃, R₄, R₅, R₆, R₇ and R_s designate, independently of one another, a hydrogen atom, a hydroxyl group, alkyl, alkyl substituted by a hydroxyl group, amino or acyl, alkoxy, nitro, halogen, SO₃H, CHO, CO₂H, SO₃Na, - CO₂R 'wherein R' denotes alkyl or an alkali metal provided that:

at least two groups Rj, R₂, R₃, R₄, R₅, R_e, R? or R_s denote hydroxyl and that when Rt and R₂ designate OH, R₅, R &lt;5, R₇, R_s designating hydrogen, then at least one of the two groups R₃, R₄ is different from hydrogen, or when Rj and R₃designate OH, R₂ and R₄ designating hydrogen, one or two of the substituents R₅, R₆, R₇ and R₈ designating hydroxyl, then at least one of the substituents R_s, R₆, R₇ and R₈ is different from hydrogen, alkyl or halogen.

Preferred alkyl groups have 1 to 4 carbon atoms and in particular are methyl or ethyl.

The alkali metals represented by R 'preferably denote sodium, potasium.

The more particularly preferred compounds according to the invention are the following compounds:

1,4-dihydroxyanthraquinone,

1.2.4- trihydroxyanthraquinone,

1,2,7-trihydroxyanthraquinone,

1,2,5,8-tetrahydroxyanthraquinone,

3-carboxy 1,2,4-trihydroxyanthraquinone,

2-carboxy 1-methyl 3,5,6,8-tetrahydroxyanthraquinone,

3-sulfo 1,2,4-trihydroxyanthraquinone,

3-sulfo 1,2-dihydroxyanthraquinone,

5.8, -dichloro-1,4-dihydroxyanthraquinone,

1,8-dihydroxy-3-hydroxymethylanthraquinone.

Other compounds of particular interest in the context of the present invention are the following compounds:

1,2-dihydroxy-4-nitroanthraquinone,

2- sulfo 1,4-dihydroxyanthraquinone,

2,6-disulfo 1,4-dihydroxyanthraquinone,

3-nitro 1,2,4-trihydroxyanthraquinone,

1.2.5- trihydroxyanthraquinone,

3-sulfo 1,2,6-trihydroxyanthraquinone,

3-nitro 1,2,6-trihydroxyanthraquinone,

3-sulfo 1,2,7-trihydroxyanthraquinone,

3-sulfo-1,4,5-trihydroxyanthraquinone,

1.2.4.5.8- pentahydroxyanthraquinone,

1.2.4.5.6.8-hexahydroxyanthraquinone,

3.7-disulfo 1,2,4,5,6,8-hexahydroxyanthraquinone,

1.2.4.5.7.8-hexahydroxyanthraquinone,

3-nitro 1,2,4,5,7,8-hexahydroxyanthraquinone,

2-methyl 1,3-dihydroxyanthraquinone,

2-carboxy-1,3-dihydroxyanthraquinone,

2-methyl 1,6-dihydroxyanthraquinone,

6-methyl 1,2,5-trihydroxyanthraquinone,

5-carboxy-1,2,4-trihydroxyanthraquinone,

7-chloro-3-methyl-1,5,6,8-tetrahydroxyanthraquinone,

2- carboxy-3-methyl 1,5,6,8-tetrahydroxyanthraquinone,

3-methyl-1,2,4,7,8-pentahydroxyanthraquinone,

3-methyl 1,2,5,6,7,8-hexahydroxyanthraquinone,

3-methyl 6-methoxy 1,5,7,8-tetrahydroxyanthraquinone,

1.2.6- trihydroxyanthraquinone,

1,8-dihydroxy-3-carboxyanthraquinone.

The family of hydroxyanthraquinones is particularly rich in natural compounds, these compounds belonging especially to the family of polyhydroxyanthraquinones unsubstituted or substituted by carboxylic groups, halogen, alkyl or substituted alkyl.

Among the natural compounds belonging to the family of the above-mentioned hydroxyanthraquinones, mention may be made more particularly of:

Table 1

<img file="CH651202A5_D0002.tif" />

<td colspan="10">Substituents</td>

<td>Usual name</td><td></td><td>r₂</td><td>r₃</td><td>r₄</td><td>r₅</td><td>r₆</td><td>r₇</td><td>r₈</td><td>Origin</td>

<td>3-Méthylalizarine</td><td>OH</td><td>OH</td><td>ch₃</td><td></td><td></td><td></td><td></td><td></td><td>Digitalis spp</td>

<td>6-Méthylalizarine</td><td>OH</td><td>OH</td><td></td><td></td><td></td><td>-ch₃</td><td></td><td></td><td>Hymenodyctyen Excelsum coprosma parviflora</td>

<td>Xanthopurpurine</td><td>OH</td><td></td><td>OH</td><td></td><td></td><td></td><td></td><td></td><td>Rubia spp - Gallium spp, etc.</td>

<td>rubiadin</td><td>OH</td><td>CH₃</td><td>OH</td><td></td><td></td><td></td><td></td><td></td><td>Rubia tinctorium - Morinda spp - Coprosma spp</td>

<td>Lucidine</td><td>OH</td><td>CH, OH</td><td>OH</td><td></td><td></td><td></td><td></td><td></td><td>Coprosma spp - Asperula odorata</td>

<td>Nordamnacanthal</td><td>OH</td><td>CHO</td><td>OH</td><td></td><td></td><td></td><td></td><td></td><td>Morinda spp - Damnacanthus major</td>

<td>munjistin</td><td>OH</td><td>COOH</td><td>OH</td><td></td><td></td><td></td><td></td><td></td><td>Rubia spp - Rubia cordifolia</td>

651 202

Table 1 (continued)

<td colspan="10">Substituents</td>

<td>Usual name</td><td>Ri</td><td>r₂</td><td>r₃</td><td>R4</td><td>r₅</td><td>Re</td><td>r₇</td><td>r₈</td><td>Origin</td>

<td>chrysophanol</td><td>OH</td><td></td><td>ch₃</td><td></td><td></td><td></td><td></td><td>OH</td><td>Rheum spp - Rumex - Rhamnus spp.</td>

<td>2-Méthylquinizarine</td><td>OH</td><td>ch₃</td><td></td><td>OH</td><td></td><td></td><td></td><td></td><td>Tectonagrandis</td>

<td>Soranjidiol</td><td>OH</td><td>ch₃</td><td></td><td></td><td></td><td>OH</td><td></td><td></td><td>Morbida spp - Co-</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>prosino, acerosa</td>

<td>Phomarine</td><td>OH</td><td></td><td>ch₃</td><td></td><td></td><td>OH</td><td></td><td></td><td>Phoma Fove ata Di-</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>gitalis spp</td>

<td>Aloe Emodine</td><td>OH</td><td></td><td>ch₂Oh</td><td></td><td></td><td></td><td></td><td>OH</td><td>Aloe spp - Asphode</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>read albus</td>

<td>Rhein</td><td>OH</td><td></td><td>COOH</td><td></td><td></td><td></td><td></td><td>OH</td><td>Rheum spp - Rumex spp - Cassia spp</td>

<td>Anthragallol (and</td><td>OH</td><td>OH</td><td>OH</td><td></td><td></td><td></td><td></td><td></td><td>Coprosma lucida -</td>

<td>thyléthers)</td><td>OH</td><td>OH</td><td>och₃</td><td></td><td></td><td></td><td></td><td></td><td>Rubia tinctorium</td>

<td></td><td>och₃</td><td>OH</td><td>OH</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>OH</td><td>och₃</td><td>OH</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Glitter</td><td>OH</td><td>OH</td><td></td><td>OH</td><td></td><td></td><td></td><td></td><td>Rubia spp - Gallium spp - Asperula odorata</td>

<td>Pseudopurpurine</td><td>OH</td><td>OH</td><td>COOH</td><td>OH</td><td></td><td></td><td></td><td></td><td>Rubia spp - Gallium spp - Asperula spp</td>

<td>Morindon</td><td>OH</td><td>ch₃</td><td></td><td></td><td>OH</td><td>OH</td><td></td><td></td><td>Morinda spp - Coprosma australis</td>

<td>Obtusifoline</td><td>och₃</td><td>OH</td><td>ch₃</td><td></td><td></td><td></td><td></td><td>OH</td><td>Cassia obstusifolia</td>

<td>homonataloin</td><td>OH</td><td></td><td>ch₃</td><td></td><td></td><td></td><td>OH</td><td>OCH₃</td><td>Aloe spp</td>

<td>Juzunol</td><td>och₃</td><td>CH₂OH</td><td>OH</td><td></td><td>OH</td><td></td><td></td><td></td><td>Damnacanthus major</td>

<td>Norjuzunal</td><td>OH</td><td>CHO</td><td>OH</td><td></td><td>OH</td><td></td><td></td><td></td><td>Damnacanthus major</td>

<td>Juzunal</td><td>och₃</td><td>CHO</td><td>OH</td><td></td><td>OH</td><td></td><td></td><td></td><td>Damnacanthus spp.</td>

<td>Asperthécine</td><td>OH</td><td>OH</td><td>CH₂0H</td><td></td><td>OH</td><td>OH</td><td></td><td>OH</td><td>Aspergillus spp</td>

<td>Macrosporine</td><td></td><td>ch₃</td><td>OH</td><td></td><td>OH</td><td></td><td>och₃</td><td></td><td>Aitenaria spp.</td>

<td>Coelulatine</td><td>OH</td><td>ch₂Oh</td><td>OH</td><td></td><td></td><td></td><td></td><td>OH</td><td>Coelospermun reticu-</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>latum</td>

<td>physcion</td><td>OH</td><td></td><td>ch₃</td><td></td><td></td><td>OCH₃</td><td></td><td>OH</td><td>Rheum spp - Rumex</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>spp</td>

<td>Questine</td><td>OH</td><td></td><td>ch₃</td><td></td><td></td><td>OH</td><td></td><td>och₃</td><td>Frequent penicillium</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>tans - Aspergillus</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>terreus</td>

<td>Questinol</td><td>OH</td><td></td><td>ch₂Oh</td><td></td><td></td><td>OH</td><td></td><td>och₃</td><td>Frequent penicillium</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>tans</td>

<td>7-Chloroemodine (and</td><td>OH</td><td></td><td>ch₃</td><td></td><td></td><td>OH</td><td>Cl</td><td>OH</td><td>Nephroma laeviga-</td>

<td>methyl ethers)</td><td>OH</td><td></td><td>ch₃</td><td></td><td></td><td>OCH₃</td><td>Cl</td><td>OH</td><td>tum - Caloplaca</td>

<td></td><td>och₃</td><td></td><td>ch₃</td><td></td><td></td><td>OH</td><td>Cl</td><td>OH</td><td>spp</td>

<td>5,7-Dichloroémo-</td><td>OH</td><td></td><td>ch₃</td><td></td><td>Cl</td><td>OH</td><td>Cl</td><td>OH</td><td>Anaptychia obscure</td>

<td>dine</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>rata</td>

<td>7-Chlorocitroroseine</td><td>OH</td><td></td><td>ch₂Oh</td><td></td><td></td><td>OH</td><td>Cl</td><td>OH</td><td>Aspergillus tumiga-</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>you s</td>

<td>Fallacinol</td><td>OH</td><td></td><td>ch₂Oh</td><td></td><td></td><td>OCH₃</td><td></td><td>OH</td><td>Teloschist spp Xanthoria spp</td>

<td>Carvioline</td><td>och₃</td><td></td><td>ch₂Oh</td><td></td><td></td><td>OH</td><td></td><td>OH</td><td>Penicillium roseopur-</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>pureum</td>

<td>Fallacinal</td><td>OH</td><td></td><td>CHO</td><td></td><td></td><td>och₃</td><td></td><td>OH</td><td>Xanthoria spp - Ca-</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>loplaca spp</td>

<td>Emodic acid</td><td>OH</td><td></td><td>COOH</td><td></td><td></td><td>OH</td><td></td><td>OH</td><td>Penicillium cyclopium - Xanthoria parietina</td>

Table I (continued)

<td colspan="10">Substituents</td>

<td>Usual name</td><td>R</td><td>r₂</td><td>Rs</td><td>r *</td><td>r₅</td><td>r₆</td><td>r₇</td><td>r₈</td><td>Origin</td>

<td rowspan="2">Parietal acid</td><td>OH</td><td></td><td>COOH</td><td></td><td></td><td>och₃</td><td></td><td>OH</td><td>Xanthoria spp - Ca-</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>loplaca spp</td>

<td>Endocrocine</td><td>OH</td><td>co₂h</td><td>ch₃</td><td></td><td></td><td>OH</td><td></td><td>OH</td><td>Nephromopsis endo-</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>crocea</td>

<td>Dermoluteine</td><td>OH</td><td>COOH</td><td>ch₃</td><td></td><td></td><td>OH</td><td></td><td>och₃</td><td>Dermocybe</td>

<td>5-Chlorodermolu-</td><td>OH</td><td>COOH</td><td>ch₃</td><td></td><td>Cl</td><td>OH</td><td></td><td>och₃</td><td>Dermocybe spp.</td>

<td>teine</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Dermocybine</td><td>OH</td><td></td><td>ch₃</td><td></td><td>OH</td><td>och₃</td><td>OH</td><td>OH</td><td>Cortinarius blood</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>neus</td>

<td rowspan="2">Nalgiovensine</td><td>OH</td><td></td><td>ch₂ ch-ch₃</td><td></td><td></td><td>och₃</td><td></td><td>OH</td><td>Penicillium nalgium</td>

<td rowspan="2"></td><td rowspan="2"></td><td rowspan="2">1 OH</td><td rowspan="2"></td><td rowspan="2"></td><td rowspan="2"></td><td rowspan="2"></td><td rowspan="2"></td><td rowspan="2">vensis</td>

<td></td>

<td rowspan="2">Nalgiolaxine</td><td>OH</td><td></td><td>ch₂ch-ch₃</td><td></td><td></td><td>och₃</td><td>Cl</td><td>OH</td><td>Penicillium nalgium</td>

<td rowspan="2"></td><td rowspan="2"></td><td rowspan="2">1 OH</td><td rowspan="2"></td><td rowspan="2"></td><td rowspan="2"></td><td rowspan="2"></td><td rowspan="2"></td><td rowspan="2">vensis</td>

<td></td>

<td>Ac. Ptilométrique</td><td>OH</td><td>COOH</td><td>nC₃H₇</td><td></td><td></td><td>OH</td><td></td><td>OH</td><td>Ptilometra australis</td>

<td>Islandicine</td><td>OH</td><td></td><td>ch₃</td><td>OH</td><td></td><td></td><td></td><td>OH</td><td>Penicillium spp.</td>

<td>Helminthosporine</td><td>OH</td><td></td><td>ch₃</td><td></td><td>OH</td><td></td><td></td><td>OH</td><td>Pyrenolora graminea - Helminthospore</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>rium spp</td>

<td>Digitopurpon</td><td>OH</td><td></td><td>ch₃</td><td>Oh</td><td>OH</td><td></td><td></td><td></td><td>Digitalis purpura</td>

<td>Copareolatin (and</td><td></td><td></td><td>ch₃</td><td>OH</td><td></td><td>OH</td><td>OH</td><td>OH</td><td>Coprosma areolata</td>

<td>methyl ethers) 7-Hydroxyémodine</td><td>OH</td><td></td><td>ch₃</td><td></td><td></td><td>OH</td><td>OH</td><td>OH</td><td>Heliococcus confusus</td>

<td rowspan="2">Dermoglaucine</td><td>OH</td><td></td><td>ch₃</td><td></td><td></td><td>och₃</td><td>OH</td><td>OH</td><td>Cortinarius blood</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>neus</td>

<td>Majoronal</td><td>OH</td><td>CHO</td><td>OH</td><td>OH</td><td>och₃</td><td></td><td></td><td></td><td>Damnacanthus major</td>

<td>Isoerythrolaccine</td><td>OH</td><td>OH</td><td>OH</td><td></td><td></td><td>OH</td><td></td><td>ch₃</td><td>Laccifer lacca</td>

<td>Ac. cêréoalbolinique</td><td>OH</td><td>OH</td><td>OH</td><td></td><td></td><td>OH</td><td>COOH</td><td>ch₃</td><td>Ulbolt-ceroplasts</td>

<td>Ac. kermesic</td><td>OH</td><td></td><td>OH</td><td>OH</td><td></td><td>OH</td><td>COOH</td><td>ch₃</td><td>Kermococcus ilicis</td>

<td>Ac. carminic</td><td>OH</td><td>glucoside</td><td>OH</td><td>OH</td><td></td><td>OH</td><td>COOH</td><td>ch₃</td><td>Dactylopius coccus</td>

<td>Ac. laccaic D</td><td>OH</td><td></td><td>OH</td><td></td><td></td><td>OH</td><td>COOH</td><td>ch₃</td><td>Laccifer lacca</td>

<td>Xanthorine</td><td>OH</td><td></td><td>ch₃</td><td></td><td>OH</td><td>ch₃</td><td></td><td>OH</td><td>Xanthoria elegans -</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Laurerapurpurina</td>

<td>Valsarin I</td><td>OH</td><td></td><td>ch₃</td><td></td><td>OH</td><td>OH</td><td>Cl</td><td>OH</td><td>Valsaria rubricosa Lasallia papulosa</td>

<td>Valsarine II</td><td>OH</td><td></td><td>ch₃</td><td>OH</td><td></td><td>OH</td><td>Cl</td><td>OH</td><td>Valsaria rubricosa Lasallia papulosa</td>

<td>Clavorubine</td><td>OH</td><td>COOH</td><td>ch₃</td><td></td><td>OH</td><td>OH</td><td></td><td>OH</td><td>Claviceps purpurea</td>

<td>2,5,7-trihydroxy emodin</td><td>OH</td><td>OH</td><td>ch₃</td><td></td><td>OH</td><td>OH</td><td>OH</td><td>OH</td><td>Mypcoblastus sanguinarius</td>

<td>Boletol</td><td>OH</td><td>OH</td><td></td><td>OH</td><td>COOH</td><td></td><td>OR -*</td><td>COOH</td><td>Boletus spp.</td>

<td>Dermorubine</td><td>OH</td><td>COOH</td><td>ch₃</td><td>OH</td><td></td><td>OH</td><td></td><td>och₃</td><td>Dermocybe spp.</td>

<td>5-Chlorodermoru- bine</td><td>OH</td><td>COOH</td><td>ch₃</td><td>OH</td><td>Cl</td><td>OH</td><td></td><td>och₃</td><td>Dermocybe spp.</td>

<td>Erythroglaucine</td><td>OH</td><td></td><td>ch₃</td><td>OH</td><td></td><td>och₃</td><td></td><td>OH</td><td>Aspergillus spp Xanthoria elegans</td>

<td>Cynodontine</td><td>OH</td><td></td><td>ch₃</td><td>OH</td><td>OH</td><td></td><td></td><td>OH</td><td>Helminthosporium</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>spp</td>

<td></td><td>OH</td><td>ch₃</td><td></td><td>OH</td><td>OH</td><td>ch₃</td><td></td><td>OH</td><td>Curvularia spp, etc.</td>

<td>Aurantioobtusine</td><td>och₃</td><td>OH</td><td>ch₃</td><td></td><td></td><td>OH</td><td>och₃</td><td>OH</td><td>Cassia obtusifolia</td>

<td>Obtusine</td><td>och₃</td><td>OH</td><td>ch₃</td><td></td><td></td><td>och₃</td><td>och₃</td><td>OH</td><td>Cassia obtusifolia</td>

<td>Rubrocomatuline</td><td>Oh</td><td></td><td>Oh</td><td>CO (CH₂)₂CH₃</td><td>OH</td><td>och₃</td><td></td><td>OH</td><td rowspan="2">Comatula spp</td>

<td>6-methyl ether</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

651 202

Table 1 (end)

<td colspan="10">Substituents</td>

<td>Usual name</td><td>R</td><td>r₂</td><td>r₃</td><td>r₄</td><td>r₅</td><td>r₆</td><td>r₇</td><td>r₈</td><td>Origin</td>

<td>Ventimaline Viminaline</td><td>OH och₃</td><td>Oh Oh</td><td>ch₃ch₃</td><td>Oh OH</td><td></td><td></td><td>OH OH</td><td>OH och₃</td><td>Ventilago viminalis Ventilago viminalis</td>

The natural compounds can be used in the context of the present invention either in the form of their isolated molecules or, where appropriate, in the form of C or O-glucosides or else in the form of extracts or plants containing them. Particularly preferred plants or plant extracts being those shown in Table 1 above.

The dyeing compositions of human hair according to the present invention are therefore essentially characterized in that they contain, in a cosmetically acceptable medium, at least one dye corresponding to formula I defined above.

These compositions contain these dyes preferably in proportions of between 0.005 to 10% by weight and preferably of 0.01 to 7% by weight.

The compositions for dyeing human hair according to the invention can be in various forms such as liquids, creams, gels, oils, powder or any other form suitable for dyeing hair. They can in particular be packaged in aerosol flasks in the presence of a propellant.

These compositions may be used in the form of coloring lotions, in which case the application is not followed by rinsing or coloring shampoos, dyeing or coloring poultices, in which case the application is followed. a rinse and possibly a shampoo.

One of the particularly preferred embodiments of the compositions according to the invention consists of the presentation in the form of a poultice. In this case, the hydroxyanthraquinones according to the invention and preferably the hydroxyanthraquinones of natural origin that can adopt the various forms mentioned above are prepared in the form of a powder stable in storage and introduced into a solid medium that can be composed of powder, flour, of starchy or mucilaginous substances which are diluted at the time of use with a suitable liquid so as to form a mixture having a consistency suitable for being applied to the head.

The powders used in the poultices according to the invention may consist of insoluble substances such as silicas, plants, clays, pulverized plants after the extraction of their active ingredients by solvent or also the plants containing the hydroxyanthraquinones. natural origin according to the invention. The liquid used to dilute the powder may consist of water and / or cosmetically acceptable solvents such as alcohols, glycols, and oils. The viscosity generally obtained after mixing varies between 300 and 3500 cPo.

It is of course possible to introduce in addition to hydroxyanthraquinones of natural origin other hydroxyanthraquinones according to the invention, as well as other natural or synthetic dyes. As another natural coloring agent, lawsone, juglone, indigo and the plants or extracts containing these dyes may be mentioned.

The cosmetically acceptable medium of the other embodiments of hair dye compositions according to the invention may be aqueous and its pH may vary between 2 and 11 and be adjusted to the desired value by means of alkalinizing agents such as ammonia, alkaline carbonates, alkanolamines such as mono-, di- or triethanolamine, alkylamines, or acidifying agents such as, for example, hydrochloric acid, sulfuric acid, citric acid, etc.

These compositions may also contain anionic, cationic, nonionic and / or amphoteric surfactants or mixtures thereof. Mention may be made more particularly of the preferred surfactants, soaps, alkylbenzenesulfonates, alkylnaphthalenesulphonates, sulphates, ether sulphates, and sulphonates of fatty alcohols, quaternary ammonium salts such as trimethylketylammonium bromide and bromide. cetylpyridinium, fatty acid diethanolamides, polyoxyethylenated or polyglycerolated acids, alcohols or amides, polyoxyethylenated or polyglycerolated alkylphenols. The surfactants are present in the compositions according to the invention in proportions of between 0.1 and 55% by weight and preferably between 1 and 40% by weight relative to the total weight of the composition.

These compositions may also contain organic solvents to solubilize compounds that are not sufficiently soluble in water. Among these solvents may be mentioned, for example, lower alkanols such as ethanol and isopropanol, polyols such as glycerol, glycol or glycol ethers such as ethylene glycol monobutyl ether, ethylene glycol, propylene glycol, diethylene glycol monoethyl ether and monomethyl ether, and similar products or mixtures thereof. These solvents are preferably taken in proportions ranging from 1 to 60% by weight and more particularly from 3 to 30% by weight relative to the total weight of the composition.

The compositions may also contain anionic, nonionic, cationic or amphoteric polymers in amounts ranging from 0.1 to 5% by weight.

The compositions in accordance with the invention may be thickened preferably with compounds chosen in particular from sodium alginate, gum arabic, cellulose derivatives such as methylcellulose and hydroxyethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose and various polymers having this function such as in particular derivatives of acrylic acid. It is also possible to use mineral thickeners such as bentonite. These thickening agents are preferably present in proportions of between 0.1 and 5% by weight and in particular between 0.5 and 3% by weight relative to the total weight of the composition.

Reducing agents and antioxidants such as, for example, sodium sulfite, thioglycolic acid, thiolactic acid, sodium bisulfite, ascorbic acid and hydroquinone can also be added to the compositions according to the invention. These agents are advantageously present in the composition in proportions of between 0.05 and 1.5% by weight relative to the total weight of the composition.

Naturally, it is possible to add to the compositions according to the invention any other adjuvants conventionally used in hair dyeing compositions such as, in particular, penetrating agents, sequestering agents, buffers and perfumes.

It goes without saying that the compositions according to the invention may also contain other direct dyes chosen more particularly from the anthraquinone dyes other than the mentioned hydroxyanthraquinones, the azo dyes, the nitro derivatives of the benzene series, the indophenols, the indamines and indoanilines, hydroxylated derivatives of benzaldehyde, etc.

The compositions according to the invention may also contain so-called oxidation dyes, that is to say compounds which are not dyes in themselves but which are converted into dyes by condensation in an oxidizing medium. The oxidation dyes are distinguished, on the one hand, by the para-type oxidation dye precursors chosen from diaminobenzenes, diaminopyridines and aminophenols, the functional groups of which are in para relative to one another, ortho-type oxidation dye precursors whose functional groups are ortho to each other and, on the other hand, compounds called modifiers, shaders or couplers which are so-called meta derivatives selected from metadiaminobenzenes, methadiaminopyridines, meta-aminophenols, meta-diphenols and phenols.

These compositions may also contain so-called rapid oxidation dyes which are dye precursors of the benzene series comprising on the ring three substituents chosen from hydroxyl, methoxy and amino groups and capable of oxidizing directly in air.

The dyes are preferably present in proportions ranging from 0.005 to 10% by weight.

More particularly advantageous results are obtained for the above-described compositions containing polyhydroxyanthraquinones which are unsubstituted or substituted with nonacidic groups, at alkaline pH levels advantageously between 7 and 12.

When the compositions according to the invention contain polyhydroxyanthraquinones substituted with acidic groups such as carboxylic or sulphonic groups, particularly advantageous results are obtained for acidic pHs of between 2 and 7.

The hair dyeing method according to the invention can essentially be characterized in that at least one composition as defined above is applied to the hair before or after shampooing and is allowed to be applied for a period that may vary. between 5 and 60 min and preferably between 5 and 40 min, the hair is rinsed and dried. Hair styling composition can also be applied to the hair after shampooing and the hair is then dried.

The hair coloring can also be carried out according to multi-step processes at least one of which consists in applying a dye of formula I. These multi-step processes can implement compositions having different pHs depending on the nature of the dyes present. . In the context of the invention, it is possible to design the dyeing in several stages by using a composition containing polyhydroxyanthraquinones with an acid group and having a pH of between 2 and 7 and in a second step a composition containing a polyhydroxyanthraquinone at an alkaline pH of 7 to 12 or vice versa.

The following examples are intended to illustrate the invention without being limiting in nature.

Example 1

The following composition is prepared:

1,2,4-Trihydroxyanthraquinone 1 g

Wax of Lanette O 20 g

Copra monoethanolamide 5 g

Sipon LA 30 10 g

2-Amino 2-methylpropanol qsp pH 10

Distilled water qs 100 g

This composition is a burgundy cream. Applied 30 min on a natural chestnut hair, it gives the hair after rinsing, shampooing and drying a reflection

651 202

This purple styling lotion is applied to dark blond hair. After shaping and drying, the hair is adorned with an iridescent reflection.

Example 3

The following composition is prepared:

Sodium salt of 1,2-dihydroxy-3-sulphoanthraquinone monohydrate

<td></td><td>1.0 g</td>

<td>lawsone</td><td>0.3 g</td>

<td>Cetyl alcohol</td><td>17,0g</td>

<td>Mergital CS 15 / E</td><td>6.0 g</td>

<td>Oleic alcohol</td><td>3.0 g</td>

<td>Citric acid</td><td>qs pH 3</td>

<td>Distilled water</td><td>qsp 100 g</td>

<td colspan="2">This yellow cream is applied on brown hair</td>

<td>clear.</td><td></td>

<td colspan="2">After 20 minutes of application and rinsing, the hair has a reflection</td>

<td>deep red coppery.</td><td></td>

<td>Example 4</td><td></td>

<td>The following composition is prepared: 1,2,5,8-tetrahydroxyanthraquinone</td><td>0.7 g</td>

<td>1,4-Dihydroxyanthraquinone</td><td>1.3 g</td>

<td>Wax of Lanette O</td><td>20.0 g</td>

<td>Copra monoethanolamide</td><td>5.0 g</td>

<td>Sipon LA 30</td><td>10.0 g</td>

<td>2-Amino 2-methylpropanol</td><td>qs pH 9.6</td>

<td>Distilled water</td><td>qsp 100 g</td>

<td colspan="2">This composition is a purplish-brown cream.</td>

<td>It is applied 30 min on a chestnut hair.</td><td></td>

<td colspan="2">After rinsing, shampooing and drying, the hair has a</td>

<td>ash reflection.</td><td></td>

<td>Example 5</td><td></td>

<td>The following composition is prepared: 1-Methyl-2-carboxy-3,5,6,8-tetrahydroxyanthraquinone</td><td>0.6 g</td>

<td>3-Carboxy 1,2,4-trihydroxyanthraquinone</td><td>0.3 g</td>

<td>Cetyl alcohol</td><td>17.0 g</td>

<td>Mergital CS 15 / E</td><td>6.0 g</td>

<td>Oleic alcohol * -</td><td>3.0 g</td>

<td>Citric acid</td><td>qs pH 2.7</td>

<td>Distilled water</td><td>qsp 100 g</td>

<td colspan="2">This cream carmine color is applied 30 minutes on</td>

<td>light brown hair.</td><td></td>

<td colspan="2">After rinsing, shampooing and drying, these hair are nuanced</td>

<td>by a purple reflection.</td><td></td>

<td>Example 6</td><td></td>

<td>The following composition is prepared: 1,2,5,8-Tetrahydroxyanthraquinone</td><td>0.6 g</td>

<td>Ι-Ν-β-hydroxyethylamino 2-methoxy-4-nitro benzene</td><td>0.2 g</td>

<td>Ι-π-β-hydroxyethylamino 3-nitro 4-aminobenzene</td><td>0.1g</td>

<td>Sactipon 8533</td><td>25.0 g</td>

<td>Coconut fatty acid diethanolamide</td><td>5.0 g</td>

<td>2-Butoxyethanol</td><td>1.0 g</td>

<td>monoethanolamine</td><td>qs pH 9.6</td>

<td>Distilled water</td><td>qsp 100 g</td>

This dark purple-brown foaming liquid is a coloring shampoo.

It is applied to light brown hair with a significant percentage of white hair.

After 15 minutes of laying and rinsing, the hair is colored in a light ash-brown shade and the white hair is covered in the same tone.

Example 7

The following composition is prepared:

mahogany red very bright.

Example 2

The following composition is prepared:

1,2,4-Trihydroxy-3-carboxyanthraquinone 0.05 g

Vinyl acetate / crotonic acid copolymer (90/10) 1.8 g

Vinylpyrrolidone / vinyl acetate copolymer (60/40) 0.4 g

Ethyl alcohol 96 qsp 50 ° alcoholic

Triethanolamine qsp pH 6

Distilled water qs 100 g

<td colspan="2">651,202</td>

<td>1,2-dihydroxy-3-sulfoanthraquinone sodium salt</td><td></td>

<td>monohydrate</td><td>0.1g</td>

<td>Vinyl acetate / crotonic acid copolymer (90/10)</td><td>1.8 g</td>

<td>Vinylpyrrolidone / vinyl acetate copolymer (60/40)</td><td>0.4 g</td>

<td>Ethyl alcohol 96 ° qsp:</td><td>50 ° alcoholic</td>

<td>triethanolamine</td><td>qs pH 5</td>

<td>Distilled water</td><td>qsp 100 g</td>

<td colspan="2">This composition constitutes a styling lotion which is</td>

<td>apply on a blonde hair.</td><td></td>

<td colspan="2">The hair, after shaping and drying, have a reflection</td>

<td>pearly gold.</td><td></td>

<td>Example 8</td><td></td>

<td>The following composition is prepared: 1,2,7-Trihydroxyanthraquinone</td><td>0.4 g</td>

<td>1-Amino 2-nitro 4-hydroxybenzene</td><td>0.1g</td>

<td>Ι-Ν-β-hydroxyethylamino 2-nitro 4-hydroxybenzene</td><td>0.3 g</td>

<td>Wax of Lanette O</td><td>20.0 g</td>

<td>Copra monoethanolamide</td><td>5.0 g</td>

<td>Sipon LA 30</td><td>10.0 g</td>

<td>2-Amino 2-methylpropanol</td><td>qsp pH 9.9</td>

<td>Distilled water</td><td>qsp 100 g</td>

<td colspan="2">This brown-red cream is placed on brown hair</td>

<td>dark.</td><td></td>

<td>After 30 min, the product is rinsed.</td><td></td>

<td colspan="2">After shampooing and drying, we obtain a hair dyed</td>

<td>with an intense and deep copper red reflection.</td><td></td>

<td>Example 9</td><td></td>

<td>The following composition is prepared: 1,2,4-Trihydroxyanthraquinone</td><td>0.05 g</td>

<td>1,2,5,8-Tétrahydroxyanthraquinoiie</td><td>0.3 g</td>

<td>Paratoluylenediamine dihydrochloride</td><td>0.3 g</td>

<td>aminophenol</td><td>0.1g</td>

<td>meta-aminophenol</td><td>0.1g</td>

<td>resorcinol</td><td>0.4 g</td>

<td>hydroquinone</td><td>0.15 g</td>

<td>Sinnopal NP9</td><td>22.0 g</td>

<td>Sinnopal NP4</td><td>22.0 g</td>

<td>Propylènegiycol</td><td>11.0 g</td>

<td>96 ° ethyl alcohol</td><td>8.0 g</td>

<td>Sodium bisulfite solution, 35 ° B</td><td>U g</td>

<td colspan="2">Pentasodium salt of diethylenetriamine pentaacetic acid 2.4 g</td>

<td>Ammonia at 22 ° B Distilled water qs 100 g</td><td>10.2 g</td>

This purple-black liquid composition gives, by weight-for-weight dilution to hydrogen peroxide 20 volumes, a gel which is applied for 30 minutes to a dark blond hair.

After rinsing and shampooing the hair is colored in a light ashy blond shade.

Example 10

The following composition is prepared:

1-methyl 2-carboxy 3,5,6,8-tetrahydroxyanthraquinone 5.0 g

Juglone 1.0 g

Rye flour 15,0g

Fallax pulverized bark 15g

Chestnut leaves sprayed 60.0 g

Citric acid 4.0 g

This yellowish powder is mixed at the time of use with 3.5 times its weight of warm water. The resulting mixture of pH 3.3 and brick color has the consistency of a poultice.

Applied 20 minutes on blond hair, it brings them after rinsing and shampooing a bright golden reflection.

Example 11

5,8-Dichloro-1,4-dihydroxyanthraquinone 0.7 g

Wax of Lanette O 20 g

Copra monoethanolamide 5 g

Sipon LA 30 10 g

2-Amino 2-methyl-1-propanol qsp pH 9.5

Distilled water qs 100 g

This composition is a cream of red color. Applied 30 minutes on light blonde hair, it gives them after rinsing, shampooing and drying, a pearly reflection.

Example 12

1,8-Dihydroxy-3-hydroxymethylanthraquinone 2 g

Saponary powder 30 g

50 g corn flakes

Wheat flour 8 g

Sodium carbonate anhydrous 10 g

This powder, of beige color, is mixed at the time of use with three times its weight of warm water; the mixture thus obtained, brown-green color, pH 9.8, has the consistency of a poultice.

Applied 30 minutes on blonde hair, it gives them after rinsing and drying a beige coppery reflection.

The different trade names used in the preceding examples are explained in more detail below:

Lanette wax O: cetyl alcohol and stearyl alcohol 50-50 mixture sold by the Henkel Company.

Sipon LA 30: 20% ammonium lauryl sulphate solution sold by Henkel Company.

Mergital CS15 / E: cetylstearyl alcohol with 15 mol of ethylene oxide sold by Henkel.

Sactipon 8533: Sodium alkyl ether sulphate sold by Lever Company.

Sinnopal NP4: Nonylphenol oxyethylenê with 4 mol of ethylene oxide sold by the Henkel Company.

Sinnopal NP9: Nonylphenol oxyethylenê with 9 mol of ethylene oxide sold by the Henkel Company.

R