GB2119411A - Composition based on quinone dyestuffs for use in hair dyeing and process for the preservation of quinone dyestuffs - Google Patents

Abstract

Compositions, which are stable on storage, of certain benzoquinone and naphthoquinone dyestuffs in an anhydrous solvent containing a non- ionic surface-active agent are used for the preparation of hair dyeing compositions. The compositions contain at least one quinone dyestuff of formula <IMAGE> in which the groups R1-R8 may be H, OH, CH3 or OCH3 in accordance with a specified substitution table. The solvent may be a saturated alcohol, polyol, glycol ether, ester of an ethylene glycol monoalkyl ether, saturated fatty acid ester of a saturated alcohol or a mixture. Surface active agents may be added.

Description

SPECIFICATION Composition based on quinone dyestuffs for use in hair dyeing and process for the preservation of quinone dyestuffs The present invention relates to a process making it possible to preserve quinone dyestuffs which are certain benzoquinones or naphthoquinones, to the compositions making it possible to preserve these dyestuffs, and to the use of these compositions in the preparation of hair-dyeing compositions.

2-Hydroxynapthoquinones and benzoquinones are dyestuffs which are in themselves known but most of them have not been used hitherto in hair dyeing. The use of such dyestuffs in hair dyeing has formed the subject of British Patent Applications Nos 82 34178 and 82 341 79.

2-Hydroxy-1 ,4-naphthoquinone, also called lawsone, which is one of the dyestuffs responsible for henna dyeing, has also been known for a long time.

The 2-hydroxynaphthoquinones mentioned in British Patent Application No 82 34179, correspond to the following formula:

in which R1 denotes hydrogen, hydroxyl, alkoxy, nitro, halogen, alkyl or acyl and R2, R3, R4 and R5 independently of one another denote hydrogen, hydroxyl, alkoxy, alkyl or acyl, at least one of the substituents R1 to R5 being other-than hydrogen. In this formula, R2 and R5 cannot simultaneously denote hydroxyl if R1, R3 and R4 denote hydrogen. The alkoxy or alkyl groups preferably denote groups having 1 to 4 carbon atoms, and the acyl groups have from 2 to 4 carbon atoms.

The benzoquinones disclosed in British Patent Application No 82 341 78 correspond to the formula:

in which R1 and R3 independently of one another denote hydrogen, hydroxyl, alkoxy or optionally hydroxylated alkyl and R2 and R4 independently of one another denote hydrogen, hydroxyl, alkoxy, alkyl having 1 to 3 carbon atoms or phenyl optionally substituted by OH, these compounds having at most two alkyl or alkoxy groups on the quinone nucleus.

These compounds have good tinctorial strength on hair when they are used as direct dyestuffs.

However, they present certain problems insofar as they are sparingly soluble, in particular in water, and insofar as they are also unstable in aqueous solution during storage.

One way of overcoming this problem is to use them in powder form with other pulverulent products serving as carriers. On dilution, a colouring poultice can be obtained.

This method of use, although very advantageous, nevertheless has the shortcoming that the dyestuff must be dissolved at the time of use, that is to say at the time when the powder is made into a paste with water. The tinctorial strength is therefore limited by the rate of solubilisation and the solubilisation limit of the abovementioned dyestuffs.

We have discovered that, although these dyestuffs lose their tinctorial strength, on storage, in aqueous compositions normally used in hair dyeing, benzoquinones or naphthoquinones which contain at least one hydroxy or methoxy group but not more than two methoxy groups and not more than four hydroxy groups preserve this tinctorial strength in a surprising way during storage in anhydrous solvents.

The present invention accordingly provides solutions of certain quinone dyestuffs in an anhydrous solvent or mixture of anhydrous solvents as well as a process for the preservation of these dyestuffs in the anhydrous solvent or solvents.

The solutions or compositions according to the invention are essentially characterised in that they contain at least one quinone dyestuff corresponding to the formulae:

in which R1, R2, R3, R4, R5, R6, R, and R8 have the meanings below:

Compound R1 R2, R, R4 R5 R" R7 R8 1 H H H H H OH 2 OH H H H H OH - - 3 H H H OH H OH - - 4 H H H H OCH3 OH - - 5 OCH3 H H H H OH - - 6 H OH H H H OH - - 7 H H OCH3 H H OH - - 8 H OH H H H OCH3 - - 9 CH3 H H - H H OH - - 10 H OCH3 H H OCH3 OH - 11 OCH3 OH H H H H - - 12 H H OH H H OH - 13 H H H H OH OH - 14 CH3 H H H OH OH - 15 H - H OH OH H OH - 16 OH OH H H OH OH - - 17 - - - - - - OH OCH3 18 - - - - - - OCH3 OCH3 19 - - - -- -- -- OH H in an anhydrous solvent or mixture of anhydrous solvents, in the presence of a non-ionic surface-active agent.

The term "anhydrous" is to be understood as meaning solvents or mixtures of solvents which do not contain more than 1% of water. These solvents are cosmetically acceptable and include, in particular, lower (e.g. of 1 to 6 carbon atoms) saturated monoalcohols such as ethanol and isopropanol, long-chain (e.g. of at least 7 carbon atoms) saturated monoalcohols such as cetyl alcohol, polyols such as alkylene glycols, for example ethylene glycol, propylene glycol, glycerol and diethylene glycol, glycol ethers such as mono-, di- and tri-ethylene glycol monoalkyl ethers, for example ethylene glycol monoethyl ether, ethylene glycol monobutyl ether and diethylene glycol monoethyl ether, esters such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, and saturated fatty acid esters of saturated lower alcohols, such as isopropyl myristate or palmitate.The preferred compositions contain, in particular, ethanol, cetyl alcohol, propylene glycol, ethylene glycol monoethyl ether or ethylene glycol monobutyl ether.

In a preferred embodiment of the invention the anhydrous medium consists of one or more of the abovementioned anhydrous solvents and of one or more anhydrous non-ionic surface-active agents so that the composition contains at least 15% of solvent(s) and at least 20% of surface-active agent(s).

The non-ionic surface-active agents which can be used are chosen, in particular, from amongst polyoxyethyleneated fatty alcohols, polyoxyethyleneated alkylphenols or naphthols and polyglycerolated fatty alcohols, The dyestuffs used according to the invention are suitably present in these compositions, by themselves or in association, in amounts from 0.001 to 5% by weight and preferably from 0.005 to 2% by weight relative to the total weight of the anhydrous composition.

The compositions according to the invention can contain an anhydrous alkaline or acidifying agent. Examples of agents used for this purpose are citric acid, ascorbic acid, acetic acid, lactic acid and alkanolamines, preferably those which are completely substituted on the amine group, for example dimethylaminoethanol.

When an acidifying agent is used, the particularly preferred dyestuffs are dyestuffs 1 to 6 and 8 to 1 9 in the above table, and in the case where an alkaiising agent is used, the particularly preferred dyestuffs are dyestuffs 2 to 7 in the above table.

Preferred embodiments of the invention therefore consist of these two types of composition, namely, on the one hand, compositions having an acid pH after dilution with water and containing dyestuffs 1 to 6 and 9 to 11 , and, on the other hand, compositions having an alkaline pH after dilution with water and containing dyestuffs 2 to 8.

Apart from the compounds described above, the anhydrous compositions according to the invention can contain numerous additives, the only condition being that they contain less than 1% of water.

For this purpose, there may be mentioned, amongst the other additives, perfumes, sequestering agents, thickeners, hair-treating agents, antioxidants, vegetable or mineral oils, preservatives and organic salts.

The compositions can also contain other dyestuffs intended for use in hair dyeing and which are direct dyestuffs. It is possible, in particular, to make use of natural direction dyestuffs of low stability in aqueous solution. The following may be mentioned in particular amongst these types of dyestuffs: haematoxylin, which is the dyestuff present in logwood, brasilin, which is the dyestuff present in brazilwood, and also henna extract Examples which may be mentioned of other colouring extracts obtained from colouring plants are extracts of madder, wild camomile, curcuma and annatto.

The direct dyestuffs, other than those corresponding to the formulae (I') and (II'), which can be used according to the invention are in themselves well known; they include in particular, anthraquinone dyestuffs, azo dyestuffs, triarylmethane dyestuffs, azine dyestuffs and nitrobenzene derivatives such as nitrophenylenediamines, nitroaminophenols, dinitroaminophenols, nitroaminobenzenes and nitrodiphenylamines. It is preferred to use anthraquinone dyestuffs and in particular the hydroxyanthraquinones described in French Patent Application No. 82/03,294, (British Application No 82 05761).

The dyestuffs other than those of the formula (I') or (II') are suitably present in the anhydrous dyeing compositions according to the invention in amounts from 0.01 to 3% by weight, preferably from 0.05 to 2% by weight relative to the total weight of the anhydrous composition The compositions according to the invention can be stored for long periods without there being any deter:oration in the tinctorial strength of the dyestuffs corresponding to the formulae (I') and (II').

These compositions can be applied as such to the wet hair or can be diluted just before use. In the latter case, at the time of dyeing, the compositions according to the invention are diluted with an aqueous solution so that the ratio of the composition according to the invention to-the aqueous solution is generally 0.25: 1 to 2 1 by weight The aqueous solution can be pure water, but can also be in the form of an aqueous liquid of a greater or lesser degree of thickness, such as a carrier normally used in hair-dyeing compositions. In this case, the components of the cosmetic medium can be anhydrous or non-anhydrous, cosmetically acceptable ingredients normally used in this type of composition.

The mixture produced in this way is applied to the hair for, say, 1 minute to 1 hour, preferably from 5 minutes to 30 minutes. The hair is then rinsed, optionally shampooed and dried.

The Examples which follow further illustrate the present invention.

EXAMPLE 1 2-Hydroxy-3-methyl-5,6-di methyoxy- 1 ,4-benzoquinone 0.5 g 2,3-Dihydroxy-1,4-naphthoquinone 0.4 g 2-Hydroxy-3-methoxy- 1,4-naphthoquinone 0.3 g Anhvdrous citric acid 1g Anhydrous ethyl alcohol 28.5 g SINNOPAL NP 9 26.5 g SINNOPAL NP 4 q.s.p. 100 g This liquid is mixed with 1.5 times its weight of cold water at the time of use. The gel obtained is applied to light chestnut hair for 30 minutes. The hair is rinsed and dried and then possesses a purple violet mahogany sheen.

The preservation of the tinctorial strenght of the initial composition during storage is much better than that obtained on storing the final gel.

EXAMPLE 2 2-Hydroxy-1 ,4-naphthoquinone 0.6 g 2-Hydroxy-8-methoxy-1 ,4-naphthoquinone 0.25 g Anhydrous citric acid 1 g Anhydrous ethyl alcohol- 28.5 g SINNOPAL NP 9 26.5 g SINNOPAL NP 4 q.s.p. 100 g This composition can be applied directly to wet hair; it can also be mixed with 1.5 times its weight of cold water at the time of use. The gel obtained is applied to light chestnut hair for 30 minutes. After the hair has been rinsed, it is dried. It then possesses an intense golden sheen.

In the liquid composition, the dyestuffs keep much better on storage than in the final gel applied to the hair.

EXAMPLE 3 2,3-Dihydroxy-1,4-naphthoquinone 0.5 g 2,5-Dihydroxy-1 ,4-naphthoquinone 0.3 g 8-Methoxy-2-hydroxy-1 ,4-naphthoquinone 0.15 g Anhydrous citric acid 1 g Cetyl alcohol 24 g MERGITAL CS 15 E 23 g EUTANOL G q.s.p. 100 g This cream is mixed with an equal weight of warm water at the time of use. The creamy mixture obtained is applied to light chestnut hair. After an interval of 30 minutes, the hair is rinsed and dried. It then possesses a beige coppery sheen.

The three dyestuffs in the starting composition keep better in the latter than in the composition applied to the hair.

EXAMPLE 4 2-Hydroxy-3-methoxy-1,4-naphthoquinone 0.7 g 2,5,8-Trihydroxy-1 ,4-naphthoquinone 0.05 g N,N-Dimethylaminoethanol 0.7 g Anhydrous ethyl alcohol 21.5 g SINNOPAL NP 9 31 g SINNOPALNP4 Qs.p. 100 g This liquid is diluted with 1.5 times its weight of cold water to give a gel, which is applied to deep blond hairfor 10 minutes, The hair is rinsed and dried. It then possesses an auburn sheen.

The dyestuffs keep much better in the liquid composition than in the final gel.

EXAMPLE 5 2,5-Dihyd roxy-3-m ethyl-6-methoxy-1 ,4-naphthoquinone 0.7 g 2,7-Dihydroxy-1 ,4-naphthoquinone 0.3 g Anhydrous citric acid 1 g Anhydrous ethyl alcohol 28.5 g SINNOPAL NP 9 26.5 g SINNOPAL NP 4 q.s.p. 100 g The above liquid is treated with 1.5 times its weight of water at the time of use. The gel obtained is applied to light chestnut hair for 30 minutes. The hair is then rinsed and dried. A purple-violet colouration is obtained.

The dyestuffs keep much better in the liquid composition than in the final gel applied to the hair.

EXAMPLE 6 2.3-Dihydroxy-1 ,4-naphthoquinone 0.8 g 2-N-(-HydrnxyethyI)-amino-5-hydrnxynitrnbenzene 0.1 5 g Haematoxylin 0.159 N,N-Dimethylaminoethanol 1 g Anhydrous ethyl alcohol 24 g SINNOPAL NP 9 28.5 g SINNOPAL NP 4 q.s.p. 100 g This liquid composition is mixed with 1.5 times its weight of water at the time of use. The gel obtained is applied to deep chestnut hair 30 minutes, after which the hair is rinsed and dried. It then possesses a pearlescent ashen sheen.

The tinctorial strength is preserved much better during storage of the liquid composition than if the final gel is stored.

EXAMPLE 7 2. 5-Dihydroxy-3-methyl-6-methoxy-1 ,4-benzoquinone 1.1 g 2-Hydroxy-3-methoxy- 1 ,4-naphthoquinone 0.35 g 3-Carboxy-1 ,2,4-trihydroxy-9, 1 0-anthraquinone 0.1 g Anhydrous citric acid 1 g Cetyl alcohol 24 g MERGITAL CS 15 E 23 g EUTANOL G q.s.p. 100 g This composition, which forms a cream, is diluted with its own weight of warm water at the time of use. The cream obtained is applied to deep chestnut hair for 30 minutes. After rinsing and drying, the hair possesses a purple-violet sheen.

The preservation of the dyestuffs on storage is much better in the initial anhydrous composition than in the final compositoin applied to the hair.

EXAMPLE 8 2-Hydroxy-1 ,4-naphthoquinone 0.20 g 2,5-Dihydroxy-1,4-naphthoquinone 0.15g Sodium 2-hydroxy-9, I 0-anthraquinonone-3-sulphonate monohydrate 0.40 g Anhydrous citric acid 1. g Anhydrous ethyl alcohol 28.5 g SINNOPAL NP 9 26.5 g SINNOPAL NP 4 q.s.p. 100 g This composition is in the form of a liquid, which can be applied directly to wet hair or which is mixed with 1.5 times its weight of cold water at the time of use. The gel obtained is applied to light chestnut hair. After an interval of 40 minutes, the hair is rinsed and dried. It is dyed with a coppery beige sheen.

The storage stability of the dyestuffs is much better in the liquid composition than in the final gel.

EXAMPLE 9 2-Hydroxy-3-methoxy-1 ,4-naphthoqu'inone 0.7 g 2-Hydroxy-1 ,4-naphthoquinone 0.25 g Anhydrous citric acid 1 g Cetyl alcohol 24 g MERGITAL CS 15 E 23 g EUTANOLG qsp 100 g This cream is diluted with an equal weight of warm water at the time of use. The mixture obtained is a cream, which is applied to chestnut hair for 30 minutes. After rinsing and drying, the hair possesses an intense red coppery sheen.

The dyestuffs have a much better stability in the starting composition than in the composition applied to the hair.

EXAMPLE 10 2,3-Dihydroxy-1 ,4-naphthoquinone 0.45 g 2,5-Dihydroxy- 1 ,4-naphthoquinone 0.35 g 2,7-Dihydroxy*-1 ,4-naphthoquinone 0.1 g N,N-Dimethylaminoethanol 1 g Anhydrous ethyl alcohol 24 g SINNOPAL NP 9 28.5 g SINNOPAL NP 4 q.s.p. 100 g This liquid is diluted with 1.5 times its weight of water at the time of use. The gel obtained is applied to chestnut hair for 30 minutes. The hair is rinsed and then dried. It then possesses an ashen sheen.

The dyestuffs are more stable on storage in the anhydrous liquid carrier than they would be in the gel which is applied to the hair.

EXAMPLE 11 The following composition is prepared: 2,5-Dihydroxy-3-methyl benzoquinone 0.3 g 2,5-Dihydroxy-1 ,4-naphthoquinone 0.2 g Anhydrous citric acid 1 g Anhydrous ethyl alcohol 28.5 g SINNOPAL NP 9 26.5 g SINNOPAL NP 4 q.s.p. 100 g This composition is in the form of a liquid which can be applied directly to wet hair or it can be mixed at the time of use with 1.4 x its weight of cold water. The gel obtained is applied to deep blond hair. After leaving it for 20 minutes, the hair is rinsed and dried. The hair is dyed with a mahogany sheen.

EXAMPLE 12 The following composition is prepared: 2-methoxy-5-hydroxy-1,4-naphthoquinone 0.2 g 2-hydroxy-8-methoxy-1,4-naphthoquinone 0.3 g 3-methoxy-5-hydroxy-1 ,4-naphthoquinone 0.05 g Anhydrous citric acid 0.8 g Anhydrous ethyl alcohol 25 g SINNOPALNP 9 q.s.p. 100 g This liquid composition is applied directly to moistened blond hair.

After leaving it for 25 minutes, the hair is rinsed. It possesses a light golden sheen.

If the diluted composition is stored the three quinone dyestuffs are degraded whereas they are not degraded in the anhydrous composition kept under the same conditions.

EXAMPLE 13 The following composition is prepared: 2-hydroxy-3-methyl- 1 ,4-naphthoquinone 0.6 g 2,5-dihydroxy-3-methyl-6-methoxy-1 ,4-benzoquinone 0.07 g Anhydrous citric acid 1.2 g Anhydrous ethyl alcohol 30 g Hydroxypropyl cellulose sold under the name KLUCEL G by HERCULES 0.8 g SINNOPAL NP 9 q.s.p. 100 g This thickened liquid is applied for 30 minutes to previously moistened blond hair.

After rinsing and drying, the hair possesses an ashen beige shade.

The convervation of the dyestuff in the anhydrous composition is better than that of a similar aqueous composition.

EXAMPLE 14 The following composition is prepared: 2,8-Dihydroxy-1 ,4-naphthoquinone 0.5 g 3-Methyl-2,8-dihydroxy-1,4-naphthoquinone 0.2 g 2,6,7-trihydroxy-1 ,4-naphthoquinone 0.2 g Anhydrous citric acid 1 g Cetyl alcohol 24 g Mergital CS 15 E 23 g Eutanol C q.s.p. 100 g This cream is diluted at the moment of use with an equal weight of warm water. A cream is obtained which is applied for 20 minutes to a pale chestnut head of hair which is then rinsed and dried.

The hair now possesses a coppery sheen.

The dyestuffs are kept better in the anhydrous crean than in the aqueous composition applied to the head.

EXAMPLE 15 The following composition is prepared: 2-Hydroxy-5,8-dimethoxy-1 ,4-naphthoquinone 0.05 g 2,6-dihydroxy-1 ,4-naphthoquinone 0.4 g 2,3,5,8-tetrahydroxy-1 ,4-naphthoquinone 0.3 g 2-hydroxy-3-methyl-5,6-dimethoxy- 1 ,4-benzoquinone 0.1 0.1 g Anhydrous citric acid 1 g Purified ethylene glycol monoethyl ether 25 g SINNOPAL NP 9 q.s.p. 100 g This liquid is applied for 25 minutes to a wetted pale chestnut head of hair. After rinsing and drying the hair possesses a coppery beige sheen.

The dyestuffs of this composition are more stable on storage than a corresponding aqueous composition.

In the foregoing examples, the tradenames used correspond to the following products: SINNOPAL NP 9 Nonylphenol oxyethyleneated with 9 mols of ethylene oxide, sold by HENKEL SINNOPAL NP 4 Nonylphenol oxyethyleneated with 4 mols of ethylene oxide, sold by HENKEL MERGITAL CS 15 E Cetyl-stearyl alcohol containing 15 mols of ethylene oxide, sold by HENKEL EUTANOL G Octyldodecanol sold by HENKEL

Claims (14)

1. A storage-stable composition which contains, in at least one anhydrous (as hereinbefore defined) solvent at least one quinone dyestuff of the formula

in which R1, R2, R3, R4,R5, R6, R7 and R8 have the meanings indicated below:

Compound R1, R2, R3, R4, R5, R6, R7, R8, 1 H H H H H OH - 1 H H H H H OH - 2 OH H H H H OH - 3 H H H H OCH3 OH - - 5 OCH3 H H H H OH - - 6 H OH H H H OH - - 7 H H OCH3 H H OH - - 8 H OH H H H OCH3 - - 9 CH3 H H H H OH - - 10 H OCH3 H H OCH3 OH - - 11 OCH3 OH H H H H - 12 H H OH H H OH - 13 H H H H OH OH - 14 CH3 H H H OH OH - 15 H H OH OH H OH - 16 OH OH H H OH OH - 17 - - - - - - -OH OCH3 18 - - - - - - OCH3 OCH3 19 - - - - - - OH H and an anhydrous non-ionic surface-active agent.

2. A composition according to claim 1 in which the dyestuff is present in an amount from 0.001 to 5% by weight, relative to the toal weight of the composition.

3. A composition according to claim 1 or 2 in which the solvent is a saturated alcohol, polyol, glycol ether, ester of an ethylene glycol monoalkyl ether, saturated fatty acid ester of a saturated lower alcohol, or a mixture thereof.

4. A composition according to any one of claims 1 to 3 which contains at least 15% of solvent (2) and at least 20% of surface-active agent(s).

5. A compositon according to any one of claims 1 to 4, in which the surface-active agent is a polyoxyethyleneated fatty alcohol, polyoxyethyleneated alkyiphenyl or naphthol, or a polyglycerolated fatty alcohol.

6. A composition according to any one of claims 1 to 5, which also contains at least one other anhydrous additive which is a perfume, sequestering agent, thickener, hair-treating agent, antioxidant, mineral or vegetable oil, preservative or organic salt.

7. A composition according to any one of claims 1 to 6, which contains an acidifying agent such that, after dilution with water, the composition has an acid pH, and the dyestuff of the formula (I') or (I I') is one in which R,, R2, R3, R4, R5, R6, R7 and R8 have the following meanings::

R, R2 R3 R4 R5 R6 R7 B8 H H H H H OH - - OH H H H H OH - - H H H OH H OH - - H H H H OCH3 OH - - OCH3 H H H H OH - - H OH H H H OH - - H OH H H H OCH3 - - CH3 H H H H OH - - H OCH3 H H OCH3 OH - - OCH3 OH H H H H - - H H OH H H OH - - H H H H OH OH - - CH3 ; H H H OH OH - - H H OH OH H OH - - OH OH H H OH OH - - - - - - - - OH OCH3 - - - - - - OCH3 OCH3 OH H - - - OH H

8.A composition according to any one of claims 1 to 6, which contains an alkalising agent such that, after dilution with water, the composition has an alkaline pH, and the dyestuff of the formula (I') is one in which Rr, R2, R3, R4, R5 and R6 denote the following:

R, Rz R3 R4 R5 | R6 OH H H H H OH H H H OH H OH H H H H OCH3 OH OCH3 H H H H OH H OH H H H OH H H OCH3 H H OH

9. A composition according to any one of claims 1 to 8, which contains another direct dyestuff.

1 0. A composition according to claim 1 substantially as described in any one of the Examples.

11. Process for the preservation of a dyestuff as defined in claim 1, which comprises introducing into an anhydrous solvent and a non-ionic surface-active agent a composition as claimed in any one of claims 1 to 10.

1 2. A composition as defined in claim 1 whenever obtained by a process as claimed in claim 11.

13. A process for dyeing-the hair which comprises applying at least one composition as claimed in any one of claims 1 to 10 and 12 to the hair which has been wetted with water.

14. Process for the preparation of a hair-dyeing composition intended for immediate application to the hair which comprises diiuting a composition as claimed in any one of claims 1 to 10 and 12 with a cosmetically acceptable aqueous solution.

1 5. Process according to claim 1 4 in which the weight ratio of the composition according to the aqueous solution is from 0.25 1 to 2 1.