CH637625A5 - PARAPHENYLENEDIAMINES AND TINCTORIAL COMPOSITIONS CONTAINING THEM. - Google Patents

Description

The object of the present invention is to describe new paraphenylenediamines which simultaneously exhibit, on the one hand, good harmlessness when applied to hair dye and, on the other hand, good stability of the shades obtained over time.

The present invention therefore relates to a chemical compound 55 of general formula (I):

nh (ch2) n - gold

(I)

formula in which R represents a substituted alkyl radical, the alkyl group comprising from 1 to 4 carbon atoms, n being equal to 2 or 3, as well as the corresponding acid salts.

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Among the compounds of formula (I), mention should be made of the compounds for which the radical R is a hydroxyalkyl radical; the radical R can also be an alkoxyalkyl radical in which the alkoxy group contains from 1 to 2 carbon atoms, a mesylaminoalkyl radical, an acetylaminoalkyl radical, a ureidoalkyl radical, a carbethoxyaminoalkyl radical, an aminoalkyl radical, a mono-alkylaminoalkyl radical or a dialkylaminoalkyl radical.

The present invention also relates to a dye composition for keratin fibers and in particular for human hair, characterized in that it contains, in a cosmetic vehicle, at least one compound of formula (I) or a corresponding acid salt .

In a preferred embodiment, the composition according to the invention contains from 0.001 to 6% by weight of compounds of formula (I) relative to the total weight of the composition. The pH of the dye composition according to the invention is a basic pH of, for example, between 7, 8 and 11.5. Among the alkalinizing agents which can be used, there may be mentioned ammonia, alkylamines such as ethylamine or triethylamine, alkanolamines such as mono-, di- or triethanolamine, alkylalkanolamines such as for example methyldiethanolamine, sodium or potassium hydroxides, sodium, potassium or ammonium carbonates.

The dye compositions according to the invention may contain one or more compounds of formula (I); they can also contain para-phenylenediamines other than those defined by formula (I) such as for example para-phenylenediamine, 2-methyl-5-methoxy-para-phenylenediamine, 2,6-dimethyl-3-methoxy-para-phenylenediamine, 2,6-dimethyl para-phenylenediamine , N, N- (P-hydroxyethyl) 4-amino aniline, (N-ethyl, N-carbamylethyl) 4-amino aniline. They may also contain paraaminophenols, such as, for example, paraaminophenol, 2-methyl-4-amino phenol, 2-chloro-4-amino phenol, 3-chloro-4-amino phenol. They may also contain orthophenylene diamines and orthoaminophenols substituted or unsubstituted on the amine group, and orthodiphenol (pyrocatechol).

The dye compositions according to the invention may also contain couplers, compounds which, in combination with paraphenylenediamines, paraaminophenols, lead in alkaline oxidizing medium to indamines, indoanilines and colored indophenols. For example, they can contain:

a) metaphenylenediamines such as 2,4-diamino anisole, 2,6-dimethyl metaphenylenediamine, (2,4-diamino) phenoxyethanol, (2-amino-N-methylamino-4) -phenoxyethanol, (2,4-diamino) phenyl P-methoxyethyl ether, (2,4-diamino) phenyl P-mesyl-aminoethyl ether, N-carbamylmethylamino-2 amino-4 anisole;

b) metaaminophenols such as metaaminophenol, 2-methyl-5-amino phenol, 2-methyl N- (P-hydroxyethyl) 5-amino phenol;

c) metadiphenols such as resorcin, Torcin, 2-methyl resorcin or cresorcin;

d) metaacetylaminophenols such as 2,6-dimethyl acetyl-5-amino phenol;

e) metacarbalcoxyamino-5 phenols such as 2-methoxy-carbethoxyamino-5 phenol;

f) meta-ureidophenols such as 2-methyl ureido-5 phenol;

g) hydroxy-6phenomorpholine;

h) 3-amino-4-methoxyphenol;

i) diamino-2,6 pyridine;

j) naphthols such as a-naphthol.

The compositions according to the invention can also contain direct dyes and, and in particular, nitro dyes of the benzene series such as for example N- (P-dihydroxyethanol) amino-1 nitro-3 N'-methylamino-4 benzene; N, N- (methyl, ß-hydroxy-ethyl) amino-1 nitro-3 N '- (P-hydroxyethyl) amino-4 benzene; N, N- (methyl, P-hydroxyethyl) amino-1 nitro-3 N'-methylamino-4 benzene; nitro-3 N- (P-hydroxyethyl) amino-4 anisole; nitro-3 N-

(P-hydroxyethyl) 4-amino phenol; (3-nitro-4-amino) phenoxyethanol; (3-nitro-N-methylamino-4) phenoxyethanol; N- (ß-hydroxyethyl) 2-amino-5-nitro anisole.

The compositions according to the invention may also contain leuco-derivatives of indoanilines and indophenols such as 4,4-dihydroxy-4'-amino-5-methylpheniphenylamine; 4,4 'dihydroxy N- (P-hydroxyethyl) 2-amino-5-methyl-2' chloro diphenylamine; 2,4-diamino-4-hydroxy-5-methyl-diphenylamine; 2,4-dihydroxy N- (P-methoxyethyl) amino-4 'diphenylamine; 2,4-dihydroxy-5-methyl-N- (P-methoxyethyl) amino-4 'diphenylamine. They can also contain dye precursors of the benzene series, comprising on the nucleus at least three hydroxyl, methoxy or amino substituents such as 2,6-diamino hydrochloride dihydrochloride, 2,6 N diamino trihydrochloride, N-ethylamino-4 phenol, 2,4-diamino dihydrochloride phenol, 1,2,4-trihydroxy benzene, 2,3,5-trihydroxy toluene, 4-methoxy-2-amino N- (P-hydroxyethyl )aniline.

It is also possible to add to the composition according to the invention water-soluble, anionic, cationic, nonionic or amphoteric surfactants. Among the surfactants which are particularly usable, mention may be made of alkylbenzenesulfonates, alkylnaphthalenesulfonates, sulfates, ethersulfates and sulfonates of fatty alcohols, quaternary ammonium salts such as trimethylketylammonium bromide, cetylpyridinium bromide, diethanolamides fatty acids, polyoxyethylenated acids and alcohols and polyoxyethylenated alkylphenols. Preferably, the surfactants are present in the compositions according to the invention in a proportion of between 0.5 and 30% by weight and, preferably, between 4 and 25% by weight relative to the total weight of the composition .

It is also possible to add, in the compositions according to the invention, organic solvents to dissolve compounds which are not sufficiently soluble in water. Among the solvents which can advantageously be used, mention may be made, by way of examples, of ethanol, isopropanol, glycerin, glycols such as butyl glycol, ethylene glycol, propylene glycol, monoethyl ether and diethylene glycol monomethyl ether and the like. The solvents can advantageously be present in the composition in a proportion ranging from 1 to 40% by weight and, preferably, from 5 to 30% by weight relative to the total weight of the composition.

The thickening products which can be added to the compositions according to the invention can advantageously be taken from the group formed by sodium alginate, gum arabic, cellulose derivatives such as methylcellulose, hydroxyethyl cellulose , hydroxypropylmethylcellulose, the sodium salt of carboxymethylcellulose and polymers of acrylic acid; mineral thickening agents such as bentonite can also be used. Preferably, the thickening agents are present in a proportion of between 0.5 and 5% by weight and, preferably, between 0.5 and 3% by weight relative to the total weight of the composition.

Antioxidants can also be added to the compositions according to the invention; these agents can advantageously be taken from the group formed by sodium sulfite, thioglyco-lic acid, sodium bisulfite, ascorbic acid and hydroquinone. These antioxidant agents can advantageously be present in the composition in a proportion of between 0.05 and 1.5% by weight relative to the total weight of the composition. The dye composition according to the invention may contain oxidizing agents such as hydrogen peroxide, urea peroxide, or persalts such as ammonium persulfate.

The compositions according to the invention can also contain various adjuvants usually used in cosmetics such as, for example, penetration agents, sequestering agents and perfumes. The dye composition according to the invention can be in the form of a liquid, cream, gel, aerosol or in any other form suitable for dyeing keratin fibers.

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It should be noted that the compounds of formula (I) make it possible to simultaneously obtain, in their application in hair dyeing, good safety and good shade stability over time.

For the dyeing of keratin fibers and, in particular, human hair, a composition as defined above is applied to the keratin fibers for a time of between 5 and 30 min, at a temperature close to room temperature.

The compounds of formula (I) and their salts are obtained by methods of preparation of conventional type within the reach of those skilled in the art.

In order to better understand the object of the invention, an example of the preparation of a compound of formula (I) and several examples of the use of this compound will now be described, purely by way of non-limiting illustration. dye compositions for hair.

Example 1:

Preparation of N- [ß- (ß'-hydroxyethoxy) -ethyl] - 4-amino aniline sulfate

+ h2n - (ch2) 2 -

0 - (ch2) 2 oh

1st step

->

n.h - (ch2) 2 - 0 - (ch2) 2 oh

2nd stage nh- (ch2) 2 - 0 - (ch2) 2 oh so4h2

Step 1: Preparation of Nitro-4 N- [ß- (ß'-hydroxyethoxy) ethyl] -aniline

0.2 mol (28.2 g) of parafluoronitrobenzene in 84.6 ml of diglycolamine is heated for 2 lA h between 110 and 120 ° C. After the mixture has cooled, it is poured into 300 g of crushed ice. The expected product precipitates in crystallized form. It is wrung, washed with water and dried. After recrystallization from ethanol and drying under vacuum, it melts at 78 ° C. The elementary analysis of the product obtained gives the following results:

Analysis for C10HJ4O4N2:

Calculated: C 53.09 H 6.19 N 12.39%

Found: C 53.20 H 6.32 N 12.32%

Step 2: Preparation of N- [ß- (ß'-hydroxyethoxy) ethyl] -amino-4 aniline sulfate

To 175 ml of hydroethanolic solution (15% water, 85% ethanol), 7.5 g of ammonium chloride and 58.5 g of zinc powder are added. This mixture is brought to reflux with stirring and then 0.15 mol (33.9 g) of the product obtained in the first step is added in small portions. When the addition of the nitro derivative is complete, the reaction medium is discolored; the boiling filter is collected by collecting the filtrate in a flask containing 10.5 ml of concentrated sulfuric acid and 30 ml of ethanol cooled to -10 ° C. The expected product precipitates in the form of a gum which crystallizes rapidly. It is wrung out, washed with alcohol and then with acetone. After drying under vacuum, the product melts with decomposition around 157 ° C. After recrystallization from a hydroethanolic mixture, the product obtained is subjected to elementary analysis which gives the following results:

Analysis for Ci0HlsN2O6S:

Calculated: C 40.82 H 6.12 N9.52 S 10.88%

Found: C 40.65 H 6.07 N9.53 S 10.92-10.69%

35 Example 2:

The following dye composition is prepared:

Compound of Example 1 5.88 g

Oxyethylenated oleic alcohol with 2 mol of ethylene oxide. . . 3.2g

4o Oxyethylenated oleic alcohol with 4 mol of ethylene oxide. . . 6.4g

Propylene glycol 6.4 g

Butylglycol 20 g

Ammonia at 22 ° B 10 g

Water q.s.p. 100g

The pH of this composition is equal to 10.25.

At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.

This mixture applied to naturally white hair at 90% for 20 min at 25 ° C gives them, after rinsing and sham-50 pooing, a bronze green coloring.

Example 3:

The following dye composition is prepared:

Compound of example 1 5g

55 Paraaminophenol 0.62 g

2-methyl-5-hydroxyethylamino phenol 0.28 g a-Naphtol 0.50 g

Orthoaminophenol 0.75 g

Nonylphenol with 4 mol of ethylene oxide sold under the name 60 Remcopal 334 by the company Gerland .... 12.6 g Nonylphenol with 9 mol of ethylene oxide sold under the name Remcopal 349 by the company Gerland .... 12.6 g

Butylglycol 20 g

Water q.s.p 100 g

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The pH of this composition is 10.2.

At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.

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This mixture applied to bleached hair for 20 min at 25 ° C gives them, after rinsing and shampooing, a very dark brown coloring.

Example 4:

The following dye composition is prepared:

Compound of example 1 5.5 g

Paraaminophenol 0.57 g

2-methyl-5-amino phenol 0.21 g

2,4-diamino butylbenzene dihydrochloride 0.15 g

Orthoaminophenol 0.9 g

Sodium lauryl sulfate at 19% starting oxyethylenated alcohol 20 g

Ethylenediaminetetraacetic acid 0.2 g

Sodium bisulfite at 35e B 1 g

Ammonia at 22 ° B 10g

Water q.s.p 100 g

The pH of this composition is equal to 10.1.

At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.

This mixture applied to bleached hair for 20 min at 25 ° C gives them, after rinsing and shampooing, a dark brown coloring.

Example 5:

The following dye composition is prepared:

Compound of Example 1 1.9 g

Paraaminophenol 1.42 g

Paraphenylenediamine dihydrochloride 2.38 g

2-methyl resorcin 0.95 g

6-amino dihydrochloride benzomorpholine 2.85 g

Butylglycol 19 g

Coconut fatty acid diethanolamides 5.7 g

Ammonia at 22 ° B 14.3g

Water q.s.p 100 g

The pH of this composition is 9.5.

At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.

This mixture applied to naturally white hair at 90% for 20 min at 20 ° C gives them, after rinsing and shampooing, an extremely dark blue-black coloration.

Example 6:

The following dye composition is prepared:

Compound of Example 1 0.88 g

[N- (p-hydroxyethyl) amino-2-amino-4] hydrochloride

phenoxyethanol 0.86 g

Propylene glycol 30 g

Polymers of acrylic acid having a molecular weight of 2 to 3 million and sold under the name Carbo-

pol 934 by Goodrich Chemical Co 2.7 g

Ammonia at 22 ° B 8 g

Water q.s.p 100 g

The pH of this composition is equal to 10.

At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.

This mixture applied to bleached hair for 20 min at 20 ° C gives them, after rinsing and shampooing, a royal blue coloring.

Example 7:

The following dye composition is prepared:

Compound of Example 1 0.3 g

Paraaminophenol 0.65 g

(2,4-diamino) phenoxyethanol dihydrochloride 1.80 g

Carboxymethylcellulose 3 g

Propylene glycol 27 g

Triethanolamine 10 g

Water q.s.p 100 g

The pH of this composition is 8.5.

At the time of use, 1 g of dihydroxy-2,4 N- (P-methoxyethyl) amino-4 'diphenylamine dihydrochloride is added to this composition, then 50 g of hydrogen peroxide at 20 volumes are added.

This mixture applied to naturally white hair at 90% for 20 min at 25 ° C gives them, after rinsing and shampooing, a silvery blue-gray coloring.

Example 8:

The following dye composition is prepared:

Compound of example 1 0.4 g

Paraaminophenol 0.3 g a-Naphtol 0.58 g

Propylene glycol 26 g

Carboxymethylcellulose 3.1 g

Triethanolamine 10 g

Water q.s.p 100 g

The pH of this composition is equal to 8.7.

Just before application, 1 g of 2,4-dihydroxy-methyl-5 N- (P-methoxyethyl) -amino-4'-diphenylamine dihydrochloride is added to this composition, then 80 g of hydrogen peroxide are added to the mixture. 20 volumes.

This mixture applied to naturally white hair at 90% for 20 min at 30 ° C gives them, after rinsing and shampooing, a metallic gray coloring with purple reflections.

Example 9:

The following dye composition is prepared:

Compound of example 1 3g

N, N- (P-hydroxyethyl) 4-amino aniline sulfate 3 g

Paraaminophenol 0.08 g

2-methyl-5-amino phenol 0.02 g

Resorcin 0.4 g

(2,5-diamino) phenoxyethanol dihydrochloride 0.04 g

Oxyethylenated oleic alcohol with 2 mol of ethylene oxide ... 4.5 g

Oxyethylenated oleic alcohol with 4 mol of ethylene oxide. . . 4.5g

Coconut fatty acid diethanolamides 10 g

Hydroquinone 0.1 g

Sodium bisulfite at 35 ° B 1 g

Sodium salt of diethylenetriaminepentaacetic acid. . 2 g

Diethylene glycol monomethyl ether 4.5 g

Butylglycol 8 g

Ethanol at 96 ° 8 g

Ammonia at 22 ° B 10 g

Water q.s.p 100 g

The pH of this composition is 10.2.

At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.

This mixture applied to naturally white hair at 90% for 20 min at 30 ° C gives them, after rinsing and shampooing, a very ashy brown coloring.

Example 10:

The following dye composition is prepared:

Compound of example 1 2g

N, N- (ethyl, p-mesylaminoethyl) amino-4 dihydrochloride

aniline 1 g

Paraphenylenediamine dihydrochloride 0.5 g

Paraaminophenol 0.62 g

2-methyl-5-amino phenol 0.3 g

2,6-Dimethyl-5-acetylamino phenol 0.2 g

Metaaminophenol 0.1 g

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Sodium lauryl sulfate 19% starting oxyethylenated alcohol 20 g

Ethylenediaminetetraacetic acid 0.2 g

Ammonia at 22 ° B 10 g

Sodium bisulfite at 35 ° B 1 g

Water q.s.p 100 g

The pH of this composition is 10.2.

At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.

This mixture applied to naturally white hair at 90% for 20 min at 25 ° C gives them, after rinsing and shampooing, a red copper brown coloring.

Example II:

The following dye composition is prepared:

Compound of Example 1 0.2 g

2-methyl-5-carbethoxyamino phenol 0.2 g

2,6-dimethyl-3-methoxy-paraphenylenediamine dihydrochloride 0.52 g

Nitro-3 N'-methylamino-4 N, N- (P-hydroxyethyl) aniline. . 1.5g

Butylglycol 20 g

Polymer of acrylic acid having a molecular weight of between 2 and 3 million, manufactured by the company Goodrich Chemical Co 3.2 g

Ammonia at 22 ° B 5 g

Water q.s.p 100 g

The pH of this composition is equal to 9.9.

At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.

This mixture applied to naturally white hair at 90% for 15 min at 25 ° C gives them, after rinsing and shampooing, a silvery gray-purple coloration.

Example 12:

The following dye composition is prepared:

Compound of example 1 3 g

Paratoluylenediamine dihydrochloride 1.5 g

Paraaminophenol 0.7 g

2-methyl-N- (P-hydroxyethyl) 3-amino phenol 0.4 g

(2,4-diamino) phenoxyethanol dihydrochloride 0.15 g

N-methylamino-4 phenol 0.6 g

Metaaminophenol 0.11g

Nitro-3 N- (P-hydroxyethyl) 4-amino phenol 0.05 g

Oxyethylenated oleic alcohol with 2 mol of ethylene oxide. . . 4.5g

Oxyethylenated oleic alcohol with 4 mol of ethylene oxide. . . 4.5g

Propylene glycol 8.3 g

Ammonia at 22 ° B 9 g

Sodium bisulfite at 35 ° B 1 g

Water q.s.p 100 g

The pH of this composition is equal to 9.9.

At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.

This mixture applied to bleached hair for 20 min at 25 ° C gives them, after rinsing and shampooing, a very dark brown color with purple reflections.

Example 13:

The following dye composition is prepared:

Compound of example 1 3 g

N, N- (ethyl, carbamylmethyl) 4-amino aniline 2 g

Paraaminophenol 0.8 g

0.2 g resorcin

2-methyl-5-carbethoxyamino phenol 0.3 g

2-methyl-N- (P-hydroxyethyl) -5-amino phenol 0.3 g

Nitro-3 N- (P-hydroxyethyl) amino-6 anisole 0.1 g

Butylglycol 5 g

Laury alcohol oxyethylenated with 10.5 mol of ethylene oxide 5 g

Ammonia at 22 ° B 10 g

Water q.s.p 100 g

The pH of this composition is equal to 10.

At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.

This mixture applied to naturally white hair at 90% for 20 min at 25 ° C gives them, after rinsing and shampooing, a tobacco coloring.

Example 14:

The following dye composition is prepared:

Compound of example 1 1.17 g

Metaaminophenol 0.43 g

Oxyethylenated oleic alcohol with 2 mol of ethylene oxide. . . 4.5g

Oxyethylenated oleic alcohol with 4 mol of ethylene oxide ... 4.5 g

Coconut fatty acid diethanolamides 10 g

Hydroquinone 0.1 g

Sodium bisulfite at 35 ° B 1 g

Sodium salt of diethylenetriaminepentaacetic acid. . 2 g

Propylene glycol . 4.5g

Butylglycol 8 g

Ethanol 95 ° 8 g

Ammonia at 22 ° B 10 g

Water q.s.p 100 g

The pH of this composition is 10.6.

At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.

This mixture applied to naturally white hair at 90% for 20 min at 25 ° C gives them, after rinsing and shampooing, a gray-blue coloring.

Example 15:

The following dye composition is prepared:

Compound of Example 1 0.23 g

(2,4-diamino) phenoxyethanol dihydrochloride 0.19 g

Sodium lauryl sulfate 19% starting oxyethylenated alcohol 20 g

Ethylenediaminetetraacetic acid 0.2 g

Ammonia at 22 ° B 10 g

Sodium bisulfite at 35 ° B 1 g

Water q.s.p 100 g

The pH of this composition is 10.8.

At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.

This mixture applied to bleached hair for 15 min at 25 ° C gives them, after rinsing and shampooing, a sky blue coloring.

Example 16:

The following dye composition is prepared:

Compound of Example 1 0.73 g

2-methyl-N- (P-hydroxyethyl) -5-amino phenol 0.42 g

Butylglycol 5 g

Laury alcohol oxyethylenated with 10.5 mol of ethylene oxide 5 g

Ammonia at 22 ° B 10 g

Water q.s.p 100 g

The pH of this composition is 10.5.

At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.

This mixture applied to bleached hair for 20 min at 25 ° C gives them, after rinsing and shampooing, an intense purple coloring.

Example 17:

The following dye composition is prepared:

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Compound of Example 1 0.35 g

2,6-Dimethyl-5-acetylamino phenol 0.21 g

Sodium lauryl sulfate at 19% starting oxyethylenated alcohol 20 g

Ethylenediaminetetraacetic acid 0.2 g

Ammonia at 22 ° B 10 g

Thioglycolic acid 1 g

Water q.s.p 100 g

The pH of this composition is 10.8.

At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.

This mixture applied to bleached hair for 20 min at 25 ° C gives them, after rinsing and shampooing, a light sky blue coloring.

Example 18:

The following dye composition is prepared:

Compound of Example 1 0.98 g

N, N- (ethyl, carbamylmethyl) 4-amino aniline 1.8 g

[N- (P-hydroxyethyl) amino-2-amino-4] hydrochloride

phenoxyethanol 0.104 g

Nitro-3 N- (P-hydroxyethyl) 4-amino phenol 0.36 g

95 ° ethanol 14.5 g

Triethanolamine 6.3 g

Water q.s.p 100 g

The pH of this composition is equal to 8.6.

At the time of use, 60 g of hydrogen peroxide are added to 20 volumes.

This mixture applied to naturally white hair at 90% for 20 min at 25 ° C gives them, after rinsing and shampooing, a very dark purple coloration.

Example 19:

The following dye composition is prepared:

Compound of Example 1 1.18 g

Resorcin 0.43 g

Sodium lauryl sulfate 19% starting oxyethylenated alcohol 20 g

Ethylenediaminetetraacetic acid 0.2 g

Ammonia at 22 ° B 10 g

Sodium bisulfite at 35 ° B 1 g

Water q.s.p 100 g

The pH of this composition is 10.7.

At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.

This mixture applied to naturally white hair at 90% for 20 min at 25 ° C gives them, after rinsing and shampooing, a light beige golden coloration.

Example 20:

The following dye composition is prepared:

Compound of Example 1 1.1g

N, N- (ethyl, mesylaminoethyl) amino-4 dihydrochloride

aniline 3.1 g

[N- (P-hydroxyethyl) amino-2-amino-4] hydrochloride

phenoxyethanol 0.11g

Nitro-3 N- (P-hydroxyethyl) 4-amino phenol 0.33 g

Ethanol at 96 ° 16 g

Triethanolamine 6 g

Water q.s.p 100 g

The pH of this composition is equal to 8.2.

At the time of use, 60 g of hydrogen peroxide are added to 20 volumes.

This mixture applied to naturally white hair at 90% for 25 min at 22 ° C gives them, after rinsing and shampooing, a very dark navy blue coloring.

Example 21:

The following dye composition is prepared:

Compound of Example 1 1.1g

N, N- (ethyl, mesylaminoethyl) amino-4 dihydrochloride

aniline 3, 1 g

[N- (P-hydroxyethyl) amino-2-amino-4] hydrochloride

phenoxyethanol 0.11g

Nitro-3 N- (P-hydroxyethyl) 4-amino phenol 0.33 g

1,2,4-trihydroxy benzene 0.9 g

Ethanol at 96 ° 16g

Triethanolamine 6 g

Water q.s.p 100 g

The pH of this composition is equal to 7.9.

At the time of use, 60 g of hydrogen peroxide are added to 20 volumes.

This mixture applied to naturally white hair at 90% for 25 min at 20 ° C gives them, after rinsing and shampooing, a coppery brown coloring.

Example 22:

The following dye composition is prepared:

Compound of Example 1 0.98 g

N, N- (ethyl, carbamylmethyl) 4-amino aniline 1.8 g

1,2,4-trihydroxy benzene 0.90 g

[N- (P-hydroxyethyl) amino-2-amino-4] hydrochloride

phenoxyethanol 0.104 g

Nitro-3 N- (P-hydroxyethyl) 4-amino phenol 0.36 g

Ethanol at 96 ° 14.5 g

Triethanolamine 6.3 g

Water q.s.p 100 g

The pH of this composition is 8.5.

At the time of use, 60 g of hydrogen peroxide are added to 20 volumes.

This mixture applied to bleached hair for 20 min at 25 ° C gives them ", after rinsing and shampooing, a dark reddish copper color.

Example 23:

The following dye composition is prepared:

Compound of example 1 lg

Paraphenylenediamine dihydrochloride 0.6 g

(2,4-diamino) phenoxyethanol dihydrochloride 0.48 g

Dihydroxy-4,4 '2-amino-5-methyl diphenylamine 0.52 g

Hydroxy-4 amino-2 methyl-5 N, N- (P-hydroxyethyl) amino-

4 'diphenylamine 1 g

Sodium lauryl sulfate 19% starting oxyethylenated alcohol 20 g

Ethylenediaminetetraacetic acid 0.2 g

Triethanolamine 10g

Sodium bisulfite at 35 ° B 1 g

Water q.s.p 100 g

The pH of this composition is 8.4.

At the time of use, 60 g of hydrogen peroxide are added to 20 volumes.

This mixture applied to bleached hair for 20 min at 20 ° C gives them, after rinsing and shampooing, an extremely dark purple coloring.

Example 24:

The following dye composition is prepared:

Compound of example 1 2 g

Orthodiphenol 0.374 g

[N- (P-hydroxyethyl) amino-2-amino-4] hydrochloride

phenoxyethanol 0.03 g

2-methyl-5-amino phenol 0.1g

Nonylphenol 4 mol ethylene oxide 16 g

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Nonylphenol with 9 mol of ethylene oxide 16g

Propylene glycol 10g

Bisulfite solution at 35 ° B lg

Ammonia at 22 ° B 7 g

Water q.s.p. . . 100g 5

The pH of this composition is equal to 9.9.

At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.

This mixture is applied 20 min at room temperature to bleached white hair. After rinsing and shampooing, it gives them a steel gray coloring.

It is understood that the method of preparation and the examples of composition given above are in no way limiting and may give rise to any desirable modifications, without thereby departing from the scope of the invention.

R

Claims (19)

637,625 1. Chemical compound of general formula: nh- (ch2) n - or formula in which R represents a substituted alkyl radical, the alkyl group comprising from 1 to 4 carbon atoms, n being equal to 2 or 3, as well as the corresponding acid salts. 2. Compound according to claim 1, characterized in that R is a hydroxyalkyl, alkoxyalkyl, mesylaminoalkyl, acetyl-aminoalkyl, ureidoalkyl, carbethoxyaminoalkyl, aminoalkyl, mono-or dialkylaminoalkyl radical. 3. Dye composition for keratin fibers and in particular for human hair, characterized in that it contains, in a cosmetic vehicle, at least one compound according to one of claims 1 or 2. 4. Composition according to claim 3, characterized in that it contains from 0.001 to 6% by weight of one or more compounds according to one of claims 1 or 2 relative to the total weight of the composition. 5. Composition according to one of claims 3 or 4, characterized in that its pH is between 7, 8 and 11.5. 6. Composition according to claim 5, characterized in that the alkalizing agents used are taken from the group formed by alkylamines, alkanolamines, alkylalkanolamines, hydroxides and carbonates of sodium, potassium or ammonium. 7. Composition according to one of claims 3 to 6, characterized in that it contains, in addition to the compounds according to one of claims 1 or 2, at least one other oxidation dye taken from the group formed by para-phenylenediamines, para-amino phenols, orthophenylenediamines, orthoaminophenols and orthodiphenol. 8. Composition according to one of claims 3 to 7, characterized in that it contains at least one coupler. 9. Composition according to claim 8, characterized in that the coupler (s) is (or are) chosen (s) from the group formed by metaphenylenediamines, metaaminophenols, metadiphenols, metaacetylaminophenols, metacarbalcoxy -5-amino phenols, meta-ureidophenols, hydroxy-6 phenomor-pholine, Famino-3 methoxy-4 phenol, a-naphthol, diamino-2,6 Pyridine. 10. Composition according to one of claims 3 to 9, characterized in that it contains at least one direct dye. 11. Composition according to claim 10, characterized in that it contains at least one dye taken from the group formed by nitro dyes of the benzene series. 12. Composition according to one of claims 3 to 11, characterized in that it contains at least one leuco-derivative of indo-anilines and / or indophenols. 13. Composition according to one of claims 3 to 12, characterized in that it contains at least one product taken from the group formed by dye precursors of the benzene series, comprising on the nucleus at least three substituents taken from the group formed by hydroxyl, methoxy or amino groups such as 2,6-diamino dihydrochloride hydroquinone, 2,6-diamino trichlorhydrate, 4-N-ethylamino-phenol, 2,4-diamino dihydrochloride phenol, 1,2,4,4-trihydroxy benzene, 2,3,5-trihydroxy toluene, 4-methoxy-2-amino-N- (P-hydroxyethyl) aniline. 14. Composition according to one of claims 3 to 13, characterized in that it contains at least one water-soluble surfactant in a proportion of between 0.5 and 30% by weight and, preferably, between 4 and 25% by weight relative to the total weight of 5 the composition. 15. Composition according to one of claims 3 to 14, characterized in that it contains at least one organic solvent in a proportion of between 1 and 40% by weight and, preferably, between 5 and 30% by weight. relative to the total weight of the composition. 16. Composition according to one of Claims 3 to 15, characterized in that it contains at least one thickening product in a proportion of between 0.5 and 5% by weight and, preferably, between 0.5 and 3% by weight relative to the total weight of the composition. 17. Composition according to one of claims 3 to 16, character- 15 sée by the fact that it contains at least one antioxidant in a proportion of between 0.05 and 1.5% by weight relative to the total weight of the composition. 18. Composition according to one of claims 3 to 17, characterized in that it contains at least one adjuvant taken in the 20 group formed by penetrating agents, sequestering agents and perfumes. 19. Composition according to one of claims 3 to 18, characterized in that it is in the form of liquid, cream, gel or aerosol. 20. Composition according to one of claims 3 to 19, characterized in that, at the time of use, it contains oxidizing agents such as hydrogen peroxide, urea peroxide or persalts. 21. Composition according to one of claims 3 to 20, character- 30 sée by the fact that, at the time of use, it contains leucodé-rivés of indoanilines or indophenols. It is known that paraphenylenediamines play a very well known role in the oxidation dyes of keratin fibers and in particular of the hair, whether they are used alone or in combination with metaphenylenediamines, metaaminophenols or metadiphenols. So that an oxidation dye, and in particular a paraphenylenediamine, can be selected for hair dyes, it must have, when it is applied in a hair dye, good safety and it is also necessary to 45 that the shades conferred on the hair, during application in an oxidizing alkaline medium, are stable over time and, in particular, resist light, weathering and shampooing for the duration which usually separates two successive hair dyes.