FR2488133A1 - Hair dyeing compsn. contg. violet nitro dye - and yellow nitro dye, for use on treated hair - Google Patents

Abstract

A non-mutagenic or very weakly mutagenic compsn. for the direct dyeing of human hair contains (a) at least 1 violet nitro dye with a Munsell shade of 7.5P-10PB, and (b) at least 1 yellow nitro dye with a Munsell shade of 10-2.5Y. The ratio of concn. by wt. of (a):(b) is 1-3, and the dyes are present in proportions such that their coeffts. of selectivity are about equal, and are 3-8 when determined at a concn. by wt. of 0.1-0.6%. The dyes (a) and (b) have the same stability to light, shampooing and perspiration. The concn. of (a)+(b) is 0.04-2.5wt.%. A natural, uniform shade can be obtd. from the root of the hair to the tip, on hair where the sensitivity varies along the length due to, e.g. permanent waving.

Description

Dye compositions for hair based on direct nitro dyes and dyeing process using said compositions.

 The present invention relates to new dye compositions intended for the direct dyeing of human hair, and in particular permed, natural or bleached hair.

 Combinations of dyes are frequently used in hair dyeing to obtain various shades. This is how we have already used, for obtaining natural hair dye compositions comprising direct nitro violet dyes in combination with direct nitro yellow dyes.

 A difficulty arises, however, when using such combinations of dyes on hair whose sensitivity to hair dyes differs from root to tip. This is particularly so for hair whose roots are natural and whose ends have already undergone various treatments such as bleaching or perming. It is very difficult, in this case, to obtain a good leveling color from the root to the tip of the hair, which is stable over time t when two or more dyes are used in combination. In fact, we can see different colors depending on the degree of awareness of the hair.

 The Applicant has discovered that it is possible to obtain, on hair whose degree of sensitization varies from root to tip, a natural shade whose shade is substantially the same from root to tip by using a dye composition comprising at least a violet nitro dye and at least one yellow nitro dye chosen from certain particular groups so that the violet dye and the yellow dye neutralize each other perfectly, have a substantially equal selectivity and have substantially the same fastness to light, shampoos and perspiration.

 The difference in the rise of the dye on the hair fiber is called selectivity of a dye, depending on whether the latter is more or less sensitized by a treatment such as perm.

 The Applicant has therefore found that if dyes of selectivity and substantially equal solidity were used in a dye composition, these dyes had the same type of behavior on a hair differently sensitized from root to tip and subjected to the action of light, washing or perspiration and thus obtaining a dye having a shade the intensity of which can be weakened during such a subsequent action, but the reflection of which remains the same from root to tip, whatever whatever the differences in sensitization of the hair to the dye when going from the root to the tip.

 Thus, a violet dye and a yellow dye of substantially similar selectivity and solidity, for example both rising more strongly on the tips of the hair having undergone a perm treatment, will for example be weakened in the same way by light, washing or perspiration, so that the reflection of the shade will be kept from the root to the tip of the hair since the two dyes will have the same behavior.

 The result sought by the applicant is achieved in accordance with the invention if a dye composition is used comprising at least one violet nitro dye having a shade according to Munsell ranging from 7.5 P to 10 PB and at least one yellow nitro dye having a shade according to Munsell ranging from 10 Y 2.5 Y, these dyes having a substantially identical selectivity coefficient ranging from 3 to 8 when it is determined for a weight concentration between 0.1 and 0.6% and substantially the same solidities in the light, in shampoo and in perspiration.

 An additional condition for the purple and yellow dyes to neutralize is that the ratio of their weight concentrations (sum of violets / sum of yellows) is between 1 and 3.

 The present invention therefore relates to a dye composition for the direct dyeing of human hair, which comprises at least one violet nitro dye having a shade according to Munsell ranging from 7.5 P 9 10 PB and at least one yellow nitro dye having a shade according to Munsell ranging from 10 Y to 2.5 Y, these purple and yellow dyes being used respectively in a weight concentration ratio ranging from 1 to 3 and having a substantially identical selectivity coefficient ranging from 3 to 8, when the latter is determined for a concentration by weight of between 0.1 and 0.6%.

We know that according to Munsell's notation, a color is defined by the formula
HV / C in which the three parameters respectively designate the shade or whueZ (H), the intensity or "value" (V) and the purity or wchromaticite (C), the inclined line being a simple convention.

 The shade H can be expressed by a number followed by one or two letters characterizing the color, P meaning for example purple, B blue and Y yellow.

 With regard to Munsell's notation, reference is made to the publication of Official Digest, April 1964, page 375, fig. 2.

 Since the selectivity of a dye varies with its concentration, it is more rational to define for a given dye, its selectivity coefficient at a given concentration. This coefficient thus makes it possible to compare different dyes with each other.

The selectivity coefficient of a dye can be determined as follows
A lock of natural hair that is not sensitized, that is to say that has not undergone perm treatment, is dyed using a dye composition containing the dye X at a CO weight concentration, under conditions fixed dyeing with regard to support, pH, temperature, etc. We obtain an intensity VO.

A sensitized lock is dyed, that is to say having undergone a permanent treatment under the same dyeing conditions, but with dye compositions containing decreasing weight concentrations of dye X, C1,
C2 ... Cn
The concentration Cn is sought for which the same intensity is obtained on the sensitized lock as on the non-sensitized lock with the CO concentration by dye X.

dans laquelle R1 désigne le radical 2-hydroxyéthyle, R2 le radical -hydroxyéthyle ou méthyle et R3 le radical ss -hydro xyéthyle, méthyle ou bien le radical ss-aminoéthyle lorsque R2 désigne le radical ss -hydroxyéthyle, et comme colorants jaunes, les o- ou p-nitroanilines de formule

dans laquelle R4 désigne de l'hydrogène, R5 le groupe isopropyle et R6 le groupe amino, ou bien R4 désigne le groupe ss-hydroxyéthyloxy, R5 de l'hydrogène et R6 le groupe méthyla mino ou 0 -hydroxyéthylamino , ou bien R4 désigne le groupe ,dihydroxypropyloxy, R5 de l'hydrogène et R6 le groupe amino, méthylamino ou 0-hydroxyéthylamino, ou encore R4 désigne le groupe g -hydroxyéthylamino, R5 le groupe méthoxy et R6 de l'hydrogène, ou bien encore R4 désigne le groupe méthoxy, R5 de l'hydrogène et R6 le groupe -hydroxye'thylamino,-hydroxy- propylamino ou /j b'- dihydroxypropylamino. The selectivity coefficient of the dye X at the CO concentration in the given support is then defined as being the ratio
SCo = CO / Cn
According to a preferred embodiment of the invention, the applicant uses as purple dyes, 2-nitro-p-phenylenediamines of formula

in which R1 denotes the 2-hydroxyethyl radical, R2 denotes the -hydroxyethyl or methyl radical and R3 denotes the ss -hydro xyethyl, methyl radical or else the ss-aminoethyl radical when R2 denotes the ss -hydroxyethyl radical, and as yellow dyes, the o - or p-nitroanilines of formula

in which R4 denotes hydrogen, R5 the isopropyl group and R6 the amino group, or else R4 denotes the ss-hydroxyethyloxy group, R5 denotes hydrogen and R6 denotes the methyla mino or O-hydroxyethylamino group, or alternatively R4 denotes the group, dihydroxypropyloxy, R5 of hydrogen and R6 the amino group, methylamino or 0-hydroxyethylamino, or R4 denotes the group g -hydroxyethylamino, R5 denotes the methoxy group and R6 of hydrogen, or also R4 denotes the methoxy group , R5 of hydrogen and R6 the group -hydroxye'thylamino, -hydroxy-propylamino or / j b'- dihydroxypropylamino.

 The Applicant has found that the above dyes used in combination in a dye composition not only made it possible to obtain neutral and natural shades whose reflection is preserved when passing from non-sensitized parts to sensitized parts of the hair and is only attenuated without being modified by light, shampoos and perspiration, but also that these dyes had the very interesting property of being non-mutagenic or only very weakly mutagenic.

In the present description, the non-mutagenic nature of the dyes is appreciated in the Ames test, on Salmonella
Typhimurium, with or without S 9 mix, activated or not by Arochlor (prior treatment of rats with Arochlor), and this, on the five strains TA 1535, TA 1537, TA 100, TA 1538 and TA 98.

The Ames test is described in particular in the following publications - Ames BN; KAMMEN HO; YAMASAKI E. "Dyes are mutagenic;
Identification of a variety of mutagenic Ingredients "
Proc. Nat. Acad. Sci. USA, vol. 72, no. 6, p. 2423-2427 (June 1975) - Ames BN; J. Mc CANN and E. YAMASAKI, Methods for detecting carcinogens and mutagens with Salmonella mammalian microsome mutagenicity test, Mutation Res., 31 (1975) p. 347-364.

 According to another characteristic of the present invention, the sum of the concentrations of the purple dyes and yellow dyes contained in the dye compositions of the invention can range from 0.04% to 2.5% by weight.

The dye compositions according to the invention may contain, in addition to the purple dyes and the yellow dyes indicated above, other nitro dyes making it possible to obtain
hold more or less red shades and more or less cui
and thus vary the reflection of the nuances.

These dyes must always have selectivity
lower than that of the purple and yellow dyes of formula
(I) and (II).

dans laquelle R7 désigne de l'hydrogène et R8 un groupe amino ou 0 -hydroxyethylamino, ou bien R7 désigne le groupe amino et
R8 de l'hydrogène.Dyes particularly suitable for being
used in combination with the aforementioned purple and yellow dyes are the 3-nitro-aminophenols of formula

in which R7 denotes hydrogen and R8 denotes an amino or O-hydroxyethylamino group, or else R7 denotes the amino group and
R8 of hydrogen.

 The Applicant has also found that the red dyes of formula (III) above mentioned also have the property of being non-mutagenic or very weakly mutagenic in the Ames test.

 The dye compositions according to the invention may contain 0.001 to 2.5% by weight and preferably 0.005 to 1.5% by weight of one or more of the dyes of formula (III) above.

 The dye compositions according to the invention may comprise, in an aqueous vehicle, in addition to the direct nitro dyes defined above, a solvent, for example an alcohol such as ethyl alcohol, isopropyl alcohol or benzyl alcohol or a glycol or glycol ether such as for example butylglycol, ethylene glycol, propylene glycol, ethylcellosolve, carbitol or butylcarbitol, in concentrations of between 0.5 and 20% by weight and preferably between 2 and 10% by weight.

 They can also contain anionic, cationic, amphoteric or nonionic surfactants, or a mixture thereof, in concentrations generally between 0.05 and 50% by weight and preferably between 0.5 and 10% by weight.

 By way of nonlimiting examples, mention may be made, among the anionic surfactants used alone or as a mixture, of the alkaline salts, the magnesium salts, the ammonium salts, the amine salts or the alkanolamine salts of the following compounds - alkyl sulfates, alkyl ether sulfates, alkylamide sulfates, ethoxylated or not, - alkyl sulfonates, alkylamide sulfonates, alphaolefins sulfonates, - alkyl sulfoacetates, the alkyl radicals of these compounds having a linear chain from C12 to C181 - fatty acids such as lauric acid , myristic, oleic, ricinoleic, palmitic, stearic, coconut oil or hydrogenated coconut oil acids, carboxylic acids of polyglycolic ethers.

Among the cationic surfactants which can be used alone or as a mixture, there may be mentioned in particular
- salts of fatty amines,
quaternary ammonium salts such as chlorides and bromides of alkyldimethylbenzylammonium, of alkyltrimethylammonium, of alkyldimethylhydroxyethylammonium, of dimethyldistearylammonium,
- alkylpyridinium salts,
- imidazoline derivatives.

 Mention may also be made of compounds of cationic nature such as amine oxides.

 Among the amphoteric surfactants which can be used, there may be mentioned in particular - alkylamino-mono- and dipropionates, - betaines such as alkylbetaines, N-alkyl-sulfobetaines, N-alkylamino betaines, the alkyl radical containing from 1 to 22 carbon atoms, - cycloimidiniums such as alkylimidazolines.

dans laquelle R désigne un radical aliphatique, cycloaliphatique ou arylaliphatique ayant de 7 à 21 atomes de carbone et leurs mélanges, les channes aliphatiques pouvant comporter des groupements éther, thioéther et hydroxyméthylène et n2 étant un nombre entier tel que 1 4 n2 # 10; les composés de formule

H dans laquelle R désigne un radical alkyle, alkényle ou alkyiaryle ayant 8 à 22 atomes de carbone et 16n3' 10,
- les alcools, alkylphénols ou acides gras polyéthoxylés ou polyglycérolés à channe grasse linéaire en C8 à C18,
- les condensats d'oxyde d'éthylène et de propylène sur des alcools gras,
- les amides gras polyéthoxylés,
- les amines grasses polyéthoxylées.Among the nonionic surfactants, which can optionally be used in admixture with the anionics and / or cationics mentioned above, there may be mentioned
- the condensation products of a monoalcohol, of a <5-diol, of an alkylphenol, or of an amide with glycidol, for example, the compounds of formula

in which R denotes an aliphatic, cycloaliphatic or arylaliphatic radical having from 7 to 21 carbon atoms and their mixtures, the aliphatic chains can comprise ether, thioether and hydroxymethylene groups and n2 being an integer such as 1 4 n2 # 10; the compounds of formula

H in which R denotes an alkyl, alkenyl or alkyiaryl radical having 8 to 22 carbon atoms and 16n3 ′ 10,
- alcohols, alkylphenols or polyethoxylated or polyglycerolated fatty acids with a linear fatty chain at C8 to C18,
- condensates of ethylene and propylene oxide on fatty alcohols,
- polyethoxylated fatty amides,
- polyethoxylated fatty amines.

 The dye compositions according to the invention may also contain fatty amides, such as mono- and di-ethanolamides of acids derived from coconut, lauric acid or oleic acid, concentrations of between 0.05 and 10 % in weight.

 The dye compositions according to the invention may also contain thickeners such as sodium alginate or gum arabic or cellulose derivatives such as methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, in concentrations of between 0 , 5 and 15% by weight.

 In addition to the ingredients mentioned above, they may contain adjuvants such as perfumes, preservatives and sequestering agents.

 The pH of the dye compositions according to the invention can be between 6 and 11, but preferably between 8 and 10.

 It is adjusted with alkaline agents such as monoethanolamine, diethanolamine, triethanolamine, ammonia, ammonium, potassium or sodium carbonate, soda or with acidifying agents such as phosphoric and hydrochloric acids. , tartaric, acetic, lactic or citric.

 The dye compositions according to the invention can be in various usual forms such as thickened liquids, foaming liquids, aerosol foams, etc.

 They can be applied to natural, permed natural hair or to strongly or slightly discolored hair, possibly permed.

 The present invention therefore also relates to a process for dyeing human hair by direct dyeing.

 According to a preferred embodiment of the invention, the hair is subjected to a lightening treatment either with the aid of an ammonia hydrogen peroxide solution or containing alkaline agents such as aliphatic or hydroxy aliphatic amines, or using an ammoniacal solution of peroxides or alkaline persalts, such as sodium peroxide, potassium peroxide, sodium perborate, sodium percarbonate, urea peroxide or addition compounds of hydrogen peroxide and organic compounds such as melanin perhydrate, although this list is not exhaustive.

 This lightening solution is applied to the hair, it is left on for 5 to 30 minutes depending on the desired lightening, after which it is rinsed with water and the dye composition according to the invention is applied which is left on for 15 to 30 minutes at room temperature; the hair is then rinsed and dried. According to another variant, the lightening solution and the dye composition according to the invention are applied simultaneously to the hair.

After leaving on for 15 to 30 minutes, the hair is rinsed and dried.

 The dye compositions according to the invention make it possible to obtain, in all cases on permed hair, a solid coloring in a shade the reflection of which is preserved from the root to the tip of the hair, without being modified by light, shampoos or perspiration.

 The present invention will be better understood from the following nonlimiting examples.

EXAMPLE 1
A lightening solution is prepared by mixing 30 g of hydrogen peroxide at 20 volumes with 10 g of an aqueous solution containing 3.5% of ammonia and 4% of hydroxyethylcellulose. This solution is applied to hair which has undergone a perming treatment some time before, which will hereinafter be called permed-tip hair. "Leave to stand for 15 minutes, then rinse with water.

The following dye composition is also prepared
Lauric amide 15 g
Lauric acid 10 g
Butylglycol 60 g
Hydroxyethylcellulose 50 g N1, N4, N4-tri (6-hydroxyethyl) 2-nitro-p-phenylene diamine 7.0 g 2-isopropyl o-nitroaniline 3.8 g
Monoethanolamine qs pH 9
Water qs 1000 g
This composition is applied to the hair having undergone the above lightening pretreatment. After 30 minutes of exposure at room temperature, the hair is rinsed and dried. This solution provides a very even natural color. Note that this color is more intense on the permanent parts, that is to say on the tips, but that the reflection of the shade is kept from the root to the tip of the hair. It is attenuated, without being modified by light or by perspiration.

EXAMPLE 2
The lightening solution of Example 1 is applied to hair with permanent tips and simultaneously the following dye composition
Lauric amide 15 g
Lauric acid 10 g
Butylglycol 60 g
Hydroxyethyl cellulose 50 g N1-methyl-N4, N4-bis (B-hydroxyethyl) 2-nitro p-phenylenediamine 0.5 g 2-isopropyl o-nitroaniline 0.3 g
Monoethanolamine qs pH g
Water qs 1000 g
This composition provides, after 20 minutes of exposure at room temperature and rinsing with water, a very uniform natural color. It is found that substantially the same results are obtained as in Example 1.

EXAMPLE 3
We prepare the following dye composition
Lauric amide 15 g
Lauric acid 10 g
Butylglycol 60 g
Hydroxyethyl cellulose 50 g N1-methyl-N4, N4-bis (0-hydroxyethyl) - 2-nitro p-phenylenediamine 2.0 g (4-nitro 3-methylamino) phenoxyethanol 0.8 g
Monoethanolamine qs pH 9
Water qs 1000 g
This composition is applied to natural hair, permed a few weeks before. Leave to stand for 15 minutes at room temperature and rinse. This solution provides a solid natural color; the same results are also observed as above.

EXAMPLE 4
We prepare the following dye composition
Lauric amide 15 g
Lauric acid 10 g
Butylglycol 60 g Hydroxyethylcellulose 50 g N1-methyl-N4, N4-bis (0 -hydroxyethyl) 2-nitro p-phenylenediamine 1.4 g 2-isopropyl o-nitroaniline 0.9 g 3-nitro 4-ainino phenol 0.15 g
Monoethanolamine qs pH 9
Water qs 1000 g
The above composition is applied to permed hair having undergone the lightening pretreatment of Example 1. It is left to stand for 15 minutes at room temperature, then the hair is rinsed and dried.

This solution provides a very even natural blonde coloring.

The same results are noted as in Example 1.

EXAMPLE 5
We prepare the following dye composition
Lauric amide 15 g
Lauric acid 10 g
Butylglycol 60 g
Hydroxyethylcellulose 50 g N1-methyl-N4, N4-bis (-hydroxyethyl) 2-nitro p-phenylenediamine 4.6 g 3-nitro 4-amino phenol 0.3 g 3-nitro 4 - (- hydroxyethyl) amino phenol 0, 36 g (4-nitro 3-methylamino) phenoxyethanol 2.3 g
Monoethanolamine qs pH 9
Water qs 1000 g
This composition is applied to natural hair with permed ends. This solution provides, after 20 minutes of application at room temperature and rinsing with water, a very uniform dark golden blonde coloring. The reflection of the shade is also preserved from the root 9 to the tip of the hair.

EXAMPLE 6
We prepare the following dye composition
Lauric amide 15 g
Lauric acid 10 g
Butylglycol 60 g
Hydroxyethylcellulose 50 g N1-methyl-N4, N4-bis (-hydroxyethyl) 2-nitro p-phenylenediamine 4.0 g 2-isopropyl o-nitroaniline 3.5 g 3-nitro 4- (P-hydroxyethyl) amino phenol 3, 0 g
Monoethanolamine qs pH 9
Water qs 1000 g
This composition is applied to hair with permanent tips having undergone the lightening pretreatment of Example 1. This solution provides, after 20 minutes of laying at room temperature and rinsing with water, a very blond dark iridescent red coloring. united. The results are also identical to those obtained above.

EXAMPLE 7
The lightening solution of Example 1 is applied to hair with permanent tips and simultaneously the following dye composition
Lauric amide 15 g
Lauric acid 10 g
Butylglycol 60 g Hydroxyethylcellulose 50 g
N1-methyl-N4, N4-bis (-hydroxyethyl) 2-nitro p-phenylenediamine 1.1 g (4-nitro 3-methylamino) phenoxyethanol 0.5 g 3-nitro 4-amino phenol 0.06 g
Monoethanolamine qs pH 9
Water qs 1000 g
This solution provides, after 25 minutes of application at room temperature and rinsing with water, a very light natural blond color. We also note the same results as above.

EXAMPLE 8
We prepare the following dye composition
Lauric amide 15 g
Lauric acid 10 g
Butylglycol 60 g
Hydroxyethyl cellulose 50 g N1-methyl-N4, N4bis (0-hydroxyethyl) - 2-nitro p-phenylenediamine 2.6 g 2-isopropyl o-nitroaniline 2.6 g 3-nitro 4-amino phenol 0.25 g 3- nitro 44-hydroxyethyl) amino phenol 0.2 g
Monoethanolamine qs pH 9
Water qs 1000 g
This composition is applied to natural hair with permed ends; this solution brings, after 30 minutes of exposure at room temperature and rinsing 9 with water, a very even golden blonde coloring. The results are also identical to those obtained previously.

EXAMPLE 9
We prepare the following dye composition
Lauric amide 15 g
Lauric acid 10 g
Butylglycol 60 g
Hydroxyethyl cellulose 50 g 3-nitro-4-hydroxyethyl) amino phenol 3.5 g (4-nitro 3-methylamino) phenoxyethanol 2.5 g
N1, N4, N4-tri (ss -hydroxyethyl) 2-nitro p-phenylenediamine 4.5 g
Monoethanolamine qs pH 9
Water qs 1000 g
This composition is applied to hair with permanent tips having undergone the lightening pretreatment of Example 1, this solution provides, after 30 minutes of laying at room temperature and rinsing with water, a very uniform mahogany brown coloring. We also note results identical to those obtained previously.

EXAMPLE 10
We prepare the following dye composition
Lauric amide 15 g
Lauric acid 10 g
Butylglycol 60 g
Hydroxyethyl cellulose 50 g N1, N4, N4-tri (-hydroxyethyl) 2-nitro p-phenylenediamine 4g 2-isopropyl o-nitroaniline 4 g 3-nitro 4 - (- hydroxyethyl) amino phenol 4 g
Monoethanolamine qs pH 9
Water qs 1000 g
This composition is applied to hair 9 permanent ends having undergone the pretreatment-lightening of Example 1. It is left to stand for 25 minutes at room temperature, the hair is rinsed and dried. This solution provides a very solid mahogany brown coloring. We also note results that are substantially identical to those obtained previously.

EXAMPLE 11
We prepare the following dye composition
Lauric amide 15 g
Lauric acid 10 g
Butylglycol 60 g
Hydroxyethyl cellulose 50 g (4-nitro 3-methylamino) phenoxyethanol 0.85 g
N14, N4-tri (-hydroxyethyl) 2-nitro p-phenylenediamine 2.5 g 3-nitro 4-amino phenol 0.1 g
Monoethanolamine qs pH 9
Water qs 1000 g
This composition is applied to lightly bleached permed permanent hair, according to Example 1. This solution provides, after 30 minutes of application at room temperature and rinsing with water, a very uniform light blond coloring. The reflection of the shade is kept from root to tip. It is attenuated, without being modified by light or by perspiration.

EXAMPLE 12
The lightening solution of Example 1 is applied to permed hair a few weeks before and the following dye composition is applied simultaneously
Lauric amide 15 g
Lauric acid 10 g butylglycol 60 g
Hydroxyethyl cellulose 50 g N1, N4, N4-tri ($ - hydroxyethyl} 2-nitro p-phenylenediamine 1.05 g 2-isopropyl o-nitroaniline 0.55 g 3-nitro 4-amino phenol 0.10 g 3-nitro -4- (-hydroxyethyl) aminophenol 0.05 g Monoe-thanolamine qs pH 9
Water qs 1000 g
This solution provides, after 25 minutes of application at room temperature and rinsing with water, a very light golden blond color. The same results are noted as above.

EXAMPLE 13
We prepare the following dye composition
Lauric amide 15 g
Lauric acid 10 g
Butylglycol 60 g
Hydroxyethyl cellulose 50 g 2-isopropyl o-nitroaniline 0.65 g 3-nitro 4-amino phenol 0.10 g N1, N4, N4-tri (0-hydroxyethyl) 2-nitro p-phenylenediamine 1.15 g
Monoethanolamine qs pH 9
Water qs 1000 g
The composition is applied to hair with lightly bleached permanent tips according to Example 1. This solution provides, after 30 minutes of laying at room temperature and rinsing with water, a very uniform light brown coloring. The same results are noted as above.

EXAMPLE 14
We prepare the following dye composition
Lauric amide 15 g
Lauric acid 10 g
Butylglycol 60 g
Hydroxyethylcellulose 50 g
N1-methyl-N4, N4-bis ($ -hydroxyethyl) 2-nitro p-phenylenediamine 1.4 g 2-isopropyl o-nitroaniline 1.0 g 3-nitro 4-amino phenol 0.12 g (4-nitro 3 -methylamino) phenoxyethanol 0.6 g N1, N4, N4-tri (2-hydroxyethyl) 2-nitro p-phenylenediamine 1.45 g
Monoethanolamine qs pH 9
Water qs 1000 g
The composition is applied to 9 permed hair having undergone the lightening pretreatment of Example 1. This solution provides, after 20 minutes of laying at room temperature and rinsing with water, a very solid dark blond coloring. We see the same results as before.

EXAMPLE 15
We prepare the following dye composition
Lauric amide 15 g
Lauric acid 10 g
Butylglycol 60 g
Hydroxyethyl cellulose 50 g N1- (-hydroxyethyl), N4-methyl, N4 (-hydroxyethyl) 2- nitro pphenylenediamine 3g (4-nitro, 3-methylamino) phenoxyethanol 1.3 g
Monoethanolamine qs pH 9
Water qs 1000 g
This composition is applied to hair with permanent tips having undergone the lightening pretreatment of Example 1.

 After 15 minutes of laying at room temperature and rinsing with water, a very uniform natural color is obtained.

We note that this coloration is more intense on the permanent parts but that the reflection of the shade is preserved. It is attenuated, without being modified by light or by perspiration.

EXAMPLE 16
We prepare the following dye composition
Lauric amide 15 g
Lauric acid 10 g
Butylglycol 60 g
Hydroxyethyl cellulose 50 g N1-methyl, N4-methyl, N4- (9-hydroxyethyl) 2-nitro p-phenylenediamine 3 g (4-nitro 3-methylamino) phenoxyethanol 1.5 g
Monoethanolamine qs pH 9
Water qs 1000 g
This composition is applied to natural hair with permed ends. After 20 minutes of laying at room temperature and rinsing with water, a very uniform natural coloring is obtained. We also note the same results as in the previous example.

EXAMPLE 17
The lightening solution of Example 1 is applied to permed hair a few weeks before and the following dye composition is applied simultaneously
Lauric amide 15 g
Lauric acid 10 g
Butylglycol 60 g
Hydroxyethyl cellulose 50 g N1-, ethyl-N4-methyl, N4- (9 -hydroxyethyl) 2-nitro p-phenylenediamine 3 g 4-nitro 2-methoxy &commat; -hydroxyethylanine 0.7 g (3-methylamino 4- nitro) phenol 13 dihydroxypropyl ether 0.5 g
Monoethanolamine qs pH 9
Water qs 1O0Og
After 20 minutes of laying and rinsing with water, a very uniform natural coloring is obtained; we also note results similar to those obtained previously.

EXAMPLE 18
We prepare the following dye composition
Lauric amide 15 g
Lauric acid 10 g
Butylglycol 60 g
Hydroxyethyl cellulose 50 g Nt -aminoethyl} -N4, N4-bisX & hydro- xyethyl) 2-nitro p-phenylenediamine 2 g 2-isopropyl o-nitroaniline 1.6 g
Monoethanolamine qs pH 9
Water qs 1000 g
This composition is applied to natural hair with permed ends. After 30 minutes of laying at room temperature and rinsing with water, a very uniform natural color is obtained. The reflection of the shade is kept from the root to the tip. It is attenuated, without being modified by light or by perspiration.

EXAMPLE 19
We prepare the following dye composition
Lauric amide 15 g
Lauric acid 10 g
Butylglycol 60 g
Hydroxyethyl cellulose 50 g
N1-methyl-N4, N4-bis (ss -hydroxyethyl) 2-nitro.p-phenylenediamine 2 g (3-methylamino 4-nitro) phenyl, dihydroxypropyl ether 1.1 g
Monoethanolamine qs pH 9
Water qs 1000 g
This composition is applied to hair with permanent tips having undergone the lightening pretreatment of Example 1. After 25 minutes of laying and rinsing with water, a very uniform natural color is obtained. We also note the same results as above.

EXAMPLE 20
We prepare the following dye composition
Lauric amide 15 g
Lauric acid 10 g
Butylglycol 60 g
Hydroxyethyl cellulose 50 g (4-nitro, 3- 0 -hydroxyethylamino) phenoxyethanol 1.8 g N1-methyl-N4, N4-bis- (-hydroxyethyl) 2-nitro p-phenylene diamine 2.8 g 3-nitro 4- aminophenol 0.15 g Nonoethanolamine qs pH 9
Water qs 1000 g
This composition is applied to hair with permed ends previously bleached according to Example 1.

 After 20 minutes of laying and rinsing with water, a very smooth natural blonde coloring is obtained. The reflection of the shade is preserved from root to tip without being modified by light or perspiration.

EXAMPLE 21
We prepare the following dye composition
Lauric amide 15 g
Lauric acid 10 g
Butylglycol 60 g
Hydroxyethyl cellulose 50 g N1-methyl-N4, N4-bis ((3-hydroxyethyl) 2-nitro p-phenylenediamine 2.6 g (3- ss -hydroxyethylamino, 4-nitro) phenyl, Çb, 1 (- dihydroxypropyl ether 2.1 g
Monoethanolamine qs pH9
Water qs 1000 g
This composition is applied to hair with permanent tips having undergone the lightening pretreatment of Example 1. After 20 minutes of laying and rinsing with water, a very uniform natural coloring is obtained. We also note the same results as above.

EXAMPLE 22
The following dye composition is prepared
Lauric amide 15 g
Lauric acid 10 g
Butylglycol 60 g
Hydroxyethyl cellulose 50 g N1-methyl-, N4, N4-bis- (6 -hydroxyethyl) 2-nitro p-phenylene diamine 3 g 3- f3 -hydroxypropylamino, 4-nitro anisole 1.8 g
Monoethanolamine qs pH9
Water qs 1000 g
This composition is applied to natural hair with permed ends. After 25 minutes of laying and rinsing with water, a very uniform natural color is observed. The reflection of the shade is preserved from root to tip without being modified by light or by perspiration.

EXAMPLE 23
The lightening solution of Example 1 is applied to permed hair a few weeks before and the following dye composition is applied simultaneously
Lauric amide 15 g
Lauric acid 10 g
Butylglycol 60 g
Hydroxyethyl cellulose 50 g N1-methyl-N4-N4-bis- (ss-hydroxyethyl) 2-nitro p-phenylene diamine 3 g 3- 2.6 - dihydroxypropylamino, 4-nitro anisole 2g
Monoethanolamine qs pH9
Water qs 1000 g
After 15 minutes of application and rinsing with water, a very uniform natural color is obtained. The same results are noted as above.
EXAMPLE 24
The following dye composition is prepared:
Lauric amide 15 g
Lauric acid 10 g
Butylglycol 60 g
Hydroxyethyl cellulose 50 g N1-methyl-N4, N4-bis- (-hydroxyethyl) 2-nitro p-phenylene diamine 3 g 3- 2- hydroxyethylamino, 4-nitro anisole 1.3 g
Monoethanolamine qs pH9
Water qs 1000 g
This composition is applied to permed hair having undergone the lightening pretreatment of example 1. After 20 minutes of laying and rinsing with water, a very uniform natural coloring is obtained. We note that this coloration is more intense on the permanent parts but that the reflection of the shade is preserved from the root to the tip. It is attenuated, without being modified by light or by perspiration.

Claims (11)

 1. Dye composition for direct dyeing of human hair, characterized in that it comprises at least one violet nitro dye having a shade according to Munsell ranging from 7.5 P to 10 PB and at least one yellow nitro dye having a shade according to Munsell ranging from 10 Y to 2.5 Y, these purple and yellow dyes being used respectively in a weight concentration ratio ranging from 1 to 3 and having a substantially equal selectivity coefficient ranging from 3 to 8, when the latter is determined at a weight concentration between 0.1 and 0.6%.  2. Dye composition according to claim 1, characterized in that the violet nitro dye is chosen from the N-substituted 2-nitro p-phenylenediamines of formula:

 in which R1 denotes the ss-hydroxyethyl group, R2 denotes the -hydroxyethyl or methyl group, R3 denotes the 9 -hydroxyethyl or methyl group or the -aminoethyl group when R2 denotes the ss -hydroxyethyl group, and the yellow nitro dye is chosen among the o- or p-nitroanilines of formula

 in which R4 denotes hydrogen, R5 denotes isopropyl group and R6 denotes amino group, or R4 denotes ss-hydroxyethyloxy group, R5 denotes hydrogen and R6 denotes methylamino group or (3-hydroxyethylamino, or R4 denotes group  13, (-dihydroxypropyloxy, R5 of hydrogen and R6 the amino group, methylamino or 0-hydroxyethylamino or also R4 denotes the group 0 -hydroxyethylamino, R5 the methoxy group and R6 of hydrogen, or even R4 denotes the group methoxy, R5 of hydrogen and R6 the group 5-hydroxyethylamino, (3-hydroxypropylamino or y, & -dihydroxypropylamino.  3. Dye composition according to claim 1 or 2, characterized in that the purple dyes and yellow dyes are used in a total concentration ranging from 0.04% to 2.58 by weight.  4. Dye composition according to any one of claims 1 to 3, characterized in that it further comprises one or more dyes from the family of 3-nitroaminophenols of formula

 in which R7 denotes hydrogen and R8 denotes the amino or ss-hydroxyethylamino group or else R7 denotes the amino group and R8 of hydrogen.  5. Dye composition according to claim 4, characterized in that it contains 0.001 2.5% by weight of one or more dyes from the family of 3-nitroaminophenols mentioned in claim 5.  6. Dye composition according to any one of claims 1 to 5, characterized in that it comprises, in an aqueous vehicle, organic solvents such as alcohols, glycols or glycol ethers in concentrations between 0.5 and 20% by weight, and preferably between 2 and 10% by weight.  7. dye composition according to any one of claims 1 to 6, characterized in that it comprises anionic, cationic, amphoteric nonionic surfactants or their mixture in concentrations of between 0.05 and 50% by by weight, and preferably between 0.5 and 10% by weight.  8. Dye composition according to any one of claims 1 to 7, characterized in that it comprises fatty amides of concentrations between 0.05 and 108 by weight.  9. Dye composition according to any one of claims 1 to 8, characterized in that it comprises thickeners at concentrations between 0.5 and 15% by weight.  10. Dye composition according to any one of claims 1 to 9, characterized in that it has a pH of between 6 and 11 and preferably between 8 and 10.  11. A process for dyeing human hair by direct dyeing, characterized in that the hair is subjected to a lightening treatment consisting in applying to the hair a solution of ammonia hydrogen peroxide or containing alkaline agents or an ammonia solution of alkaline peroxides or persalts, of urea peroxide or of compounds of addition of hydrogen peroxide and of organic compounds, and simultaneously or after an exposure time of 5 to 30 minutes and rinsing with water, one applies on the hair, the dye composition according to any one of claims 1 to 10, it is left to stand for 15 to 30 minutes, the hair is rinsed and dried.