CA1142179A - Composition for hair dyeing, containing a para base and an ortho base - Google Patents

Abstract

The disclosure describes compounds characterized in that they correspond to the formula: <IMG> IV in which: Y signifies <IMG> R'1 and R'2 denote alkyl, mesylaminoalkyl, piperidino alkyl and hydroxyalkyl, the alkyl groups comprising 1 to 6 carbon atoms and their cosmetically acceptable salts. These tri-core compounds formed in the hair give a good leveling of the coloring.

Description

The present invention relates to compositions intended for use in hair dyeing and holding para and ortho oxidation dyes and a process hair dye.
It is well known to dye keratin fibers and, in particular, human hair with dyes oxidation.
Oxidation dyes are aromatic compounds.
of the diamine, aminophenol or phenol type well known in the state of the art.
These compounds are not generally dyes in themselves but are transformed into dyes by condensa-tion in an oxidizing medium.
One distinguishes among the oxidation dyes, a share the dye precursors by para type oxidation;
chosen from diamines, aminophenols whose groups-functional elements are in relation to each other, the - oxidation dye precursors of the ortho type and, furthermore, on the other hand, compounds called modifiers, shaders or ZO couplers which are so-called meta derivatives chosen from m-diamines, m-aminophenols and m-diphenols as well as phenols.
These oxidative dye precursors are generally actually used with couplers to obtain co-various lorations.
Among the dye precursors by oxidation of type para aforementioned9 some, although recommended since many years to be used in dyes for hair, could not be used in a satisfactory manner, in part particular in conventional systems using a coupler, due to their lack of power ~ 1 ~ t nuance of the nuances obtained with respect to the keratin fibers ques.
Selectivity is, as is well known, a significant problem in the dyeing of hair due to different sensitization of the hair depending on the locations. Indeed, the hairdresser finds himself usually in the presence of a hair whose awareness is practically nil for the root frankly lumpy, strong for previously treated parts having undergone colo-ration, discoloration or permanent and very strong for the tips which have undergone several of these treatments and which are exposed daily to the action of light and severe weather. This problem is particularly important for oxidation bases known as para including one of the nitrogen atoms is mono- or di-substituted as well as for paraphenylene-diamines whose nitrogen atom is not substituted but whose aromatic cycle is very crowded.
The Applicant has now discovered that one can will significantly increase the coloring power of these bases by using them, in association with certain pre-ortho type oxidation dyes sliders chosen ~ en particular, among the orthoaminophenols possibly subs-titrated on the nitrogen atom, orthodiphenol, orthophenylene-diamine and avoiding in the first stage any competi-tion with conventional couplers such as m-aminophenols or m-diamines.
The Applicant has discovered, among other things, that the ass-sociation of certain paraphenylenediamines with certain pre-ortho type oxidative dye sliders allowed surprisingly, to obtain a powerful coloring which is not simply the result of ~ colorings that can bring the para base and the ortho compounds separately.
~ the above association leads to dyes of good safety and having in particular good resistance tance to external agents such as light, bad weather laughs or washes.
The plaintiff also discovered that the association dye precursors by para type oxidation with, in particular ~ the ortho aminophenol led ~ so surprisingly, the formation of a compound comprising three aromatic nuclei hereinafter called "tri-nucleus compound" this after penetration into the keratin fibers and oxidation if you.
The Applicant has finally discovered that by using such an association according to a dyeing process in two steps one could get a good leveling of coloring.
~ The invention therefore relates to a composition intended born to be used in hair dye and containing a dye precursor by para normal type oxidation-not very powerful and selective and a dye precursor p ~ r ortho-type oxidation.
Another object of the invention is constituted by a hair dyeing process using such a composition.
A subject of the invention is also the industrial product.
new triel constituted by a compound ntri-nuclei ".
Other objects of the invention will result from the des-description and examples which follow.
~ A composition intended for use in a pro-ceded from dyeing keratin fibersv and, in particular, hair according to the inYention, is characterized by the fact that it contains, as an oxidation dye, only -.

~ `

~ dye precursors by para type and type oxidation ; ortho t a) at least one of this ~ dye precursors by oxy-donation being of the para type chosen from:
the compounds corresponding to the formula:

/ Rl R5 ~ 3 . R6 ~ R4 (I) in which:
- when R1 and R2 both denote a hydrogen atom, at least two of the substituents R3 ~ R4, R5 and R6 are different hydrogen and little ~ ent designate a lower alooyl group or lower alkoxy:
- when one of the groups Rl or R2 is different from hydro-gene, it can designate an alkyl group interrupted by a oxygen atom and substituted by a hydroxyl group, a substituted alkyl group p ~ r an acylamino group, ureido, mesylamino, furfuryl, sulfonamido possibly subs-formed by one or two lower alkyl groups, when the aromatic ring is not substituted or is substituted by a halogen atom, a lower alkyl group ~ or else 1one of the substituents Rl or R2 denotes an alkyl group lower optionally substituted by a hydroxy group, alkoxy; tetra hydrofur ~ uryl, R3 denoting an alkyl group lower, a halogen atom, a lower alkoxy group, R4 de ~ igniting hydrogen or a halogen atom when R3 de-hydrogen sign, R5 and R6 denoting hydrogen; preferably ~~

~ ~ 2 ~ ~

R3 is different from alkyl when Rl or R2 denotes alkyl or alkyl substituted by OH.
- when Rl and R2 are both different from hydrogen, Rl can denote hydroxyalkyl, alkyl, R2 can denote hydroxyalkyl, alkyl substituted by an acylamino group, mesylamino, carbamyl, sul ~ onamido, piperidino, Rl and R2 pou-before forming, together with the nitrogen atom to which they are linked, a piperidino or morpholino group, the nucleus aromatic not being substituted or substituted by a group-ment lower alkyl or a halogen atom and when Rl and R ~ both denote an alkyl group, R4 denotes a halogen atom, an alkyl or alkoxy group, R3, R ~, R6, being hydrogen.
. the bis-condensed precursors chosen from N, N'-diarylalkylenediamine in which the aryl groups are substituted in para by an OH or amino group optionally substituted by an alkyl group, these amines possibly being same be substituted by an alkyl group, hydroxy-alkyl, aminoalkyl described in French patent No.

2,016,123, and their salts b) at least one of the dye precursors by oxidizing tion being of the ortho type and chosen from orthoaminophenols, orthodiphenols, orthophenylenediamines, whose nucleus aromatic can carry substituents such as a group lower alkyl or alkoxy placed in such a way that the Sections 4 and 5 with respect to the OH function remain free and in which the nitrogen atom of one of the amino groups can be ~
be substituted by an alkyl group itself optionally substituted by a hydroxyl or alkoxy group so that the cosmetically acceptable salts of these precursors The dye precursors by oxidation type 7 ~

ortho preferred are chosen from: orthodiphenol, ortho-phenylene diamine, orthoaminophenols whose nucleus aro-material can carry substituents such as alkyl or alkoxy, the nitrogen atom of orthoamino phenols or orthophenylene-diamine can optionally be substituted by a group alkyl, optionally substituted by alkoxy ~ or hydroxy-alkyl.
In the above formulas, the term “grouping” is understood to mean lower alkyl, a group having 1 to 6 carbon atoms `10 and preferably a methyl, ethyl, propyl group, butyl.
Halogen preferably designates a chlorine atom.
Alkoxy denotes, preferably ~ a group having 1 to 6 atoms carbon such as methoxy, ethoxy7 propoxy.
Dye precursors by type oxidation para more particularly preferred ~ according to the invention are chosen from:
- 2,3,5,6-tetramethyl p-phenylene diamine, - 2,6-dimethyl p-phenylenediamine, - 2-methyl 5-methoxy p-phenylenediamine ~
- 2,6-dimethyl 5-methoxy p-phenylenediamine, - 4-amino N ~ / hydroxyethoxy) -ethy ~ aniline, - 4-amino N- (~ -acetylaminoethyl3 aniline ~
- 4- ~ mino N- (~-mesylaminoethyl) aniline, - 4-amino N- (~ -sulfonamidoethyl3 aniline, - 4-amino N- ~ g- (diethylsul ~ onamido) ethy ~ aniline, - 4-amino tN- ~ urfuryl) aminoanyline, - 2-methyl 4-amino N ~ methyl aniline, - 2-chloro 4-amino N-methyl aniline, - 3-chloro 4-amino M-methyl aniline, - 2-methoxy 4-amino N-methylaniline, 2 ~

- 2-chloro 4-amino N-ethyl aniline, - 2-chloro 4-amino N-butyl aniline, - 2-methyl 4-amino N- (~ -hydroxyethyl) aniline, - 2-methyl 4-amino N- (~ methoxyethyl) aniline, - 2-chloro 4-amino N- (~ -methoxyethyl) aniline, - 4-N, N (ethyl- ~ hydroxyethyl) amino aniline, - 2-methyl 4-amino N- (~ -acetylaminoethyl) aniline, - 2-chloro 4-amino N- (~ -acetylaminoethyl) aniline, - 2-methyl 4-amino N (~ -ureido ethyl) aniline, - 2-chloro 4-amino N- (~ -ureido ethyl) aniline, - 2-methyl 4-amino N- (~-mesylaminoethyl) aniline - 2-chloro 4-amino N- (~ -mésylaminoéthyl3 aniline, - 2-methyl 4-amino (N-tetrahydrofurfuryl3 aniline, - 2-chloro 4-amino (N-tetrahydrofur ~ uryl) aniline, - 2-methyl 4-amino (N-furfuryl) aniline, - N, N bis (~ -hydroxyethyl) paraphenylenediamine, - 4-amino N, N- (ethyl, ~-mesylaminoethyl) aniline, ~ 4-amino N ~ N- (ethyl, ~ -carbamylmethyl) aniline, - 4-amino N, N- (ethyl, ~ g-piperidinoethyl ~ aniline, - N, N- (~ -hydroxyethyl, ~ 5-mesylaminoethyl) p-phenylenediamin ~
- N- (4'-amino) phenyl piperidine, - N- (4'-amino) phenyl morpholine, - 3-methyl 4-am; no N, N- (ethyl, ~ -carbamyl methyl) aniline, - 3-methyl 4-amino N, N- (ethyl, ~-mesylaminoethyl) aniline, - 3-chloro 4-amino N, N-bis- (~ -hydroxyethyl) aniline, - 3-methyl 4-amino N, N-dimethyl aniline, - 3-chloro 4-amino N, N ~ dimethyl aniline, - 3-methoxy 4-amino N, N-dimethyl aniline, - N, N '- (~ -hydroxyethyl) NjN' (4-amino phenyl) tetramethylene-diamine, - N, N '- (~ -hydroxyethyl) N, N' (4-aminophenyl) dimethylene-diamine, .,, _ .. ...... . . . ........ .
, as well as the salts of organic or inorganic acids of these bases, such as hydrochloride, hydrobromide, sulfate, metho sulfate, acetate, tartrate, etc.
Among the ortho-type precursors giving re-particularly significant results we can cite the ortho-phenylenediamine, orthoaminophenol and their subs-titrated on the nitrogen atom such as, for example, N ~
hydroxyethyl) amino-2 phenol, methoxy-4 amino-2 (~ -hydroxy-ethyl ~ aniline, and ortho diphenol.
`10 Relative molar proportions of precursors dyes by para type oxidation compared to pre-ortho-type oxidative colorants sliders are included its between 30 and 0.5 and D preferably, between 20 and 1.
Other para oxidation bases can be added to the mixture of dye precursors by para oxidation and ortho compounds which have just been defined; these can be:
- paraphenylenediamines such as paraphenylenediamine, paratoluylenediamine, methoxyparaphenylenediamine, chloroparaphenylenediamine, N, N-dimethylparaphenylenediamine ~
paraaminodiphenylamine, - paraaminophenols such as paraaminophenol, 2-methyl 4-aminophenoli 3-methyl ~ aminophenol, 2-chloro 4-amino-phenol, 3-chloro 4-aminophenol, 2,6-dimethyl 4-amino-phenol, 3,5-dimethyl 4-aminophenol, ~, 3-dimethyl 4-amin3-phenol, 2,5-dimethyl 4-aminophenol, N-methylparaamino-phenol.
We can also add to the mixture of ~ bases para and the above-defined ortho compounds, one or more di-phenylamine ~ chosen ~ in particular, from diphenyl-amines of which the ~ 2 benzene nuclei are 3ubstituted in posi : tion 4 and 4 'by 2 groups such as hydroxyl and / or NOT
R ~
where R 'and R "denote independently or simultaneously: hydro-gene, alkyl, hydroxyalkyl and when R "denotes carbamyl-alkyl, mesylaminoalkyl, acetylamino alcoyle9 sul ~ oalcoyle, piperidinoalkyl, morpholinoalkyl, benzoylaminoalkyl, R 'denotes H or alkyl ~ The radicals R' and R "can form sea with the nitrogen atom to which they are attached a hetero piperidinic or morpholinic cycle. The other positions benzene nuclei can be occupied by one or more groups such as alkyl, alkoxy including the alkyl radical can form a heterocycle with a primary amine group or secondary in position 4 or 4 '; a halogen atom, a ureido, amino group optionally substituted by a group pement hydroxyalkyl, carbamylalkyl, mesylaminoalkyl, acyl or carbalcoxy.
These diphenylamines can be used in the form of their ~ els such as sulfate, hydrobromide, hydrochloride, acetate, tartrate.
These diphenylamines are described in the patents françai3 1. 222.700, 2.056.799, 2.174.473, 2 ~ 145.724, 2.262.023, 2,262,024, 2,261,750 and the patent application 75 05 503 of the - plaintiff published ~ or number 2.262.022 on September 19 1975.
We can ~ iterate for example:
- 3,5-dimethyl 4-hydroxy 4'-N, N-dimé-thylamino diphenylamine;
- 2-acetylamino 2 ', 3,5 trimethyl 4 ~ hydroxy 4' ~ -ethyl, N- (~ -me ~ ylaminoethyl ~ aminodiphenylamine ~
- 2-acetylamino 2 ', 5-dimethyl 4-hydroxy 4'- ~ N-ethyl, N-carbamylmethyl ~ aminodiphenylamine;

- 2 ', 3, 5, ~' -tetramethyl 4-hydroxy 4'-amino diphenylamine;
- 2,4-diamino 3-methoxy 4'-hydroxy dihydrochloride phenylamine;
- 3,5-dimethyl 4-hydroxy 4'-amino diphenylamine;
- 2-carbamylmethylamino 4-hydroxy 4'-N, N (di ~ -hydroxyethyl) amino 5-methyldiphenylamine;
- 3,5-dimethyl 4,4'-dihydroxy diphenylamine;
- 2'-chloro 3,5-dimethyl 4,4 'dihydroxy hydrochloride diphenylamine;
- 2,4 'diamino 4-hydroxy ~ -methyl diphenylamine;
- 2-hydroxyethylamino 5-methyl 4,4'-dihydroxy diphenylamine;
- 2-amino 5-methyl 4,4 'dihydroxydiphenylamine.
The composition according to the invention may contain a mer-captan responding, for example, to the forma R - SH (II ~
in which R denotes an alkylene group linked to a group pement -COOH, -CONH2, OH, -SH or -COOR ', R' denoting a group-alkyl alkyl substituted or not by one or more groups OH, said alkylene group possibly being substituted by one or several lower alkyl, amino and COOH groups, as well as the alkaline, alkaline earth ammonium salts of these compounds, salts derived from organic and inorganic acids.
In the above-mentioned formula II ~ the alkylene grouping preferably has 1 to 4 carbon atoms and denotes, in part ticulier, a methylene group ethylene, propylene; the alkyl group preferably designates a group having 1 to 4 carbon atoms and, in particular, methyl; the ~ salts alkali or alkaline earth are preferably the salts of sodium, potassium, calcium ~ salts of organic acids or inorganic are preferably salts derived from acid hydrochloric, ~ ul ~ uric, acetic, tartaric, etc .....

.. ...... . . . ... . . . . . ... . ... . . .

3 ~ 2 ~ 7 ~

Among the compounds of * ormule (II) mentioned above, the preferred compounds are, inter alia, thioglycoli-that, thiolactic acid, ~ -mercapto propionic acid, thioglycerol, glycerol thioglycolate, thioglycol, glycol thioglycolate, thioglycolamide, hydrochloride cysteine, mercaptosuccinic acid, ~ dimer- acid captoadip; that.
These mercaptans can be used alone or in combination mixed.
These mercaptans are preferably present in quantities less than 5 ~ 0 by weight in ~ eu not degrade hair.
A particularly advantageous realization of the in-vention resides in a composition of the aforementioned type in the-which mercaptan is present in amounts included between 1 and ~ by weight and in particular between 1.5 and 3.5%
in weight. Such compositions allow in particular to mediate the selectivity problems posed by some of the say oxidation bases.
According to a preferred embodiment of the invention, dye precursors by para type oxidation and ortho are present in quantities between approximately 0.005% and 10% by weight and, preferably ~ between 0.01 ~ and 8%
in weight.
The pH of the composition according to the invention is understood between 7 and 12 and preferably between 8.5 and 11.
It is adjusted using cosmetic alkalizing agents.
tically acceptable such as ammonia, alkylamines, amine alkanols ~ such as mono-, di- or triethanolamine, alkyl alkanolamines such as aminomethylpropanol, aminomethylpropanediol, sodium or potassium hydroxide, sodium or potassium carbonates or a mixture thereof.
This composition can, among other things, be buffered at a pH determined using inorganic or organic salts such as neutral or acidic phosphates or carbonates of ammonium, of an alkali or alkaline earth metal.
~ es compositions according to the invention can be ap-plied directly on the hair using the conventional dyeing after mixing with a cosmetic oxidant-mentally acceptable such as hydrogen peroxide.
According to a particularly advantageous embodiment, these compositions can be used in a process in consisting of two stages, firstly to apply the above-defined composition on fi ~ res for a sufficient time ~
health to permeate these and, in a second time and without intermediate rinse to apply a composition containing a oxidant present in an amount sufficient to develop the hair dye.
If desired, we can possibly, in a third time and before the oxidant has caused the development complete settlement of dye precursors by oxidation by ~ and dye precursors by ortho oxidation present on the hair, apply, without intermediate rinsing, a composition containing couplers and, in part ~ ulier, so-called meta compounds which allows to vary the nuance of the color obtained by association with said bases para and ortho compounds.
We can finally apply to the hair said position after mixing with an oxidant and then apply and until the oxidant has fully developed the dyes and without intermediate rinsing, a composition containing the coupler.

.

~ 42 ~

The plaintiff has discovered, in fact, that as for this process, the power of the coloration obtained was significantly higher than that obtained using a only composition constituted by the coupler and by the association tion of a color precursor by para and ortho oxidation.
This difference seems to be due to the fact that the coupler, when present in the base mixture para and laid ortho tends to react faster with the basics so that this coupling outweighs the condensation of the posed ortho and para para.
Among the couplers more particularly used according to the invention, mention may be made of: monopheno- derivatives lics, meta-diphenols, meta-aminophenols has function primary, secondary or tertiary or functional free amine blocked amine, metadiamines. These different classes can be represented by the general formula:

10 ~ Rg (III ~

in which:
- when it represents the phenolic couplers, only one of the substituents R7 or R8 denote OH and the other substituents different from OH denote hydrogen, alkyl ~ alkoxy, halogen, one of the positions in para or ortho with respect to the grouping OH being free or substituted by halogen or alkoxy;
- when it represents an m-diphenol, R7 and R8 denote OH, Rg and Rlo can denote hydrogen, an alkyl group, al ~ oxy or halogen, - when it represents an m-aminophenol, one of the groups R7 or R8 denotes OH and the other group denotes Rll \

in which:
Rll and R12, identical or different, denote hydrogen, al-linear or branched coyle possibly having at the end of chain; not an OH, alkoxy or amino group optionally mono or disubstituted or a heterocycle such as piperidino or morpholino; the alkyl group possibly comprising other alcohol, amine, ether oxide functions in the chain; and when one of the substituents R11 or R12 denotes acyl, carbamyl, car-bamylalkyl, the nitrogen atom of which is possibly mono-or di-substituted; alkyl- or arylsulfonyl; sulfonamidoalcoyl whose nitrogen atom is possibly mono or disubstituted;
carbethoxy; mesylaminoalkyl; the other substituent denotes hy-identical or different R9 and Rlo mean hydro-gene, halogen, linear or modified alkyl, a Zl 'group Zl meaning alkyl and being able to form with the nitrogen atom a morpholinic heterocycle;
- when it designates an m-diamine R7 and R8 denote all two a group / 13 - NOT

but may differ in the nature of the substituents R13 and R14 R13 and R14 identical or different denoting hydrogen, alkyl ; linear or branched, optionally substituted by OH, amino, alkoxy, carbamyl, alkyl- or arylsulfonyl ~ mino, one of the groups pements R13 or R14 which can designate an alkylsulfonyl group, acyl, carbamylalkoyl when the other substituent denotes hydro-uncomfortable;
R9 and Rlo, identical or different, denote hydrogen, halo-z ~

gene, linear or branched alkyl or Z2 'Z2 denoting alkyl, hydroxyalkyl, alkoxyalkyl, arylaminoalkyl, mesylamino-alkyl, ureidoalkyl, carbalkoxyalkyl; the substitution of an amine function and an etheroxide function can constitute a morpholinic cycle as well as the acid salts organic or inorganic such as hydrochloride, hydrobromide, sulfate, acetate, tartrate, etc.
In the formulas of the above couplers, the group-ment alkyl preferably indicates a group having between 1 and 6 carbon atoms such as a methyl or ethyl group, propyl, isopropyl, n-butyl, i-butyl, etc. .... alkoxy denotes a group preferably having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy etc ....; halogen means chlorine, bromine and fluorine; the substituents of the nitrogen atom are, preferably, alkyl groups having from 1 to 6 atoms of carbon.
Among the couplers corresponding to the general formula mentioned above, we will note more particularly resorcinol, 2-methyl resorcin, 4-chloro resurcin, metaaminophenol, 2,4-diamino anisole, 2-methyl 5-ureido phenol, 2,6-dimethyl 3-aminophenol, 2-methyl 5 acetylaminophenol, 2,6-dimethyl ~ -acetylamino phenol, 3-amino 4-methoxy phenol, 2-methyl 5-N- (~ -hydroxyethyl) aminophenol, metapheny-lene diamine, metatoluylene diamine, N-methyl metaamino-phenol, 6-methyl 3-aminophenol, (2,4 ~ diamino ~ phenoxy-ethanol, 3-N, N- (diethyl) aminophenol, 6-methyl 3-N- (~ -mesylamino ethyl) aminophenol, 6-methyl 3-N- (carbamylmethyl) aminophenol, 3-N- (carbamylmethyl) aminophenol, ~ -N ~
hydroxyethyl) amino 4-amino phenoxyethanol, 3-N, N- (diethyl) aminophenol, or the salts of these compounds ~
Other couplers ~ usable in the compositions /

according to the invention are for example naphthols, compounds heterocyclics such as in particular derivatives of the morpholine like 6-hydroxy benzomorpholine, 6 amino benzomorpholine, pyridine derivatives such as 2; 6-diamino pyridine or diketonic compounds and their salts.
According to a preferred embodiment of the invention, the couplers are present in quantities between about 0.00 ~% and 1 ~% by weight, and preferably between 0.01 and 8% by weight.
10` The two-step process mentioned above can still be implemented according to another advantageous embodiment of the invention using as first composition that corresponding to the above definition and additionally containing minus one mercaptan in the proportions indicated above.
In the two-step process the application time of the first composition is between ~ and 45 min and, from pre ~ erence, between 5 and 20 minutes while the action time of the oxidizing composition varies between 5 and 45 min and, preferably, between 10 and 40 minutes, the action time of the possible third composition containing the couplers varying between 5 and 45 min and preferably between 10 and 30 min.
It is possible, during this process, to realize a more or less lightening hair dye in fact sant vary the duration of exposure and the amount of oxidant. It is also possible to vary the power of the colora-tion by variation of the amount of mercaptans in the range above, the mercaptan can be added in the quanti-above mentioned just before use in composites containing the oxidizable dye.
Mercaptan can also be applied directly on the hair before application of ~ compositions intended to dye the hair.
Another embodiment of this process consists in applying firstly the first composition containing the mercaptan in the above proportions ~ inies and, in a second time and without preliminary rinsing ~ a second composition containing the oxidant as well as the dye precursors by para and ortho oxidation to dye the hair and, if necessary, Finally, apply the couplers as a last step.
~ an oxidizing composition applied in the second time contains a cosmetically acceptable oxidizing agent such as hydrogen peroxide at a concentration between 0.1 and 20% by weight, urea peroxide as well as persalts such as, for example, ammonium, sodium or sodium persulfate potassium. The pH of this composition is adjusted so as to a-see optimal development of coloring after penetration in the fiber of this composition and that applied in at first.
The compositions according to the invention containing at least a para-oxidation dye precursor of the susmen- type and an oxidation dye precursor of the ortho type, as well as oxidizing compositions or containing couplers can be used in the multi-step dyeing process still contain direct dyes or hydroxy-naphthoquinones which may be present in the composition according to the invention if they are stable in it or in the compositions applied in second time if they are stable in oxidizing medium as well as in the composition containing the coating cry. The process according to the invention therefore allows 9 only to use the coloring potential to the maximum dif ~ erent dye precursors by oxidation of the type para and ortho above but also allows to combine the action of these dye precursors with that of colo - ~ 7-, .. ,,. . ..,. . ,. . . . .. .. ...... . . ,., _ ~ 2 ~
,, direct rents not previously usable under the conditions normal use of oxidation dyes.
~ direct dyes and hydroxynaphthoquinones are present, preferably, in quantities included between about 0.005% and 3% by weight.
~ Direct dyes, more particularly used sands in the process according to the invention are the dyes anthraquinones, the nitro derivatives of the benzene series, nitrated diphenylamines chosen from nitrophenylene-diamines, ni ~ roaminophenols, dinitroaminophenols, dini-tro-aminobenzenes, nitroaminobenzenes or nitrodiphenylamines described in French patent 2,211,210. We can cite in particular:
- 1-hydroxy 2-amino 4,6-dinitro benzene;
- 2-nitro p-phenylenediamine;
- 1-amino 2-nitro 4-N-methylaminobenzenes;
- 1-hydroxy 2-amino 5-nitro benzene;

- 4-nitro m-phenylenediamine;
- l-methoxy 3-nitro 4-N- (~ -hydroxyethyl ~ aminobenzene;
~ -hydroxyethyloxy3 3-nitro 4-aminobenzene;
- 2-N- (~ -hydroxyethyl) amino 5-nitro anisole;
- 1-amino 2-nitro 4-N- (~ -hydroxyethyl) aminobenzene;
- lN-methylamino 2-nitro 4-N, N-bis- (~ -hydroxyethyl) aminobenzene;
- lN-methylamino 2-nitro 4- ~ N-methyl, N- (~ -hydroxyethyl aminobenzene;
- 3-nitro 4-N ~ hydroxyethyl ~ aminophenol;
- 2,6-dimethyl 3-nitro 4- N- (~ -hydroxyethyl) aminophenol;
- 4 -nitro o-phenylenediamine;
- 2-amino 4-nitrvphenol;
- 2-nitro 4-aminophenol;

7 ~

- 1,4-N, N-bis- (~ -hydroxyethyl) amino 2-nitro benzene;
- 1-amino 2-N- (~ -hydroxyethyl) amino 5-nitro benzene;
- 3-nitro 4-N '- (~ -hydroxyethyl) amino N, N-bis- (~ -hydroxy-ethyl) aniline;
- 2-N- (~ -hydroxyethyl) amino (~ -nitro) phenoxy ethanol;
- l-amino 2- ~ tris- (hydroxymethyl) methyl ~ amino-5 ni-trobenzene;
- lN (~ -hydroxyethyl) amino 2-nitrobenzene;
- 2-nitro 4-N '- (~ -hydroxyethyl) amino N, N-bis- ~ -hydroxy- -ethyl) aniline;
- 2-nitro 4'-bis- (~ -hydroxyethyl) amino diphenylamine;
- 2-nitro 4'-hydroxy diphenylamine;
- l-amino 3 nitro 4-N- (~ -hydroxyethyl) aminobenzene;
- ~ -N, N-bis (~ -hydroxyethyl ~ amino 5-nitrophenol;
- 1-amino 2-nitro 4-N- (~ -hydroxyethyl) amino 5-chlorobenzene;
- 3-nitro 4-aminophenol;
- ~ -amino 2-nitrophenol;
- 2-nitro 4-amino diphenylamine;
- 3-nitro 4-N '- (~ -hydroxyethyl ~ amino NN (methyl ~ g-hydroxy-ethyl) aniline;
- 3-nitro 4-N '- (~ -hydroxyethyl) ~ mino N-methyl aniline.
The hydroxynaphthoquinones more particularly pre-2-hydroxy 1,4-naphthoquinone, 5-hydroxy 1,4-naphthoquinone.
These di ~ ferent compositions usable according to the-vention can be in the form of aqueous compositions.
ses, thickened, gelled, gellable, creams or aerosol.
~ gelled or gelling compositions are obtained naked either from polyoxyethylenated nonionic compounds or polyglycerolated in the presence of solvents either from liquid fatty acid soaps such as oleic acid, or acid isostearic in the presence of solvents dan ~ an aqueous vehicle.

z ~

Fatty acids are used to form soaps at concentrations between 0.5 and 15% by weight.
~ es basifying agents used to form sa-we can be soda, potash, ammonia, mono-ethanolamine, diethanolamine, triethanolamine or their mixtures.
Among the polyoxyethylenated nonionic compounds, may particularly mention nonoxyphenol polyoxyethylenated to 4 moles of ethylene oxide and polyoxyethylenated nonylphenol to `9 moles of ethylene oxide.
These constituents are preferably present at concentrations between 5 and 60% by weightO
Among the polyglycerolated nonionic compounds, Mention may in particular be made of polyglycerolated oleic alcohol 2 moles of glycerol and oleic alcohol polyglycerolated to 4 moles of glycerol.
These constituents are present in preference to concentrations between 5 and 60 ~ o by weight.
Among the solvents which can be used, mention may be made of ethyl, isopropyl, and butyl alcohols glycols or glycol ethers, such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol, Carbitol ~ and butyl Carbitol *, benzyl alcohol.
These constituents are preferably present at concentrations included ent ~ e? and 40 ~ by weight.
All concentrations are indicated on the basis of the total weight of the dye composition.
When the compositions are in the form of cream, they are mainly made from soap or fatty alcohols in the presence of emulsiants, in a vehicle aqueous.
* Trademark Soaps can be made from acids natural or synthetic fats having 12 to 18 carbon atoms bone such as lauric acid, myristic acid, acid palmitic, and stearic acid and basifying agents -such as soda, potash, ammonia, monoethanol-amine, diethanolamine, triethanolamine. Fatty acids are contained in the creams of the invention at concentra-Preferably between 10 and 30% by weight.
Creams can also be formulated from natural or synthetic fatty alcohols between 12 and 18 carbon atoms mixed with emulsifiers. From fatty alcohols, there may be mentioned, in particular, lauric alcohol, alcohols derived from coconut fatty acids, myris alcohol-tick, cetyl alcohol, stearil alcohol, alcohol hydroxystearyl ~ The concentrations of the inventive creams tion in fatty alcohols are between 5 and 25% by weight.
The emulsifiers which can be used in the compositions according to the present invention can be fatty alcohols polyoxyethylenated or polyglycerolated such as for example alcohol polyoxyethylenated oleic comprising from 10 to 30 moles of oxide ethylene, polyoxyethylene cetyl alcohol containing 6 to 10 moles of ethylene oxide, polyuric lauryl alcohol oxyethylenated to 12 moles of ethylene oxide ~ cetyl alcohol-stearyl oxyethylenated with 10 or 15 moles of ethylene oxide, polyoxyethylene oleocetyl alcohol with 30 moles of oxide ethylene, polyoxyethylenated 10,15 stearyl alcohol or 20 moles of ethylene oxide, polyglycerolated oleic alcohol 4 moles of glycerol and synthetic fatty alcohols comprising between 9 and 15 polyoxyethylenated carbon atoms with 5 or 10 moles of ethylene oxide; you can also use polyethoxylated castor. These non-ionic emulsifiers are present in the compositions of the invention at a rate of 1 at 25% by weight.
Other emulsifiers which can be used according to the invention may be oxyethylenated or not alkyl sulfates such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium cetyl stearyl sulfate, cetyl stearyl sulfate triethanolamine, monoethanolamine lauryl sulfate or triethanolamine, oxyethylenated sodium lauryl ether sulfate comprising for example 2.2 moles of ethylene oxide, lauryl monoethanolamine ether sulfate comprising for example 2.2 moles of ethylene oxide, lauryl ether sulfate of monoethanol-oxyethylenated amine comprising for example 2.2 moles of oxide ethylene.
These constituents are present in the compositions of the invention, preferably at concentrations included between 1 and 15% by weightO
~ es creams according to the invention may contain in addition soaps, fatty alcohols and emulsifiers ~ adjuvants commonly used in such compositions as fatty amides.
Among fatty amides, preference is given to mono- or diethanolamides, acids derived from coconut, lauric acid or oleic acid in concentrations between 0 and 10% by weight, relative to the total weight of the composition.
It may be advantageous to add to the mercaptan used according to the invention an anti-oxidant intended to avoid evolutions of the dyeing power.
Mention may be made, by way of example, of sulfite, sodium bisulfite and hydrosulfite, ascorbic acid or isoascorbic, their esters and their salts, etc.

~ ~ 2 ~ ~

The concentrations of these compounds vary from 0 to 1%.
~ es compositions according to the invention can also t contain solvan-ts, thickeners, treating agents, sequestering agents, such as ethylene diamine tetra-ketic, diethylene triamine pentacetic acid or their salts, perfumes, preservatives, so-laires, etc ....
Solvents can be added to the composition in order to dissolve the dyes i ~ sufficiently soluble in water. In this case, the usable sol ~ ants are ideal ticks to those indicated above in the composition of liquids gellables.
Among the thickening agents which can be used according to the invention include sodium alginate or gum arabic, or cellulose derivatives such as methyl-cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethylcellulose, carboxymethylcellulose or carboxyvinyl polymers such as carbopols.
These constituents are present in an amount of 0.5 to 5%.
The treating agents which can be used according to the invention are intended to improve mainly the touch and the hair mixing. They can for example be poly-cationic mothers such as quaternary ether drifts of cellulo ~ e like the JR 400 * from Union Carbide, diallyldimethylammonium polychlorides like Merquats 550 * and 100 * from Merck, quaternized polymers as defined in the French bre ~ ets of the plaintiff No. 2.270.846: 2.316.271, 2.189.434, 2.333.012 published on June 24, 1977, cationic grafted and crosslinked copolymers described in the applicant's French patent application 73 22222 published under the number 2.189.439 on April 3, 1976, used alone or as a mixture, the concentration of agent * Trademark treating ranges from 0.1 to 5% by weight. The two-step process according to the invention also makes it possible to vary the consistency tance and the form of the dye support between the moment of applying the compositions to the hair and dyeing in herself. It is thus possible, in an embodiment advantageous of the invention, to apply the first composition in liquid form on the hair which promotes their impregnation tion, the second composition containing active ingredients on the first at the level of the hair by modifying its consistency for example by gelation which facilitates application dye on the hair.
The so-called "tri-nucleus" compounds which constitute another object of the invention can be represented by the form general mule:

Y ~ i3 N ~ 0 NH

Y
/ R ~
where Y means \ R ' R'l and R'2 denote alkyl, mesylaminoalkyl, piperidino alkyl and hydroxyalkyl of which the alkyl groups include bear 1 ~ 6 carbon atoms and their salts cosmetically ~ ~ 2 acoeptables.
These compounds are prepared by reacting approximately 1 mole of the corresponding aminoaniline with 1 mole of ortho-aminophenol in an oxidizing alkaline medium.
The following examples are intended to illustrate the invention without however limiting it.
EXAMPLE A
Preparation of dihydrochloride, monohydrate of N, N ~ hydroxy-ethyl, ~-mesylaminoethyl) para-phenylenediamine used in the compositions S13, Preparation of acet ~ lamino-4 N (~ O-mesylamino ethhl) anilines To a solution of 0.1 mole (32.7 g) of N- sulfate (~ -mesylaminoethyl) paraphenylenediamine in 150 ml of water, 0.2 mol (25.2 g) of sulfite is added at room temperature sodium and, gradually, with stirring, 0.13 mole (13.17 g) acetic anhydride. The addition is complete, the agitation is maintained for one hour and then the expected acetylated derivative is wrung which precipitated in crystalline form ~ e product is seated, washed with water and dried under vacuum. After a recrystalli-sation in alcohol and vacuum drying / it melts ~ 130 ~ C.

Calculated for Analysis 11 17 3 3 Found . . . . . .. _ C ~ 48, ~ 1 48.71 H% 6.27 6.15 N ~ 15.50 15.80 _% 11.81 12.01 Preparation of acetylamino-4, N, N ~ h ~ drox ~ ethYl, ~ 9-mes ~ yl-aminoeth ~ 1) anilines 0.03 ~ mole (10 g) of 4 N acetylamino is dissolved (~ --25 ~

,; , ~. ~ 7 ~

mesylamino ethyl) aniline in 31 ml of boiling water. Under stirring, 7.4 g of sodium carbonate and 0.148 are added mole (18. ~ g ~ of glycol hydrobromine. After 4 hours stirring in a boiling water bath, the reaction medium is filtered then the filtrate is left for 48 hours at 0C. We wring acetylæmino-4 N, N ~ hydroxyethyl, ~-mesylamino ethyl) aniline which precipitated in crystallized form. After recrystallization from boiling water and drying under empties the product melts at 118C.

. . _ Calculated for Analysis 13H21N3S4Find ... . .. ~
C% 49.52 49.80 H ~ 6.67 6.77 N% 13.33 13.16 S% 10.16 10 ~ 36 Preparation of dihydrochloride, monoh ~ drate of N, N ~
hydrox ~ eth ~ g-mes ~ laminoeth.yl) paraPhénJ ~ lene diamine:
We heat 30 minutes in a boiling water bath 0.0178 mole ~, 6 g) acetylamino-4 NJN ~ hydroxyethyl, ~-mesylamino ethyl) aniline in 12 ml of aqueous solution hydrochloric 5 N. ~ 'water is then removed under vacuum. After having maintained the residue for two hours under ~ ide at 60C, we obtains a chromatographically pure crystallized product ~
Molecular mass calculated for Cll H19 N3 03 S, 2 HCl, H20 ~ o ~ 3 ~ 6 Molecular mass obtained by potentiometric determination ...... 358 2 ~

. . . .,. _ Calculated for Analysis CllHl9N303s ~ 2 HCl ~ H20 Found . ....
C% 36.26 35.97 36.08 H% 6.31 6.40 6.44 N% 11.53 11.39 11.28 Cl ~ 0 19j50 19.54 19.66 EXAMPLE B
.
Preparation of N ~ hydroxyethoxy3-ethyl sulfate ~ -4-amino aniline:
F

2N (CH2) 2 - O - (CH2) 2 OH step 1 NH - (CH232 ~ ~ tCH2) 2 OH NH - (CH2) 2 ~ ~ (CH2) 2 OH

2nd stage ~ e ~ ~, 1st stage: Preparation of nitro-4 N- ~ g- (~ '-hydroxyéthyoxy ~
ethyl ~ aniline.
It is heated for 2 and a half hours between 110 and 120C
0.2 mole (28.2 g) of paraIluoronitrobenzene in 84.6 ml of diglycolamine. After cooling the mixture ~ we pour it in 300 g of crushed ice. ~ e expected product precipitates under crystallized form. We wring it out, wash it in water and dried. After recrystallization from ethanol and drying under empty, it melts at 78C, ~ 'an31yse elémen-taire the product obtained gives the following results:

~ 2 ~

. . _. _ AnalysisCalcUlé for CloH144N2 Found C% 53.09 53.20 H ~ o 6.19 6.32 N o 12.39 12.32 2nd step: Preparation of Nf ~ hydroxy sulfate-ethoxy) -ethyl ~ -amino-4 aniline.
175 ml of hydroethanolic solution (15 ~ o of water, 85% ethanol ~ 7.5 g of ammonium chloride and 58.5 are added g zinc powder. This mixture is carried ~ reflux under agitation-tion then add, in small portions, 0.15 msle (33 ~ 9 g) of the product obtained for the first step. When the addition of the nitro derivative is finished, the reaction medium is deco-lore; it is filtered boiling by collecting the filtrate in a vial containing 10.5 ml of concentrated sulfuric acid and 30 ml of cooled ethanol ~ -10C. ~ e expected product precipitates in the form of a gum which crystallizes quickly. We wring it out it is washed with alcohol and then with acetone. After drying under empty, the product melts with decomposition around 157C. After recrystallization from a hydroethanol mixture, the product obtained is 50umis in the anal ~ elementary which gives the results-following states:

. ~. . ._ Analysis Calculated for CloH18N206 Found _ _ ~. .., C% 40.82 40.65 H% 6.12 6.07 N% 9.52 9.53 S_% 10.88 10.92-10, ~ 9 ~ 2 ~ 79 EXAMPLE C
Composed of three aromatic rings of formula:

CIH2 ~ N = ~ = O

NOT
Cl 2 Cl2 CH ~ OH CH20II
In 200 ml of hydroethanolic solution (40% ethanol, 60%
of water) we dissolve:
0.022 mole (6.5 g) N, N-bis sulfate (~ -hydroxy-ethyl) amino-4-aniline and 0.023 mol (2.6 g) of orthoamino-phenol. 40 ml of ammonia are added to 22B and 100 ml of water o ~ ygénée ~ 20 volumes. After two hours of stirring ~ temperate rature room the expected product is drained. After recruiting metallization in methanol and drying under v; of the product background at 1 ~ 0C, `
Molecular mass calculated for C26H33N ~ 05: 495.
Molecular mass found by potentiometric determination in acetic acid ~ using a solution of perchloric acid as: 503 (for 3 titratable functions).
Its structure has been proven by study ~, IN.
Molecular mass: 405 per mass spectrum -2 ~ -2 ~

.
Analysis Calculated for C26H33N505 Found _ ._ C% 63, o3 62.73 H% 6.66 7.00 N% 14 ~ 14 13.90 14.12 _ _ _ __ _ 17.04-17.10 EXAMPLE No. 1 The following compositions are prepared:
Composition Sl:
2,6-dimethyl-5-methoxy dihydrochloride 10 paraphenylene diamine ............................., 2.40 g Orthoaminophenol .. O ...................... O ........... .... 0933 g Remcopal 334 * ..... ~ ....... ~ ...... 22 g Remcopal 349 * ....., ......,. ~., ... 22 g Butylglycol ......., ....... ,, ..., ..., ........................ ........ r ~ 8 g Propyl ~ ne glycol .......... ..... .... ...... ..................... .......... 8 g Crosslinked polyacrylic acid .... O.-.-. - ..- O ----- 0.5 g Masquol DTPA * ..... ~, ..... .., .............., ................. .......... 2.5 g Sodium bisulfite 35 ~ é ......................... 0.5 cc Ammonium thiolactateX .............. ~ ............. 1.5 g 20 Monoethanolamine ..................................... 7 cc Water, qs .... ~ ........................................ 103 g The ammonium thiolactate is added at the time of use.
~ S2 position:
.
Polychol 5 * ...., ..................... 0 ~ ......... ..... 0 3.3 g Polychol 20 * ~ q ~ 1 ~ 7 g Cetyl stearyl alcohol .................... ........ 5 g Oxygenated water ~ 100 volumes ............. ~ .... ....... ~ 0 g Phosphoric acid qs ................... ....... pH 3 Water, qs ................................ D ~ 00 g 30 * Cornmerce market z ~

40 g of the composition Sl are applied for 10 minutes on a very light blond hair ~ including a ~ ort percentage of white hair.
40 g of the composition is then applied without rinsing.
sition S2. After 20 minutes of applying the gel thus obtained held, we rinse, shampoo and dry the hair ; which is colored in mat dark blonde.
If, on the other hand, a identical position containing only one of the two dyes at equivalent concentration (1.3 x 10 2 mole%) is not reached than a very light ash blonde shade with paraphenylene-diamine above and dark golden blonde with orthoaminophenol, shades that are less resistant ~ several shampoos than the dye obtained with the mixture of these two co-precursors lorants by oxidation.

The following composition is prepared:
Composition S3:
4-amino N, N- (ethyl ~ carbamyl methyl) anillne .... O 1.93 g 20 Orthoaminophenol ..................................... 0.33 g Remcopal 334 * ..................................... 21 g Remcopal 349 * ..................................... 24 g Oleic acid ...................................... 4 g Butylglycol ........................................ 3 g Absolute ethyl alcohol ........................... 14 g ~ DTPA asquol * ..................................... 2.5 g Sodium bisulphite 35 Be ......................... 0.5 cc Glycerol monothioglycolate ....................... 2 ~ 5 g Baking soda ............................... 0.35 g 30 Soda ................................................ 0.07 g * ~ commercial arch Z ~ 7 ~

Ammonia at 22 Be ............., ................. ..8 cc Water, qs ..................... ~ ................. 100 g ~ e glycerol monothioglycolate is added at the time of employment.
30 g of creamy composition S3 are applied for 7 minutes on light brown hair having a low percentage of white hair.
Then apply, without rinsing, 30 g of the compound following S4 section:
10 Composition S4:
Polychol 5 * ........................................ 3.3 g Polychol 20 ....................................... 1.7 g Cetyl stearyl alcohol ........................... ~ G
Hydrogen peroxide at 100 volumes ......................... 30 g Phosphoric acid, qs, ........................ .pH 3 Water, qs ........................................ 100 g ~ -We knead the hair well and let it pause for a while.
for about 20 more minutes. After rinsing with water lukewarm, shampoo and dry ~ e, the hair is uniformly colored in dark chestnut whereas if we apply the same so an identical composition containing only one of these components ~ the concentration of 1.3 x 10 m ~ O ~ the same hair is colored in dark ash blonde with the para phenylenediamine above and in dark golden blonde with gold-thoaminophenol. ~ e more, the dark chestnut shade obtained in combining these two compounds para and ortho presents a resistance tance increased vis-à-vis several shampoos.

* ~ commercial arch EXAMPLE No. ~
The following dye composition is prepared:
Composition ~:
Sul ~ ate, N, N-bis- (~ -hydroxyethyl) monohydrate paraphenylenediamine ..........., ........................ 1.60 g Orthoaminophenol .................................. ..... 0.82 g Alfol C 16/18 E * ................................... 8 g Lanette wax E .................................. 0.5 g Cemulsol B * ........................................ 1 g 10 Oleic diethanolamide ............................... 1.5 g Ethylene diamine tetracetic acid ................ 0.3 g Ammonium thiolactate ............................. 1.25 g Ammonia at 22 Be ................................ 12 cc Water, qs ........................................ 100 g 15 g of this creamy mixture are applied to the raci born of blonde hair permed 4 months ago.
8 minutes later we distribute an additional 15 g of this cream.
me on the whole hair, and after 2 minutes, we incorporates on the entire hair 30 g of the composition tion S2 and let it sit for an additional 30 minutes.
After rinsing, shampooing and drying, we obtain a very beautiful uniform shade of dark chestnut mat more intense and significantly more solid vis ~ vis several shampoos than the shade obtained in the same way with each of the precur ~
dyes of oxidation dyes: blond - light blond with N, N-bis- (~ -hydroxyethyl) paraphenylenediamine alone above and dark golden blonde with orthoaminophenol.
EXAMPLE No. 4 The following dye composition is prepared:
* Trademark ~ ~ 2 ~ ~

N, N- dihydrochloride (ethyl, piperidinoethyl) paraphenylenediamine ................................ 3.2 Orthoaminophenol ......... ,,, ......., ................ 0.055 g Cetyl alcohol ......... O ................................ 18 g ~ ammonium aurylsulfa-te at 20 ~ o ..................... 12 g Alcohol ket ~ l stearyl with 15 moles of oxide ethylene ............................................ 3 g Lauric alcohol ....................................... 5 g Masquol DTPA * .................................... 2 ~ 5 g 10 Ammonium thioglycolate ............................... 0.4 g Ammonia at 22 Be .................................. 11 cc Water, qs .......................................... 100 g Before use, mix 7 g of this cream with 7 g of water. This creamy mixture is applied for 10 minutes on a lock of 1 g of semi-permed gray hair.
Then added 7 g of an aqueous solution at 12 ~ o hydrogen peroxide at pH 3 adjusted by phosphoric acid and leave everything for 20 minutes.
After rinsing and drying, the wick is colored in beige gray while, under the same conditions, the para-phenylene diamine alone above practically does not color this type of fiber and that orthoaminophenol does not allow only a very pale yellow color.
EXEr ~ E No. 5 The following dye composition is prepared:
Composition S6:
_ _.
N, N-bis (~ -hydroxyethyl) sulfate, monohydrate paraphenylene diamine ........., ..................... ~, 94 g Orthophenylene diamine ........................... ... 0.11 g 30 Comperlan KD * ....................................... ~ 1.75 g * Trademark ~ 4L2 ~

Ethylene glycol distearate ............................... 1 g ~ sodium aurylsulfate with 2 moles of oxide ethylene ............................................... 12 g Blanose R 530 * ............................................ 0, 1 g Ethylene diamine-tetracetic acid ...................... 0.2 g Thiolactic acid ......................................... 1 g Ammonia at 22 Be ....................................... 10 cc Water, some ............................................... 100g 40 g of this gel is applied to blond hair clear unevenly sensitized and with a strong percentage white hair.
30 g of the composition are then added to the hair.
tion S2 and, 20 minutes later, rinse, shampoo and dries the hair which is colored in ash gray while, under the same conditions, the paraphenylene diamine above provides only a light blonde shade and the ortho-phenylene diamine a light golden blonde shade, shades that are less resistant to several sham-fists as the shade obtained by mixing the two compounds para and ortho.
EXAMPLE No. 6 The following compositions are prepared:
S7 composition:
Dichlorate of N, N- ~ ethyl, ~ ~ mesylamino ethyl ~
paraphenylenediamine ................. ..., ............ 3.30 g Paraaminophenol ...................................... 0.54 g Orthoaminophenol ..................................... 0.54 g Remcopal 334 * ......................................... 21 g Remcopal 349 * ......................................... ~ 4 g 30 Oleic acid ....................................... 3 g * Trademark .,,. ",, ~ 4Z ~

Butylglycol ......................................... 3 g Absolute ethyl alcohol ............................ .14 g Ethylene diamine tetracetic acid ................. 0.2 g Cysteine hydrochloride ............................ 0.1 g Thioglycolic acid ................................ 1.7 g Ammoniaqlle à 22 Bé ................................ 12 cc Water, qs ~ ........................................ 100 g Composition S8:
Polychol 5 * ........................................ .3.3 g 10 Polychol 20 * ............................... ~ ......... 1.7 g Stearyl alcohol ................................. .5 g Hydrogen peroxide at 100 volumes ......................... 60g Phosphoric acid, qs ......................... ..pH 3 Water, qs ........................................ .100 g Composltion S ~:
Resorcin .......................................... 0.44 g ~ etaaminophenol .................................... 0.76 g Remcopal 334 * ........................................ 20 g Remcopal 349 ~ ........................................ 20 g Carbopol 934 ~ ........................................ 1.25 g Absolute ethyl alcohol .............................. 8 g Propylene glycol .................................... .6 g Ethylene glycol distearate ......................... 0.5 g Ethylene diamine tetracetic acid .................. 0.2 g Sodium bisulphite 35 Be .......................... 0.5 cc Citric acid, qs ............................... pH ~
Water, qs ......................................... 100 g 30 g of the compound are applied for 10 minutes tion S7 on hair colored in chât ~ in clear.
We then add you by kneading the hair well 1 ~ g of composition S8 and, 5 minutes later, apply * Trademark generously 15 g of the composition S9 and the everything for 25 minutes.
After rinsing, shampooing and drying, the hair are you united ~ hintly colored in brown while, in the same operating conditions, the mixture of the two "para" bases allows only puts to get a dark blond shade and the ortho-aminophenol only a dark golden blonde shade.
On the other hand, if the couplers of composition S9 are applied at the same time as the oxidation bases of the S7 composition and if this composition is then applied in two-stroke without intermediate rinsing;
1st time (10 minutes): 30 g of the S7 composition + 15 g of composition S9.
2nd time (30 minutes): 15 g of composition S8.
The same hair is only colored in chestnut mat after rinsing, shampooing and drying.
EXEr ~ P ~ E No. 7 The following dye composition is prepared:
Composltion S10.

20 N, N dihydrochloride (ethyl, ~-mesylaminoethyl) paraphenylenediamine ............................... 3.30 g Orthoaminophenol ................................... 0.33 g 2 ~ aminoethyl) amino hydrochloride anthraquinone ...................................... 0.60 g - Remcopal 33 ~ ....................................... 21 g Remcopal 349 * ....................................... 24 Oleic acid ........................................ 4 g Butylglycol .................... ~ ............................ 3 g Absolute ethyl alcohol ............................. ....... 14 g 30 Masquol DTPA * ........................................ ...... 2.5 g * Trademark ~ Z ~ 7 ~

Mercaptosuccinic acid ....... 0.5 g Thioglycola ~ e ammonium ....... 3 g Ammonia at 22 Be ............ 10 cc Water, qs .................... 100 g 40 g of this composition are applied to a hair lure light chestnut. After 12 minutes, apply, massaging the hair, 40 g of composition S2 and leaving mixing for an additional 20 minutes.
After rinsing, shampooing, then drying, one obtains a dark chestnut shade while, under identical conditions ticks, the combination of paraphenylene diamine above and anthraquinone dye allows only one shade dark golden blonde and orthoaminophenol alone, a shade golden blond.
EXAMPLE No. 8 The following dye composition is prepared:
Composi ~ ion Sll:
. _.
N, N- dihydrochloride (ethyl, ~-mesylaminoethyl) paraphenylenediamine ........... ~ .................... 3.30 g 20 Orthoaminophenol ..................................... 0.30 g Remcopal 334 * ........ ~ ................................... 22 g Remcopal 349 * ...................................... ...... 22 g Butylglycol ........................................ ...... 8 g Propylene glycol ................................... ...... 8 g Ethylene diamine tetracic acid ~ ic ................. 0.20 g Sodium bisulphite 35 Be ........................... 1 tsp Ammonia ~ 22 Be ......................... ~ ....... 10 cc Water, some ......................................... 100g Composition S12:
30 6-amino benzomorpholine .............................. 0.50 g ~ Trademark Resorcin ............................................ 0.45 g ~ etaaminophenol ...................................... 0.75 g Remcopal 334 * ........................................ 20 g Remcopal 349 * ........................................ 20 g Carbopol 934 ~ ....................................... 1.25 g Absolute ethyl alcohol .............................. 8 g Propylene glycol ..................................... 6 g Ethylene diamine tetracetic acid .................. 0.2 g Sodium bisulfite 35 ~ é ........................... 0.5 cc 10 Citric acid, qs ................................. pH 6 Water, qs .......................................... 100 g Before use, 40 g of the composition Sll are mixed with 20 g of a 12% solution of hydrogen peroxide and apply the gel thus obtained on a hair dyed brown.
15 minutes later, add 20 g of the position S12 by carefully massaging the hair and leaving this mixture in contact with the hair for 10 minutes at the end of which one rinses, performs a shampoo and dries.
The hair is colored in dark brown with reflections cen ~ res while if we apply for 30 minutes the mixture gelled of 40 g of the composition Sll with 20 g of the composition S12 and 20 g of 12% oxygenated water, this same hair is colored in bluish brown with no background.
EXAMPLE No. 9 The following dye composition is prepared:
Composition Sl ~:

N, N- (~ -hydroxyethyl dihydrochloride monohydrate, mesylaminoethyl) para-phenylenediamine ............. 3 ~ 6 g N ~ g- (~ '-hydroxyethoxy) ethyl ~ amino-4 sulfate 30 aniline ................................................ 1, ~ g * Trademark Orthoaminophenol ............... .. ..,. ,, ........... 0.5 g Alfol C 16/18 E * .................. .. ................ 8 g Lanette wax E ................. .. ............... 0.5 g Cemulsol B ~ ....................... .. ................ 1 g Oleic ethanolamide ............ .. ............... 1.5 g Masquol DTPA * ..................... .. ............... 2.5 g Thiolactic acid ................ .. ............... 1.5 g Ammonia at 22 Be ............... .. ............... 12 cc Water, qs ....................... .. ............... 100 g 40 g of this compound are applied for 10 minutes -sition on hair dyed blond and unevenly felt sibilized, then add without rinsing ~ age 40 g of the composition We homogenize this dye mass well and, 20 minutes later, rinse, shampoo and dry them hair which is colored in mat dark chestnut whereas, in the same conditions the mixture of the two para-phenylene dia-above mines colors this hair in mat dark blonde, and orthoaminophenol in dark golden blonde.
EXE ~ LE 10 The following dye composition is prepared: -Composition S14 ~
4-amino N, N- (ethyl ~ -carbamyl methyl) aniline .. ~ .. 1.95 g N (~ -hydroxyethyl) amino-2 aniline hemisulfate .. 0.60 g Remcopal 334 * ....................................... 21 g Remcopal 349 * ........................ Ø ............ 24 g Oleic acid .................................... .... 4 g Butylglycol ........................... ~ .............. 3 g Absolute ethyl alcohol ............................. 14 g 30 Ethylene diamine tetracetic acid .... O ........ 0.2 g Acid ~ o ('adipic dimercapto .................. 0, ~ g * Trademark , - -. ... ..

~ L ~ 2 ~

Cysteine hydrochloride ............................. 0.1 g Thioglycolic acid ................................. 1 g Ammonia at 22 Be .................................. 11 cc Water, some ... ~ ........................................... ....... 100 g Thioglycolic acid is introduced at the time of use.
40 g of composition S14 are applied to a che velvet dyed blond. 10 minutes later, we add in carefully massaging the hair 40 g of composition S2 and the mixture is left for an additional 25 minutes. After rinse, shampoo then dry, the hair is colored in matt chestnut while if we apply in the same way ~ on a identical composition but containing only one of the placed para and ortho at a concentration of 1.3 x 10 2 M%, this hair is colored in ash blonde with the initials -nylène diamine and in dark golden blonde with ortho phenylene diamine.
EXAMPLE E No. 11 The following dye composition is prepared:
Composition S ~ 5:

20 Orthoaminophenol ....................................... 0.54 g N, N- (~ -hydroxyethyl dihydrochloride monohydrate, -mesylaminoethyl) para-phenylenediamine ............. 3.46 g Alfol C 16/18 E * ................................. .............. 8 g Lanette wax E ..................... ......................... .. 0.5 g Cemulsol B ~ ........ ~ ...., ..................... ............ .... 1 g Oleic diethanolamide ....................................... 1.5 g Masquol DTPA * ............................. ................ 2, 5 g Thioglycolic acid ...................... .1 g Ammonia 22B ........................... 11 g 30 Water, qs ................................ 100 g * Trademark z ~

pH: lQ
10 g of this composition are applied to che-naturally want red copper light brown then after 10 minutes, we add to the hair, without rinsing beforehand,

5 g of an oxidizing milk has 18 ~ of hydrogen peroxide of composition S8 above.
We knead the hair well. After 20 minutes of exposure time, rinsing and shampooing, a color is obtained slightly dark ash brown.
If in the previous example we remove the ortho-aminophenol of the dye composition, all the rest of Description: composition, exposure time, type of hair, remaining identical, a dark golden blonde color is obtained.
EXAMPLE No. 12 The following dye composition is prepared:
Composition S16:

Orthoaminophenol ..................................... 0.22 g 4-amino dihydrochloride N, N- (ethyl, ~-mesylamino-ethyl) aniline ................., .......................... 2 g Oxyethylenated oleic alcohol with 2 moles of oxide ethylene ............................................... .4 g Oxyethylenated oleic alcohol with 4 moles of oxide ethylene ............................................... .4 g Diethanolamides of coconut fatty acids .............. 10 g Nonylphenol has 4 moles of ethylene oxide ............. 6 g Nonylphenol with 9 moles of ethylene oxide ............. 6 g Masquol DTPA * ........................................ 2 g Propylene glycol .............. O .......................... 8 g Ethanol at ~ 6 ........................................ .... 2 g 30 Sodium bisulphite at 35 Be ........................... .... 2 g Trademark _42-~ z ~ g Ammonia at 22 Be ................................... 10 g Water, qs ......................................... 100 g pH = 9.9 Before use, 40 g of this composition are mixed with 40 g of oxidizing milk at 6% of the composition Sl ~ below.
Composition S17:
Polychol 5 * .......................................... 3.3 g Polychol 20 * ......................................... 1.7 g Stearyl alcohol ..................................... 5 g Hydrogen peroxide at 100 ~ ol ................................ 20 g Phosphoric acid, qs .......................... pH 2,3 Water, qs .......................................... 100 g This mixture is applied 20 minutes to hair discolored. After rinsing and shampooing, a color is obtained.
tion gray blue silver.
If in the previous example we delete the orthoamino-phenol everything else remains unchanged you get a very blond light shade of green.
EXEMP ~ E No. 1 ~
The following dye composition is prepared:
Composition S18:
.. ...
2-N- (~ -hydroxyethyl) amino phenol ................... 0.153 g N, N- (~ -mesylamino-) dihydrochloride monohydrate ethyl, ~ -hydroxyethyl) paraphenylenediamine ......... 1d ~ 3g Mercapto 2 ethanol ................................... 2 g Remcopal 334 * ........................................ 3 g Remcopal 349 * ....................................... ~ g Oxyethylenated oleic alcohol with 2 moles of oxide ethylene .......................................... 2.5 g 30 * Trademark ~ 4 ~ 79 Oxyethylenated oleic alcohol with 4 moles of oxide ethylene .............................................. 2 , 5 g Propylene glycol ......................................... 10 g Carbopol 934 * ........................................... 0.2 g Sodium bisulfite at 35 Be .............................. 1 g Ammonia at 22 Be ....................................... 7 g Trilon B * ............................................... 0.1g Water, qs ................................... ~. 100g pH = 10.1 To 30 g of this composition is added, at the time of use9 30 g of an oxidizing milk containing 6% hydrogen peroxide from the composition S19 defined below.
Composition Sl ~:

Polychol ~ * ................................... .......... 3, 3 g Polychol 20 * .................................. .......... 1.7 g Stearyl alcohol ............................ ............ 5 g Oxygenated water at 100 vol ........................ ........... 20 g Phosphoric acid, qs ..................... ......... pH 2.3 Water, qs ................................... .......... 100 g This mixture is applied to an initial hair-ment brown discolored to straw yellow. After 10 minutes, without no prior rinsing, 5 g of the composition are applied dye S20 below.
Composition S20:

2-hydroxy 1 ~ 4-naphthoquinone ........... O ............... - 6.7 g Resorcinol ........................................ ....... 2, 3 g Propylene glycol, qs ......................... ....... 100 g We knead the hair well so as to obtain good homogenization. After 20 minutes of exposure time, rinsing and shampooing gives a golden brown color.
~ Trademark ~ 44-~ z ~

If in the example above we remove the 2-N- (f ~ -hydroxyethyl) amino phenol of dye composition S18, all the rest of the description: compositions, exposure time, the nature of the hair remaining identical, we then obtain a golden blond coloring.
EXAMPLE No._14 We prepare the following dye composition:
Composition S21:
4-amino N hydrochloride, ~ - (ethyl, 10 ~-mesylaminoethyl) aniline ............................. 3.3 g Orthoaminophenol ..................................... 0.54 g Remcopal 334 * ..................................... 21 g Remcopal 349 * ...................................... ......... 24g Oleic acid ...................................... .......... 3 g Absolute ethyl alcohol ................................ 14 g Ethylene diamine tetracetic acid ................... 0.2 g Thioglycolic acid .................................. 1.7 g Ammonia (d = 0.92) ................................. 12 ml Water, qs ........................................... 100 g 20 pH = 9.6 10 g of this composition are applied to che-naturally want golden blonde then after 5 mins of time pose, we add on the hair? without prior rinsing, 5 g of an oxidizing milk with 9 ~ 0 hydrogen peroxide of composition S22 below.
Composition S22:
. . .
Polychol 5 * ........................................... 3.3 g Polychol 20 * ......................................... 1.7 -g Stearyl alcohol ..................... O ................ 5 g 3o Hydrogen peroxide at 100 vol ................... O ............... 30 g * Trademark 21 ~
. .

Phosphoric acid, qs .................. O .... p ~ 2.8 Water, qs ....................................... 100 g We mix the hair well to get a good homogenization then, after 5 minutes of exposure time, add to the hair, without rinsing ~ age, 5 g of the following dye composition S23:
Composition S2 ~:

2-methyl 5-amino phenol .......................... ... O, 49 g Remcopal 334 * .................................... ..20 g Remcopal 349 * .................................... ..20 g Carbopol 934 * .................................... ... 1.25 g Propylene glycol ................................. ... ~ g Ethylene glycol distearate ..................... ... OD58 g ^
Ethylene diamine tetracetic acid .............. ... 0.2 g ~ sodium isulfite 35 Be ....................... ... 0.5 g Citric acid, qs ........................... .pH 6 Water, qs ...................................... ... 100 g After a good homogenization and 30 minutes of exposure time rinse and wash the hair with shampoo.
A black violet coloration is obtained.
If in the example above we delete the orthoamino-dye composition phenol S21 all the rest of the description: composition, exposure time, nature of Gheveux remaining unchanged, a light beige gray coloration is obtained nuanced purple EXE ~ IPLE No. 1 ~
The following dye composition is prepared:
Composition S24-N, N-bis ~ -hydroxyethyl sulfate) paraphenylene-3 diamine .............................................. 1 g * Trademark 7 ~

N ~ hydroxyethyl) 2-amino phenol ........ 0.5 g Alfol C 16/1 ~ E * ...................... 8 g Lanette wax E ..................... 0.5 g Cemulsol B * ........................... 1 g Oleic diethanolamide ................ 1.5 g Masquol DTPA ~ '........................ 2.5 g Thiolactic acid .................... 1 g Ammonia 22 Be ..................... 11 g Water, qs ........................... 100 g 10 pH = 10 To 10 g of this composition is added 10 g of milk oxidizing agent at 6 ~ o of hydrogen peroxide of composition S25 below.
Composition S25:
Polychol 5 * ........................................ 3.3 g Polychol 20 * ....................................... 1.7 g ; Stearyl alcohol .................................. 5 g Hydrogen peroxide at 100 vol .............................. 20 g Phosphoric acid, qs ............ O ............ pH 2.8 Water, qs ...................................... .. 100 g After a good homogenization, this method is applied.
swaddle on hair dyed in red copper. After 15 minutes laying, rinsing and shampooing tones are obtained matt dark brown.
EXAMPLE E No. 16 _ _.
The following dye composition is prepared:
Composition S26:
N, N dihydrochloride monohydrate (~ -mesylamino ~
ethyl, ~ -hydroxyethyl) paraphenylenediamine ........................ 3.6 g Ortho aminophenol ................................................ .. 0 ~ 5 g * Trademark 3-nitro 4-N '(~ -hydroxyethyl) amino N, N- (~ -hydroxyethyl) aniline ........................... .... 0.8 g Alfol C 16/18 E * ................................ .... 8 g Lanette wax E ............................... .... 0.5 g Cemulsol B * ..................................... .... 1 g Oleic diethanolamide .......................... .... 1.5 g Masquol DTPA * ................................... .... 2.5 g Thioglycolic acid ............................ .... 1 g Ammonia at 22 Be ............................. .... 11 g 10 Water, qs ....................................... .... 100 g 15 g of this mixture are applied to the roots of a golden blonde hair permed 4 months ago. 8 minutes afterwards 15 g of this same mixture are distributed over all of the hair and, two minutes later, we add to the total tee of the hair, kneading well to get a good homogenization, 30 g of an oxidizing milk with 9% hydrogen peroxide and having the following composition S27:
Composition S27:
Polychol 5 * ..................................... 0. 3.3 g 20 Polychol 20 * ...................................... .... 1.7 g Stearyl alcohol .............................. .... 5 Oxygenated water at 100 vol .......................... .... 30 g Phosphoric acid, qs ...................... ..pH 2,8 Water, qs ..................................... .... 100 g After 20 minutes of exposure time, rinsing and shampooing pooing on ob-obtains a uniform coloring, black with reflections purple.
If in the previous example we delete the gold $ hoamino-phenol, all the rest of the description of the mode of application remaining unchanged we obtain a dark chestnut with purple reflections.
,* Trademark - ~ 4 ~

EXAMPLE No. 17 The following dye composition is prepared:
Compositlon S28:
N, N- (~ -mesylamino-) dihydrochloride monohydrate ethyl, ~ -hydroxyethyl) paraphenylenediamine .......... 1.09 g 2-N- (~ -hydroxyethyl) amino phenol ................... 0.153 g Remcopal 334 * .......................................... 12 g Remcopal 349 * .......................................... 15 g 10 Oxyethylenated oleic alcohol with 2 moles of oxide ethylene ............................................ 1.5 g Oxyethylenated oleic alcohol with 4 moles of oxide ethylene ............................................ 1.5 g Propylene glycol ......................................... ~ g Sodium bisulfite 35Bé ........................... 1.2 g Trilon B * ............................................ 0.12 g Mercapto succinic acid ............................. 1.8 g Ammonia at 22 Be ..................................... 10 g Water, qs ........................................... 100 g pH = 10.1 25 g of this composition are applied to a hair lure naturally straw. After 10 minutes of exposure time 20 g of a oxidizing milk with 9 ~ 0 hydrogen peroxide and composition S27 above defined.
We mix well to obtain a good homogenization tion then after 10 minutes of exposure time we add on the hair, without rinsing ~ age and by distributing it best possible, 21 g of the dye composition S29.
Composition S29:
* Trademark 2 ~ 9 2-Methyl 5-amino 6-nitro phenol ...................... 0.15 g 3-nitro 4-N- (~ -hydroxyethyl) amino phenol ............ O, 2 g Oxyethylenated oleic alcohol with 2 moles of oxide of ethylene .......................................... 5 g Oxyethylenated oleic alcohol with 4 moles of oxide ethylene ........................................... 10 g Propylene glycol ..................................... 10 g Triethanolamine, qs .............................. pH = 7 Water, qs .......................................... 100 g After 15 minutes of exposure time, rinsing and shampoo gives a very ashy brown color.
If in the example we remove the 2-N- (~ -hydroxy-ethyl) amino phenol of dye composition S28 all rest of description remaining unchanged we get a chestnut very light golden.
EXAMPLE No. 18 The following dye composition is prepared: -Composition S30:
Orthoaminophenol .................................... 0.54 g 20 4-NN dihydrochloride (ethyl, ~-mesylaminoethyl) amino aniline .... O ....................................... 3.72 g Oxyethylenated oleic alcohol with 2 moles of oxide ethylene .......................................... ..... 4.5g Oxyethylenated oleic alcohol with 4 moles of oxide ethylene .......................................... ..... 4 ~ 5 g Coconut fatty acid diethanolamides ............ 10 g Thioglycolic acid .............................. ... 0.17 g Bisul ~ ite of sodium at 35 Be ...................... ... 1 g Masquol DTPA * ................................. ... 2 g 30 Propylene glycol ................................... ~ 4.5 g ~ commercial arch 2 ~ L ~
.

Butylglycol ........................................... 8 g Ethanol 96 ......................................... 8 g Ammonia at 22 Be .................................. 10 g Water, qs .......................................... 100 g pH = 9.5 10 g of this composition are applied to che-naturally want white at 90 ~ 0 then after 10 min of time pose, add on the hair, without prior rinsing, 5 g an oxidizing milk with 18% hydrogen peroxide, of composition S8.
The hair is kneaded well to obtain good homogeneity.
then, after 25 minutes of exposure time, the hair, without prior rinsing, 5 g of the composition tinc-toroid S31 below:
Composition S ~ 1:
3-Nitro 4-N- (~ -hydroxyethyl) amino phenol .......... 1.02 g Remcopal 334 * ........................................ 12 g Remcopal 349 ~ '....................................... 15 g Oxyethylenated oleic alcohol with 2 moles of oxide ethylene ........................................... 1.5 g 20 Oxyethylenated oleic alcohol with 4 moles of oxide ethylene ........................................... 1.5 g Propylene glycol ...................................... 6 g Sodium bisulfite 35Bé ......................... 19 2 g Trilon B ~ 0.12 g Triethanolamine, qs ............................ pH = 6.5 Water, qs .......................................... 100 g After a good homogenization and 5 minutes of leave on, rinse and wash the hair. We get a very dark purple coloring.

If in the previous example we remove the ortho-~ Trademark .

aminophenol, all the rest of the description remains unchanged we obtain a bronze green coloration.
EXEM_LE No. 1 ~
The following dye composition is prepared:
Composition S ~ 2:
2-N- (~ -hydroxyethyl) amino phenol .................. 0.31 g 4-N, N- (ethyl, ~-mesylamino-) hydrochloride ethyl) amino aniline ................................ le98 g Hydroxyethylcellulose, .............................. 1 g 10 Butylglycol ............ ............................. 5 g Ammonium acetate .................................. 4 g Ammonium lauryl sulfate ............................ 0.1 g Ammonia at 22Bé .................................. 10 g Water, qs ......................................... 100 g pH = 9.8 At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.
This mixture applied 20 min at 20C to natural hair.
turral white at ~ 0% gives them, after rinsing ~ age and shampoo, a silver gray coloring. If in the composition tion S32 we remove the ortho compound while keeping the rest ~
of the unchanged composition as well as the mode of application, obtains a light yellow coloring.
EXAMPLE No. 20 . .
The following dye composition is prepared:

; Composition S ~:

2-N- (~ -hydroxyethyl ~ amino phenol ................... 0.6 g N, N ~ hydroxy dihydrochloride, monohydrate ethyl ~ ~-mesylaminoethyl) para-phenylenediamine ... 4 g ~ 19% alcohol sodium auryl sulfate oxyethylenated starting., ............................... 20 g Trilon B * ............................................ 0.1 g Triethanolamine ......., ......., ....................... 10 g Thioglycolic acid ................................. 0.5 g Water, some .......................................... 100g pH = 8.1 At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.
This mixture applied 20 minutes at 25C on che-want discolored gives them after rinsing, age and shampoo a very dark gray coloring.
If in this example we remove the ortho compound while keeping the rest of the composition unchanged as well as the mode of application, o o holds a petroleum green coloring asse7. dark.
EXAMPLE E No. 21 .....
The following dye composition is prepared:
Composition S34:
20 N, N '- (~ -hydroxyethyl) N, N' - tetrachloride amino phenyl) tetramethylene diamine ................. 2 g Orthoaminophenol ,,, ........., ..., .......................... 0.2 g - Oxyethylenated oleic alcohol with 2 moles of oxide ethylene ....................................... ........ , 4.5 g - Oxyethylenated oleic alcohol with 4 moles of oxide ethylene, ................., ........, ................... .. 4.5 g Diethanolamide of coconut fatty acids .................. 10 g Sodium bisulfite at 35Bé .............................. 1 g Masquol DTPA * ............................................ 2 g 30 Propylene glycol ........................................ 4.5 g ,:,. . ~. _.

Butyl glycol ............ 8 g Ethanol 96 ........... 8 g Ammonia at 22Bé ..... 10 g Water, qs ............ 100 g pH = ~, 8 At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.
This mixture is applied to hair naturally white at 90 ~ 0. After 20 minutes of exposure time, rinsing and shampoo we get a gray blue color.
If in the previous example we delete the ortho aminophenol, the rest of the description remains unchanged on obtains a pale silvery green coloring.
EXAMPLE E No. 22 The following dye composition is prepared:
Composition S ~:
~. ~
2,6-dimethyl 3-methoxy dihydrochloride paraphenylenediamine ..................................... 2.39 g Orthodiphenol ............................................ 0.83 g Alfol C 16/18 E * ~ 7.2 g Lanette wax E ..... ~ ................................ 0.45 g Cemulsol B * ............................................. .O , gg Oleic diethanolamide ................................... 1.35 g Masquol DTPA * ......... ............................... 2.25 g Ammonia at 22 Be ..................................... 10 g Water, ~ .sp ............................................. 100g At the time of use, 100 g of hydrogen peroxide are added 20 volumes.
This mixture is applied 20 minutes to hair discolored whites. After rinsing and shampooing, a gray coloring shaded with green.
* Trade mark - ~

~ 4 '~

If in the previous example we remove the ortho-diphenol, the rest of the description remains unchanged, we brings almost no color to discolored hair starting res.
EXAMPLE # 23 The following dye composition is prepared: -Composition S ~ 6;
4-N, N dihydrochloride (ethyl, ~-mesylaminoethyl) amino aniline ....................................... 3.31 g 10 Orthodiphenol ......................................... 1.10 g Oxyethylenated oleic alcohol with 2 moles of oxide ethylene .......................................... 4.5 g Oxyethylenated oleic alcohol with 4 moles of oxide ethylene .......................................... 4, ~ g Diethanolamides of coconut fatty acids ................ 10 g Sodium bisulfite solution 35 Be ................ 1 g Masquol DTPA * ........................................... 2 g Propylene glycol ...................................... 4.5 g Butylglycol ......................................... 8 g 20 Ethanol 96 ......................................... 8 g Ammonia at 22 Be ................................. 10 g Water, qs ......................................... 100 pH = 10 At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.
This mixture is applied to white hair colored; after 20 minutes of exposure time, rinsing and shampooing pooing, we obtain a gray blue color ~ oncé.
If in the previous dye composition we remove orthodiphenol, all the rest of the description * Trademark -55 ~

7 ~

remaining unchanged, a light bronze green coloration is obtained EXEr ~ LE No. 24 The following dye composition is prepared:
Composit on S37:
4-N, N- hydrochloride (ethyl, ~ ~ mesylaminoethyl) amino aniline ........................................ 3.30 g Orthodiphenol ........................................ 1.10 g Alfol C 16/18 E * ..................................... 8 g Lanette wax E .................................... 0.5 g 10 Cemulsol B * ................... ..... . .................. 1 g Oleic diethanolamide ........... ......... ............ 1.5 g Masquol DTPA * .................... ......... ............ 2, ~ g Ammonia at 22Bé ............... ......... ............ 11 g Mercapto-2 ethanol .......... O ......................... 1.7 g Water, qs ......................................... .. 100 g pH = 9.6 50 g of this composition are applied to che-want 90% whites. After 10 minutes of exposure time, add on the hair, without prior rinsing, 50 g of milk oxidant ~ 6% hydrogen peroxide of composition S17 described in Example 12.
We mix the hair well to get a good homogenization. After 10 minutes of exposure time we add ~ 5 of the following dye composition S38:
Composition S ~ 8:
6-amino benzomorpholine dihydrochloride ............. 0.05 g Oxyethylenated oleic alcohol with 2 moles of oxide ethylene ............................................ 4.5 g Oxyethylenated oleic alcohol ~ 4 moles of oxide 30 ethylene .............................................. 4.5g * Trademark Ethomeen 12 * ~ ......................... ,,., ............. 4.5 g Diethanolamides of coconut fatty acids .............. ...... 9 g Propylene glycol ..................................... ..... 3.6 g Butylglycol, ......................................... ...... 8 g Ethanol 96 ........................................ ..... 5, 4 g Sodium bisulphite at 35 Be ......................... ...... 1 g Ammonia at 22Bé ................................... ...... 10 g Water, some .......................................... ..... 100g We knead the hair well. After 10 min of time of laying, rinsing and shampoo we get a blue coloring black.
If in the previous example we delete the ortho-;
diphenol in the dye composition S37 -all the rest of the description remains unchanged we get a coloring green bottle.
EXEMP1E No. 2 The following dye composition is prepared:
Composition S ~ 9 4-N, N- (ethyl, ~ -piperidino-) hydrochloride 20 ethyl) amino aniline ................................... 2.5 g Orthodiphenol ....................................... 0.2 - g Oxyethylenated oleic alcohol with 2 moles of oxide ethylene ........................................... 2, ~ g Oxyethylenated oleic alcohol with 4 moles of oxide ethylene ........................................... 2.5 g Remcopal 334 * ......................................... 3 g Remcopal 349 * ......................................... 4 g Propylene glycol ....................................... 10 g Car ~ opol 934 * .. ~ .............................., ........... 0.2g 30 Sodium bisulfite ~ 35 Be ............................ 1 g * Trademark - ~ 7-Trilon B ~ ... .......................................... 0, 1 g Water, qs. .......................................... 100 g pH = 9.7 At the time of use at 10 g of this composition dye, add 5 g of oxidizing milk to 18% of oxy-gene of composition S8 described in Example 6. This mixture is applied to bleached white hair.
After 15 minutes of exposure time, apply on hair, without rinsing ~ prior cage 5 g of the dye composition 10 riale S40 of the following composition:
Composition S40:
2-Methyl 5-N- ~ -hydroxyethyl) amino phenol ............ 0.3 g 2-N- (~ -hydroxyethyl) amino 5-nitro anisole ............ 0.12 g Oxyethylenated oleic alcohol with 2 moles of oxide ethylene ............................................. 2, 5 g Oxyethylenated oleic alcohol with ~ moles of oxide ethylene ...................................., ........ 2, 5 g Remcopal 334 ~ ....................................... .... 3 g Remcopal 349 * ........................................ .... 4 g 20 Propylene glycol ....................................... ... 10 g Carbopol 934 * ........................................ .. 0.2 g Sodium bisulphite at 35 Be ......................... .... 1 g Trilon B * ............................................ .. 0 , 1 g Water, qs .......................................... .. 100 g pH = 9, ~
We knead the hair well. After 10 minutes of time pose, rinse and shampoo we get a gray color tin.
If in this example we supp ~ ime the orthodiphenol of the dye composition S39 all the rest of the description * Trademark remaining unchanged, a pinkish beige coloration is obtained.
EXAMPLE E No. 26 The following dye composition is prepared:
Composition 541:
4-N, N- (ethyl, ~ -carbamylmethyl) amino aniline ....... 2.12 g Orthodiphenol ....................................... 0.54 g Oxyethylenated oleic alcohol with 2 moles of oxide ethylene .......................................... 2.5 g Oxyethylenated oleic alcohol with 4 moles of oxide 10 ethylene ............................................ 2, 5 g Remcopal 334 * ....................................... 3 g Remcopal 3 ~ 9 * ....................................... 4 g Propylene glycol .................................... 10 g Carbopol 934 * ....................................... 0.2 g Mercapto-2 ethanol .................................. 2 g Bisul ~ ite solution at 35Bé ....................... 1 g Trilon ~ .......................................... 0 ~ 1 g Ammonia at 22Bé .................................. 7 g Water, qs ......................................... 100 g 20 pH = 9.7 20 g of this composition are applied to hair naturally straw blonde. After 5 minutes of exposure time add to the hair, without rinsing beforehand 5 g of a milk oxidant with 18% hydrogen peroxide of composition S8 described in Example 6.
After having kneaded the hair well to obtain a good homogenization we wait 20 minutes then rinse and washing hair. There is a black brown coloration. Yes in the previous composition we remove the orthodiphenol `-all the rest of the description remains unchanged we get a light chestnut color.
* Trademark -EX ~ MP_E_No. 27 The following dye composition is prepared:
Composition S
N, N 'tetrachlorhydrate ~ hydroxyethyl) N, N'-(4-amino phenyl) tetramethylene diamine .................... 3.8 g Orthodiphenol .......... ....... ... ... .......... 0.28 g Oxyethylenated oleic alcohol with 2 moles of oxide ethylene ...................... .... .... ............ .. 4.5 g Oxyethylenated oleic alcohol with 4 moles of oxide 10 ethylene ........................ .... .... ............ .. 4.5g Coconut fatty acid diethanolamides ..................... 10 g Thioglycolic acid ....................................... 0.2 g Sodium bisulfite 3 ~ Be .................................. 1 g Masquol DTPA ~ ............................................... 2 g Propylene glycol ........................................... ~, 5 g Butylglycol ................................................. 8 g Ethanol 96 ............................................... 8 g Ammonia at 22Bé .......................................... 10 g Water, some ............................................... 100 g pH = 10.2 10 g of this composition are applied to che-naturally want light brown.
After 8 minutes of exposure time, add to the che want, without prior rinsing, 10 g of oxidizing milk with 9 ~ 0 of water oxygenated, of composition S27 described in Example 16.
We mix the hair well to get a good homogenization, After 10 minutes of exposure time, rin ~ age and shampoo we obtain a brown-black coloring nuanced with purple.
If in this example we remove the orthodiphenol from * Trademark :.

42 ~ 7 ~

the dye composition, while keeping the rest unchanged from the description, a dark green coloration is obtained.
EXEMP ~ E_No. 28 The following dye composition is prepared:
Composition S4 ~:
N, N 'tetrachlorhydrate (~ -hydroxyethyl) N, N' - (4-amino phenol) 2-ol propylene diamine ................ 4.1 ~ g Orthodiphenol ....,., .... ,,. ,, .. O, ..................... 0.33 g 2-Nitro 4-N ', N' - (~ -hydroxyethyl) amino 10 N (~ -hydroxyethyl) aniline ............................ 0.50 g Oxyethylenated oleic alcohol with 2 moles of oxide ethylene ,,,., .., .., ........... ,, ......., ............... .4.5 g Oxyethylenated oleic alcohol with 4 moles of oxide ethylene ...,. ,,,. ,,,,,,,,, ....., .., ~ ,, .. ,,, ............. .4.5 g Coconut fatty acid diethanolamide ................... 10 g 35Be sodium bisulfite solution, ~ ................. 1 g Masquol DTPA * ..................., ...., ................ 2 g Propylene glycol ............. ............ ............ .4.5 g Butylglycol.,. ,,, ......,., ~ ...,. ,,, ... ~, ....., .. ,, O 8 g 20 Ethanol 96 ..................., ......, ......... ..... 8 g Ammonia at 22 Be ..., ......., .., ............. .... 10 g Water, qs ... O ........................., ........... .... 100 g pH = 9.6 At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.
This mixture applied 20 minutes to natural hair.
turALLY golden blond their con ~ era after rin ~ age and sham-pooing a dark ash brown coloring with purple reflections If in the above example we remove the ortho-diphenol, ~ out the rest of the description remains unchanged * Trademark a green-yellow coloration is obtained.
EXAMPLE No. 2 ~
The following dye composition is prepared:
Composition S44:
N, N 'tetrachlorhydrate - (~ -hydroxyethyl) N, N'-(4-amino phenyl) tetramethylenediamine ....., ................ 2.07 g Orthodiphenol. ,,,,,,,,,. ,,., ... O,. ,,. ,,. ,,,,.,., .. 0.33 g Oxyethylenated oleic alcohol with 2 moles of oxide ethylene. ,, ..., .., .... ,,, ..., .O ........................ .... 4.5 g Oxyethylenated oleic alcohol ~ 4 moles of oxide ethylene ......... ,,, .., ..., ............................ .... 4.5 g 12 '''' ~ ---...................................... 4, ~ g Diethanolamides of coconut fatty acids ......................, 9 g Propylene glycol ............................................. 3.6 g Butyl glycol ................................................ ., 8 g Ethanol 96 ............................................... 5.4 g Sodium bisulfite at 35Bé .............., ..................... 1 g Ammonia at 22Bé., ...., ....... ~ ........................ 10 g Water, qs ......................................... .... 100 g 20 pH = 10 At the time of use, 100 g of hydrogen peroxide are added 20 volumes.
This mixture is applied to bleached hair to white. After 20 minutes of exposure time, rinsing or shampooing a silvery blue gray coloration is obtained.
If in the above example we remove the ortho-diphenol, all the rest of the description remains unchanged a light bronze green coloration is obtained.
E ~ EMPLE No. ~ 0 ~ 0 The following dye composition is prepared:
* Trademark -62_ Composition S4 ~:
4-N, N-bis ~ -hydroxyethyl sulfate) paraphenylenediamine.,. ,,., ..,., ..,.,. ,,. ,,., .......... ~, 03 g Orthodiphenol,. ,, .. ,,.,.,.,. ,,,,,,, .. ,,,,,. ,,,, ... 0.33 g Oxyethylenated oleic alcohol with 2 moles of oxide ethylene ,,,,,, ......,. ,,,, ..,. ,,,,,, ..., ...., ........ 4, 5 g Oxyethylenated oleic alcohol with 4 moles of oxide ethylene ~ ,,,. ,,,,, .. ,,, O. ,,,,., ....... ,,., .., ........ 4, ~ g in 12.-.................................,.,.,. ,, 4 5 g 10 Diethanolamides of coconut fatty acids ...................... 9 g Propylene glycol ......................................... 3, ~ g Butylglycol ,,,,,,,,,,,,,,,,,,,,,,,,.,. ,,,,,,, 8 g Ethanol ~ 96. ,, ...... .., ..........., ....................... .. 5.4 g Sodium bisulfite ~ 35Bé ,,,,, .. ,, ..,.,.,.,., .., 1 g Ammonia at 22 Be ,,,,,,, .. ,,,,,,,,,,,,,,, ,,,,,. ,, 10 g Water, some ......................................... ...... .... 100 g pH = 10 At the time of use, 100 g of hydrogen peroxide are added to 20 volumes.
This mixture applied 20 minutes at room temperature on bleached white hair their co ~ era, after rin ~ age and shampoo, coloring: dark blue gray.
If in this example we remove the orthodiphenol, all the rest of the description remaining identical we get a light bronze green coloring.
EXAMPLE No, 31 The following dye composition is prepared:
Composition S46 N, N- (~ -hydroxyethyl dihydrochloride monohydrate, 30 ~-mesylaminoethyl) para-phenylenediamine ..... ~ ....... 1.73 g * Co D erce brand 2 ~ 7g ~

Orthodiphenol ............ . ............................. .0.275 g Oxyethylenated oleic alcohol ~ 2 moles of oxide ethylene .............. ~ ................................ .4.5 g Oxyethylenated oleic alcohol with 4 moles of oxide ethylene ........................................... .... .4.5 g Diethanolamides of coconut fatty acids .................. 10 g Sodium bisulfite 35 Be ......, ....................... 1 g Masquol DTPA * .......... ~ ............................ .2 g Propylene glycol .................................... .4.5 g 10 Butyl glycol ........................................... ~ G
Ethanol 96 ........................................ 8 g Ammonia ~ 22 Be ...., ............................. 10 g Water, qs ............ '............................. 100 g pH = 10.2 At the time of use, 60 g of hydrogen peroxide are added to 20 volumes.
This mixture applied to bleached hair very golden straw blonde for 25 minutes gives them, after rinse and shampoo a smoky gray color. If in the same example we remove the orthodiphenol all the rest of the description remains unchanged a soft coloring is obtained delay.
EXAMPLE E No. 32 The following dye composition is prepared:
Composition S47:
4-amino dihydrochloride N, N- (ethyl, mesylamino-ethyl) aniline. ....... .... .... 3.3 g Orthoaminophenol ............ ...... ................... 0.33 g 2-hydroxyethylamino 5-methyl 4,4'-dihydroxy-30 diphenylamine ................. ...... ................... 0.66 g Trademark ~

... . . . . . . ..
,,:,. , ... ~. . ~ ..

Remcopal 334 * ........................................ 21 g Remcopal 349 * ........................................ 24 g Oleic acid ......................................... 4 g Butylglycol ........................................... 3 g Absolute ethyl alcohol .............................. 14 g Masquol DTPA * ....................................... 2.5 g Sodium sulphite ................................... 1 g ; Glycerol thioglycolate ........................... 1.5 g Baking soda ................................ 0.4 g 10 Soda .............., ..........., ................. ... 0 , 1 g Ammonia at 22 Be ................................. 10 cm3 Water, qs ......................................... 100 g Mercaptan is introduced at the time of use.
40 g of composition S47 are applied to a che hair dyed blond 2 months ago by colora ~ ion dioxy-donation.
10 minutes after adding 40 g of the composition S2 which is left in contact with the hair during for an additional 20 minutes.
After rinsing, shampooing and drying, the hair are uniformly colored in light pearly dark chestnut while the same composition applied conventionally-for 30 minutes, color this hair in blonde the roots and brown on the sensitized parts.
EXAMPLE No. ~
The following dye composition is prepared: -Composition S ~ 8:
4 ~ amino dihydrochloride N, N- (ethyl, mesylamino-ethyl) aniline ..................................... 3.3 g 30 Orthoaminophenol ..................................... 0, ~ 3 g * Trademark ~ 65-z ~

2-hydroxyethylamino 5-methyl 4,4'-dihydro ~ y diphenylamine ....................................... 0.66 g Remcopal 334 * ....................................... 21 g Remcopal 349 * ....................................... 24 g Oleic acid ....................................... 4 g Butylglycol ......................................... 3 g Absolute ethyl alcohol ............................. 14 g Masquol DTPA * ....................................... 2, ~ g Sodium sulfite ................................... 1 g 10 Glycerol thioglycolate ...... -.............. O ........ 1.5 g Bicar ~ soda onate ................................ 0, ~ g Soda ............................................... 0, 1 g Ammonia ~ 22Bé .................................. 10 cm3 Water, qs ......................................... 100 g Mercaptan can be introduced at the time of use.
40 g of composition S48 are applied to a che velvet dyed blond 2 months ago by oxy coloration donation.
10 minutes after adding s ~ ns rinse 40 g of composition S2 which is left in contact with the hair during for an additional 20 minutes.
After rinsing, shampooing and drying, the hair are uniformly colored in light pearly dark chestnut while the same composition applied conventionally-nelle for 30 minutes, color this hair blonde on the roots and in ~ run ~ ur the sensitized parts.

The following dye composition is prepared:
Composition S49:
Sulfate 4-N- (~ -mésylaminoéth ~ l ~ am; no aniline .... 1.98 g * Trademark / --21 ~

Orthoaminophenol .. .. ... ... ,, ..., .................... 0.25 g Oxyethylenated oleic alcohol with 2 moles of oxide ethylene ........... .... ... ..... ................. .... 4.5 g Oxyethylenated oleic alcohol with 4 moles of oxide ethylene ........... .... ... ..... ................. .... 4.5 g Ethameen 12 * '' ~ - - .............................. 4.5 g Diethanolamides of coconut fatty acids ................ 9 g Propylene glycol ....................................... 3.6 g Butylglycol ......., ....., ............................. 8 g 10 Ethanol 96 ............... .............................. 5, 4 g Sodium bisulfite 35Bé ............................ 1 g Ammonia at 22 Be ..................................... 10 g Water, qs ............................................ 100 g pH = 10 At the time of use, 80 g of hydrogen peroxide are added 20 volumes. This mixture applied 20 minutes at room temperature you on naturally white hair ~ 90 ~ o gives them after rinsing and shampooing an ash gray color.
If in this example we remove orthoaminophenol, all the rest of the description remaining identical we get a beige coloring.
EXE ~ PLE ~ 5 The following dye composition is prepared:
Composition S50:; ~
4-N- (~ -hydroxyethyl) amino 3-chloro sulfate aniline ................................................ 2 84 g Orthoaminophenol ....................................... 0.83 g Oxyethylenated oleic alcohol ~ 2 mole ~ of oxide ethylene ............................................. 2, 5 g 30 Oxyethylenated oleic alcohol ~ 4 moles of oxide * Trademark . ~. .

2 ~

ethylene ........................................... 2.5 g Remcopal 334 * .......................................... 3 g Remcopal 349 * .......................................... 4 g Propylene glycol ...................................... 10 g Carbopol ............................................. 0.2 g Sodium bisulfite 35Bé ............................ 1 g Trilon B * ......................................... ~. 0.1g ~ mmonic ~ 22Bé ..................................... 7 g Water, qs .......................................... 100 g pH = 10.0 At the time of use, 100 g of H 2 O 2 are added to 20 volumes.
This mixture applied 25 minutes on natural hair-slightly white at 90% gives them after rinsing and shampooing a light ash gray color.
If in this example we remove orthoaminophenol all the rest of the description remains unchanged we do not bring practically no color to the starting hair.
EXAMPLE ~
The following dye composition is prepared:
CompositiGn S ~ l:
Sul ~ ate 4-N monohydrate, N- (ethyl, ~ -mesyl-amino ethyl) amine 2-methyl aniline .................. 4.36 g Orthodiphenol ........................................ 1.10 g Oxyethylenated oleic alcohol ~ 2 moles of oxide ethylene ............... ~ ............................... 4.5g Oxyethylenated oleic alcohol with 4 moles of oxide ethylene ............... O ............................... 4.5g Diethanol coconut fatty acid amides ............ 10 g 30 Bisul ~ ite de sod; um ~ 35Bé ............................ 1 g Trademark Z17 ~
,., Masquol DTPA *. ....... . . ...... ................... 2 g Propylene glycol ................. ..................... 4.5 g Butylglycol ............ 8 g Ethanol 96 .......... 8 g Ammonia ~ 22Bé .... 10 g Water, qs ........... 100 g pH = 10.2 At the time of use, 100 g of H20 are added 20 volumes.
This mixture applied to bleached hair during for 20 min ~ room temperature gives them after rinsing and a tin coloring shampoo.
If in this same example we delete the orthoamino-phenol all the rest of the description remains unchanged on obtains a very light pinkish beige coloring.
XAMPLE ~ 7 The following dye composition is prepared:
Composition S ~ 2:
4-N, N- hydrochloride (ethyl, ~-mesylaminoethyl) 20 amino aniline ........ .... ... .... ........ .. 3.3 g Orthoaminop ~ enol .......... .... ............... ..... .... 0.3 g Oxyethyl oleic alcohol ~ born with 2 moles of oxide ethyl ~ ene ............... .... ............... ..... .... 2, 5 g Oxyethylenated oleic alcohol ~ 4 moles of oxide ethylene ................ .... ............... ..... .... 2.5 g Remcopal 334 * ............. .... ............... ..... ...... 3 g Remcopal 349 * ............. .... ............... ..... ...... 4 g Propylene glycol .......... .... ............... ..... ..... 10 g Carbopol 934 * ............. .... ............... ..... .... 0.2 g 30 Bisul ~ ite of sodium at 35Bé ............................. 0.1 g * Trademark Trilon ~ * ............................................... 7 g Ammonia a 22Bé ....................................... 7 g Water, qs ............................................. 100 g pH - 9.7 At the time of use at 10 g of this composition dye is added 10 g of H202 ~ 20 volumes.
This mixture is applied to deco white hair browned for 15 min. After this exposure time, apply without rinse 5 g of the following dye composition S53.
10 Composition S5 ~:
2,6-diamino pyridine ................................... O, 24 g - ~
Resorcin .............................................. 0.45 g Metaamine phenol ....................................... 0.75 g Remcopal 334 * ..................................... 12 g Remcopal 349 * ~ 15 g Oxyethylenated oleic alcohol ~ 2 moles of oxide ethylene ........................................ .1.5 g Oxyethylenated oleic alcohol with 4 moles of oxide ethylene ........................................ .1 ~ 5 g zO Propylene glycol .................................... .6 g Sodium bisulfite 35Bé ........................ 1i2 g Trilon B * ......................................... 0.12 g Triethanol amine, qs .......................... pH = 6.8 Water, qs ....................................... 100 g We knead the hair well. After 10 min of time of laying, rin ~ age and shampoo we obtain a gray coloring dark blue metallic.
If in this example we remove the orthoamino phenol all the rest of the description remains unchanged, we get a blue-green coloration.
* Trademark 7 ~

10 g of composition S52 are applied to hair naturally white at 90% for 15 minutes. We add then without rinsing ~ prior age 10 g of H202 at 20 volumes in mala-xant well and leave the contact 10 minutes.
5 g of the dye composition are then applied next:
Composition S 4:
.. .. ~
Dimethyl 2 6-acetamino-5 phenol ....................... 0.48 g 10 Resorcin ...................................... ~ ....... 0, 4 ~ g Metaaminophenol ....................................... 0.75 g Remcopal 334 * ......................................... 12 g Remcopal 349 * ......................................... 1 ~ g Oxyethylenated oleic alcohol with ~ moles of oxide ethylene .......................................... 1.5 g Oxyethylenated oleic alcohol with 4 moles of oxide ethylene ........................................... 1.5 g Propylene glycol ..................................... 6 g Sodium bisulfite 35Bé .......................... 1.2 g 2020 Trilon B * ............................................ 0, 12 g Methanolamine, qs ................................ pH = ~, 8 Water, qs .......................................... 100 g After a good homogenization and 10 min of time of installation we rinse and wash the hair.
We get a steel gray coloring, if we remove in cat example orthoaminophenol, all the rest of the remaining unchanged, a light gray coloration is obtained.
EXAMPLE 3 ~
The following dye composition is prepared:
Composition S5 ~:
~ Trademark 4-N, N- (ethyl, ~-mesylamino-) hydrochloride ethyl) amino aniline .., .., .., ........,., ..., .............. 3.3 g Orthodiphenol ........., ................................... 1.1 g Oxyethylenated oleic alcohol with 2 moles of oxide ethylene ............, .................................. 4.5 g Oxyethylenated oleic alcohol with 4 moles of oxide ethylene ................................... ............ 4.5 g in 12 '' ~ -. .............................. 4.5 g Diethanolamides of coconut fatty acids .............. 9 g 10 Propylene glycol ....................................... 3.6 g Butylglycol ..........., ................................... 8 g Ethanol ~ 96 ........................................ ..... 5, 4 g Sodium bisulfite at 35Bé .......................... 1 g Ammonia at 22Bé ...., ................................... 10 g Water, some .......................................... ..... 100g pH = 10.0 10 g of this composition are applied to che-naturally want white ~ 90%. After 10 minutes of exposure time 10 g of H20 are added to the hair without prior rinsing to 20 volumes. 0 ~ mix the hair well. After 10 minutes of exposure time add 10 g of the dye composition next:
Composition S ~ 6:
(29 4-diamino) phenoxyethanol dihydrochloride ...... 0.08 g - Remcopal 334 * ...................................... 12 g Re ~ copal 349 * ................., ...... ~ .............. 15 g Oxyethylenated oleic alcohol ~ 2 moles of oxide ethylene ...................., ..................... .1.5 Oxyethylenated oleic alcohol with 4 moles of oxide 30 ethylene, ........................................... 1.5g * Trademark 2 ~

Propylene glycol ............., ........................ 6 g 35Be sodium bisulfite ..................... ...... 1.2 g Trilon B * ....................................... ...... 0, 12 g Triethanol amine, qs ........................ ...... pH = 6, 8 Water, qs ..................................... ...... 100 g We knead the hair well. After 15 minutes of exposure time, rinsing and shampooing is obtained light blue gray; if in this example we remove the ortho-diphenol all the rest of the description remains unchanged on gets a blue color.

10 g of composition S5 ~ are applied to bleached hair. After 10 minutes of exposure time, add on the hair, without rinsing ~ prior age 10 g of H202 ~ 20 vo-lumes. We mix the hair well to get a good homogenization.
After 10 minutes of exposure time, 10 g of the following dye composition:
Composition ~:
20 c ~ - naphthol ..................., ........................ 0.035 g Oxyethylenated oleic alcohol with 2 moles of oxide ethylene ............................................ 4.5g Oxyethylenated oleic alcohol ~ 4 moles of oxide ethylene ..............................., ............ 4.5 g een 12 ~ -...................................... 4.5g Diethanolamides of coconut fatty acids ............... 9 g Propylene glycol..................................... . 3.6g Butyl glycol .......................................... 8 g Ethanol 96 ........................................... ~, 4 g 30 Na 35Bisulfi ~ e ....................., ............ 1 g Ammonia 22Bé ........................., ............ 10 g * Trademark 3L7 ~

Water, q sp. .......................................... 100 g We knead the hair well. After 10 min of time application, rinsing, shampoo, we get a gray color anthracite.
If in this example we remove the orthodiphenol -all the rest of the description remaining unchanged we get a light bronze green coloring.

The following dye composition is prepared:
Composition S $ 8:
4-N, N- (ethyl, ~-mesylaminoethyl) dihydrochloride amino aniline .............................................. 3, 3 g Orthoaminophenol .............................................. 0.3 g 4,4'-diamino diphenyl amine sulfate ................... 0.3 g Oxyethylenated oleic alcohol with 2 moles of oxide ethylene ............................................... 4.5g Oxyethylenated oleic alcohol ~ ~ moles of oxide ethylene ............................................... 4.5g Diethanol amides of coconut fatty acids .................. 10 g 20 Sodium bisulphite ~ 3 ~ B ................................... 1 g Masquol DTPA ~ ............................................. 2 g Propylene glycol ......................................... 4, ~ g Butylglycol ........ ~ ..................... ~ .................. .... 8 g Ammonia at 22Bé. ...................................... 10 g Water, qs ....... ............ ~ ........................... .. 100 g 10 g of this mixture are applied to hair whites discolored for 10 min. 10 g of water are then added oxygenated ~ 20 volumes. We mix the hair well and we takes 20 min ~ room temperature. After rinsing and sham-pooing we get a very dark gray coloring ~ reflections * ~ commercial arch -purple.
If in this example we delete the orthoamino phenol all the rest of the description remains unchanged on obtains a medium ash brown color.

The following dye composition is prepared:
Composition S ~ g:
4-N, N ~ dihydrochloride (ethyl, ~-mesylaminoethyl) aniline amine ........................................ 3.3 g 10 Orthoaminophenol ....................................... 0.33 g 2-amino 5-methyl-4-hydro ~ y 4'-N-methylamino diphenylamine ....., ........ .......... ............ 0.66 g Oxyethylenated oleic alcohol with 2 moles of oxide ethylene ................. ........... ............... .... 2.5 g Oxyethylenated oleic alcohol with 4 moles of oxide eth ~ vlene ...................................... ~ 2,5 g Remcopal 334 ~ ........................................ 3 g Remcopal 349 * ........................................ 4 g Propylene glycol .................................... 10 g Carbopol 934 * ...................................... 0.2 g Sodium bisulfite at 25Bé ....................... 1 g Trilon 3 * ............................................ 0.1 g Ammonia ~ 22Bé ............. ................... 7 g Water, qs .......................................... 100 g pH = 9. ~
10 g of this composition are applied to che-naturally want white ~ 90%. 10 minutes later we add you without preliminary rinsing 10 g of H202 ~ 20 volumes which are left in contact with the hair 20 min extra.
After rinsing and shampooing this mixture gives them * Trademark a smoke gray coloring with purple reflections.
If in this example we remove the orthoamino phenol, all the rest of the description remains unchanged we get a light ash beige color.

The following dye composition is prepared:
Composition S60:
4 ~ N, N- monohydrochloride (ethyl, ~ -carbamylethyl) amino aniline .........................., ............ 1.9 ~ g N (~ -methoxy-thyl) amino-2- monohydrochloride aniline ........................................... 0.57 g Oxyethylenated oleic alcohol with 2 moles of oxide ethylene ........................................., 2.5 g Oxyethylenated oleic alcohol with 4 moles of oxide ethylene ....................................... .... 2.5 g Remcopal 334 * ............................ 3 g Remcopal 349 * ............................ 4 g Propylene glycol ........................ 10 g Carbopol 934 * ........................... 0.2 g 20 Sodium bisulfite 3 ~ Be ................ 1 g Trilon B * ............................................ 0.1 g Ammonia a 22Bé ..................................... 7 g Water, qs .......................................... 100 g pH = 9.7 10 g of this composition are applied to che-naturally want white at 90 ~ 0, 10 min later we add by kneading the hair well 6 g of H ~ 02 ~ 20 volumes and leaves 20 additional minutes.
After rinsing and shampooing, a color is obtained.
silver mouse gray.
* Trademark ~ Z ~ 7S ~

If in this example we remove the hydrochloride from N ~ methoxyethyl) amino-2 aniline, all the rest of the cription remaining unchanged we get a bronze coloring clear.
EX ~ MP ~ E 44 The following dye composition is prepared:
Composition S61:
.
4-N, N- (ethyl, ~ hydroxyethyl) amino sulfate aniline ..............., ....,.,. ,, ......, ............ 2.7 ~ g 10 Ortho diphenol .......... ~ ................ ............. 0.50 g Oleic alcohol oxya- ~ hylenated to 2 moles of oxide ethylene ....................................., ......... 4.5g Oxyethylenated oleic alcohol ~ 4 moles of oxide ethylene ............, ...................... 4.5 g e 12 '-------................................ 4 5 g Diethanolamides of coconut fatty acids .............. 9 g Propylene glycol ..................................... 3.6 Butylglycol .......................................... 8 g Ethanol 96 ........................................ 5.4 g 20 Bisul ~ sodium ite ~ 35Bé ............................ 1 g Ammonia a 22Bé, ... ........., ............. 10 g Water, qs ........... ....., ................. 100 g pH = 10.0 At the time of use, add 100 g of oxy water gene ~ 20 volumes. This mixture applied 20 minutes at tempera ~ ure ambient on naturally white hair ~ 90 ~ o their ~ era after rinsing and shampooing a steel gray coloring.
If in this example we delete O-aminophenol, all the rest of the description remaining unchanged we get a light beige gray coloring.
Trade mark ~ ~ Z ~ 7 ~

The following dye composition is prepared:
Composition S62:
. .
4-N sulfate, N - tethyl, ~ -hydroxyethyl) amino aniline................................................. ...... 2.78 g Orthoaminophenol .......... ~ ..... ~ ....................... 0.654 g Oxyethylenated oleic alcohol with 2 moles of oxide ethylene .......................................... ..... 4.5 g Oxyethylenated oleic alcohol with 4 moles of oxide 10 ethylene .................. ~ ........................... ... 4.5 g 12 '''~. ......................................,. 4.5g Diethanol coconut fatty acid amides ......................... 9 g Propylene glycol ............................................... 3 , 6 g Butyl glycol ................................................ ..... 8 g Ethanol ~ 96 ............................................... ... 5.4 g Sodium bisulfite at 35Bé ...................................... 1 g Ammonia at 22 ~ Be ............................................. 10 g Water, some ............... ~ ............................... 100g pH = 10.0 At the time of use, 100 g of hydrogen peroxide are added to 20 volumes. This mixture applied 20 min ~ temperature am-biante on naturally white hair at 90% their fère after rinsing and shampooing a silver gray coloring.
If in this example we delete O-aminophenol, all the rest of the description remains unchanged we get a light beige gray coloring.
* Trademark % ~ 7 ~

The commercial products mentioned in the examples ples above have the following meanings:
* Remcopal 334: designates oxyethylenated nonylphenol 4 moles of ethylene oxide sold by the Gerland Company.
* ~ E ~ 2: denotes oxyethylenated nonylphenol to 9 moles of ethylene oxide sold by the Gerland Company.
~ Masquol DTPA: designates the pentasodium salt of the acid diethylene triamine pentacetic sold by the PROTEX Company.
* Pol.ychol ~: designates lanolin fatty alcohol oxyethylenated ~ 5 moles of ethylene oxide sold by CRODA LTD.
* Polvchol 20: designates lanolin fatty alcohol oxyethylenated to 20 moles of oxide of ethylene sold by the CRODA Company LTD.
* Alfol C 16/18 E: designates cetylstearyl alcohol ven- -of by the CONDEA Company.
Lanette wax E: designates cetylstearyl sulfate of sodium sold by HENKEL Soeiété.
Cemulsol B: designates ethoxylated castor oil sold by RHONE POULENC.
Amphoteric I: designates the compound / ~ 2H5 iH2 ~ CO - NH - CH2 - CH2 - CH2 - N
R - NH - CH - COONa C2H5 R represents the alkyl radicals coconut fatty acids.

2 ~

* Carbopol 934: designates cross-linked polyacrylic acid sold by GOODRICH CHEMICALS.
* Comperlan KD: designates coconut diethanolamide sold by the HENKEL Company.
* Blanose R 530: designates the sodium salt of carboxy-methylcellulose.
* Ethomeen 12: designates the oxyethylenated oleylamine ~ lZ
-moles of ethylene oxide sold by the ARMOON HESS CHEMICAL LTD.
10 * Trilon ~: denotes ethylene diamine tetra-ketic.

This request is a division of request number 325,001 filed on April 5, 1979 in the name of the applicant company.
* Trademark

Claims (2)

The embodiments of the invention about which an exclusive right of property or privilege is claimed, are defined as follows: 1. Compounds characterized by the fact that they respond tooth to the formula:

IV
in which:
Y means R'1 and R'2 denote alkyl, mesylaminoalkyl, piperidino alkyl and hydroxyalkyl of which the alkyl groups include bear 1 to 6 carbon atoms and their salts cosmetically acceptable. 2. Compound according to claim 1, characterized by the fact that it corresponds to formula IV in which R'1 and R'2 denote hydroxyethyl.