The present application relates to a composition for the
oxidation dyeing of keratin fibres, and in particular of human keratin
fibres such as the hair, with one or more nonionic derivative(s) of
cellulose modified with one or more particular hydrophobic group(s),
one or more fatty acid ester(s), and one or more oxidation dye(s)
The invention also relates to the use of this composition for
dyeing keratin fibres and also to the dyeing process using this
composition.
It is known practice to dye keratin fibres, and in particular
human hair, with dye compositions containing oxidation dye
precursors, generally known as oxidation bases, such as ortho- or para-
phenylenediamines, ortho- or para-aminophenols and heterocyclic
compounds. These oxidation bases are colourless or weakly coloured
compounds which, in combination with oxidizing products, can give
rise, by means of an oxidative condensation process, to coloured
compounds.
It is also known that it is possible to vary the shades obtained
with these oxidation bases by combining them with couplers or
colouring modifiers, the latter being chosen in particular from aromatic
meta-diamines, meta-aminophenols, meta-diphenols and certain
heterocyclic compounds such as indole compounds.
The variety of the molecules involved as oxidation bases and
couplers makes it possible to obtain a rich palette of colours.
The "permanent" colouring obtained by virtue of these
oxidation dyes should, moreover, meet a certain number of
requirements.
Thus, it should have no toxicological drawbacks, it should
allow shades to be obtained in the desired strength, and it should show
good fastness with respect to external agents such as light, bad
weather, washing, permanent-waving, perspiration and rubbing.
The dyes should also allow white hair to be covered and,
finally, should be as nonselective as possible, i.e. they should make it
possible to obtain the smallest possible differences in colouring along

the same keratin fibre, which is generally differently sensitized (i.e.
damaged) between its tip and its root.
Moreover, the compositions obtained should, in addition, have
good rheological properties, while at the same time conserving good
colouring properties. In particular, these compositions should not run
on the face or out of the areas intended to be dyes, when they are
applied, in particular after mixing with an oxidizing agent.
Improving the power of dyeing by combining a para-phenylene-
diamine oxidation base and at least one nonionic amphiphilic polymer
such as hydroxycellulose modified with a hydrophobic group is already
known from application WO 98/03150.
However, these compositions do not entirely meet the
abovementioned requirements and can be improved, especially in terms
of dyeing properties, in particular in terms of dyeing selectivity and
power. The aim of the present invention is to obtain stable hair dyeing
compositions, in particular in the form of creams, which are easy to
prepare and to apply, which may contain high concentrations of dyes in
the form of salts, which have good rheological qualities and which
produce strong, relatively nonselective colourations that withstand the
various attacks that keratin fibres may be subjected to.
This aim is achieved by the present invention, a subject of
which is a dye composition for keratin fibres, and in particular for
human keratin fibres such as the hair, comprising, in a medium suitable
for dyeing:
(A) one or more nonionic derivative(s) of cellulose comprising one or
more hydrophobic substituent(s) containing from 8 to 30 carbon atoms;
(B) one or more C8-C30 fatty acid ester(s); and
(C) one or more oxidation dye(s).
The dye compositions according to the invention have in
particular the following properties:
• they make it possible to obtain compositions with a
viscosity corresponding to a cream, which are stable over
time,
• they stand out by virtue of the fact that they could be
easily mixed with the oxidizing composition,
• they stand out by virtue of the rheological qualities of the

creams obtained (good viscosity of cream as a mixture),
• they are easy to apply after mixing with the oxidizing
composition at the time the dyeing is carried out
(qualities of use on the head).
In addition, the compositions according to the invention make it
possible to obtain compositions capable of producing colourings with
varied, chromatic, powerful, aesthetic and relatively nonselective
shades which are uniform over all the keratin fibres, and in particular
human keratin fibres such as the hair, and which are highly resistant to
the various attacks to which the fibres may be subjected.
Another subject of the present invention comprises a process
for dyeing keratin fibres, in which the cosmetic composition according
to the invention is used.
A third subject of the invention relates to the use of this
cosmetic composition for dyeing keratin fibres, and in particular
human keratin fibres such as the hair.
Other features, aspects, subjects and advantages of the present
invention will emerge more clearly on reading the description and the
examples which follow.
Unless otherwise indicated, the limits of the ranges of values
which are given in the context of the present invention are included in
these ranges.
The term "derivative(s) of cellulose" is intended to mean one
(or more) compound(s) comprising at least one cellobiose unit having
the following structure:

in which one or more hydroxyl group(s) may be substituted.
The nonionic derivative(s) of cellulose with hydrophobic
substituent(s) (A) in accordance with the present invention are
amphiphilic polymers that are associative in nature. In fact, they
comprise hydrophilic units and hydrophobic units and are capable of
interacting and of associating with one another or with other

molecules, reversibly, in particular, by virtue of the presence of their
hydrophobic chains.
Preferably, the cellulose derivative of the invention is a
cellulose ether comprising one or more hydrophobic substituent(s)
containing from 8 to 30 carbon atoms.
The nonionic derivative(s) of cellulose with hydrophobic
substituent(s) in accordance with the present invention are generally
prepared from water-soluble nonionic ethers of cellulose, in which all
or some of the reactive hydroxyl functions are substituted with one or
more hydrophobic chain(s) containing from 8 to 30 carbon atoms,
preferably from 10 to 22 carbon atoms, and even better still 16 carbon
atoms. The reaction steps involved in the preparation of the cellulose
derivatives of the invention are known to those skilled in the art
The nonionic ethers of cellulose chosen for preparing the
nonionic derivatives of cellulose with hydrophobic substituent(s)
according to the invention preferably have a degree of nonionic
substitution, for example of methyl, hydroxyethyl or hydroxypropyl
group(s), that is sufficient to be water-soluble, i.e. to form a
substantially clear solution when they are dissolved in water at 25°C at
the concentration of 1% by weight.
The nonionic ethers of cellulose chosen for preparing the
nonionic derivatives of cellulose with hydrophobic substituent(s)
according to the invention preferably have a relatively low number-
average molar mass, of less than 800 000 g/mol, preferably ranging
from 50 000 to 700 000 g/mol, and more preferably ranging from
200 000 to 600 000 g/mol.
Preferably, the cellulose derivative of the invention is a
hydroxyethylcellulose comprising one or more hydrophobic
substituent(s) containing from 8 to 30 carbon atoms.
The nonionic derivatives of cellulose used according to the
invention are substituted with one or more aliphatic or aromatic,
saturated or unsaturated, linear, branched or cyclic C8-C30 hydrocarbon
chain(s), that may be attached to the cellulose ether substrate via an
ether, ester or urethane bond, preferably an ether bond.
According to one embodiment, the hydrophobic substituent(s)
used as substituents of the nonionic derivatives of cellulose according

to the present invention are C8-C30, preferably C10-C22, alkyl, arylalkyl
or alkylaryl groups.
Preferably, the hydrophobic substituent(s) according to the
present invention are saturated alkyl chains.
According to a preferred embodiment, the hydrophobic
substituent(s) according to the present invention are cetyl groups.
The nonionic derivatives of cellulose with hydrophobic
substituent(s) according to the invention have a viscosity of preferably
between 100 and 100 000 mPa.s, and preferably between 200 and
20 000 mPa.s, measured at 25°C in a solution at 1% by weight of
polymer in water, this viscosity being determined conventionally using
a Brookfield LVT viscometer at 6 rpm with the No. 3 spindle.
The degree of hydrophobic substitution of the hydrophilic
nonionic derivatives of cellulose used according to the invention
preferably ranges from 0.1% to 10% by weight, more preferably from
0.1% to 1% by weight, and particularly preferably from 0.4% to 0.8%
by weight, of the total weight of the polymer.
Among the nonionic derivatives of cellulose with hydrophobic
substituent(s) that can be used in the compositions of the invention,
mention may preferably be made of the cetyl hydroxyethylcelluloses
sold under the names Natrosol Plus Grade 330 CS and Polysurf 67 CS
(INCI: Cetyl Hydroxyethylcellulose) by the company
Aqualon/Hercules.
The concentration of nonionic derivative(s) of cellulose with
hydrophobic substituent(s) (A) of the compositions according to the
invention preferably ranges from 0.01% to 10% by weight, in particular
from 0.05% to 3% by weight, and more preferably from 0.1% to 1% by
weight, relative to the total weight of the composition.
The fatty acid ester(s) (B) that can be used according to the
invention are monoesters or polyesters, preferably chosen from the
monoesters, diesters and triesters derived from the reaction of linear or
branched, saturated or unsaturated, optionally hydroxylated monoacids
or diacids containing from 8 to 30 carbon atoms, with saturated or
unsaturated, linear, branched or cyclic monoalcohols or polyols
comprising from 2 to 1000 carbon atoms and from 1 to 30 hydroxy!
group(s).

The fatty acids considered are, for example, stearic acid,
palmitic acid, lauric acid, oleic acid and myristic acid.
The monoalcohols or polyols considered are, for example,
ethanol, isopropanol, isooctanol, dodecanol, stearyl alcohol, ethylene
glycol, propylene glycol, glycerol, polyethylene glycols, polypropylene
glycols, glucose, methyl glucose, sorbitol, sorbitol anhydride and
pentaerythritol.
The monoalcohols and polyols which are not polyethylene
glycols and/or polypropylene glycols may be optionally
polyoxyalkylenated, and more particularly polyoxyethylenated and/or
polyoxypropylenated, the number of moles of ethylene oxide and/or of
propylene oxide per mole of ester then being preferably between 2 and
400, better still between 2 and 200.
Preferably, the monoalcohols or polyols, if they are other than
polyethylene glycols and/or polypropylene glycols, are not
polyoxyalkylenated.
The fatty acid ester(s) that can be used according to the
invention are generally nonionic, i.e. they do not comprise ionic
charges.
By way of example of esters that may be used according to the
invention, mention may be made of isopropyl myristate, stearyl
stearate, myristate or palmitate, ethylene glycol monostearate or
distearate, polyethylene glycol monostearate or distearate, such as
PEG-40 stearate, sorbitan monopalmitate, glyceryl isostearate,
propylene glycol dipelargonate, 2-ethylhexyl palmitate, sorbitan
tristearate, di(2-ethylhexyl) sebacate, glyceryl trihydroxystearate, cetyl
stearate, palmitate or myristate, and myristyl stearate, palmitate or
myristate.
Preferably, if the alcohol of the ester is a polyol, then this
alcohol contains more than 3 carbon atoms.
The concentration of fatty acid ester(s) (B) of the compositions
according to the invention preferably ranges from 0.01% to 10% by
weight, in particular from 0.2% to 10% by weight, and more preferably
from 0.5% to 6% by weight, relative to the total weight of the
composition.
The composition according to the invention may also comprise

one or more fatty acid amides. The fatty acid amide(s) that can be used
according to the invention are amides derived from the reaction of an
alkanolamine and of a C14-C30 fatty acid. They are preferably chosen
from the amides of a C2-C10 alkanolamine and of a C14-C30 fatty acid,
and even more preferably from the amides of a C2-C6 alkanolamine and
of a C14-C22 fatty acid.
The alkanolamine may be a monoalkanolamine or a
dialkanolamine. The fatty acid may be saturated or unsaturated, and
linear or branched.
The fatty acid amide(s) that can be used according to the
invention are generally nonionic, i.e. they do not comprise ionic
charges.
The amide of an alkanolamine and of a C]4-C30 fatty acid is
preferably chosen from:
- oleic acid diethanolamide, such as the amide sold under the
trade name Mexanyl® GT by the company Chimex,
- myristic acid monoethanolamide, such as the amide sold under
the trade name Comperlan® MM by the company Cognis,
- soybean fatty acid diethanolamide, such as the amide sold
under the trade name Comperlan VOD by the company Cognis,
- stearic acid ethanolamide, such as the amide sold under the
trade name Monamid® S by the company Uniqema,
- oleic acid monoisopropanolamide, such as the amide sold
under the trade name Witcamide® 61 by the company Witco,
- linoleic acid diethanolamide, such as the amide sold under the
trade name Purton® SFD by the company Zschimmer Schwarz,
- stearic acid monoethanolamide, such as the amide sold under
the trade name Monamid® 972 by the company ICI/Uniqema,
- behenic acid monoethanolamide, such as the amide sold under
the trade name Incromide® BEM by Croda,
- isostearic acid monoisopropanolamide, such as the amide sold
under the trade name Witcamide® SPA by the company Witco,
- erucic acid diethanolamide, such as the amide sold under the
trade name erucic acid diethanolamide by the company Stearineries
Dubois,
- ricinoleic acid monoethanolamide, such as the amide sold

under the trade name ricinoleic monoethanolamide by the company
Stearineries Dubois.
The concentration of fatty acid amide(s) of the compositions
according to the invention preferably ranges from 0 to 10%, in
particular from 0.2% to 10% by weight, and more preferably from 0.5%
to 6% by weight, relative to the total weight of the composition.
According to a particular embodiment, the dye compositions of
the invention comprise, in a medium suitable for dyeing:
(A) one or more nonionic derivative(s) of cellulose comprising one or
more hydrophobic substituent(s) containing from 8 to 30 carbon atoms
as defined above;
(B) (i) one or more amide(s) of an alkanolamine and of a C14-C30 fatty
acid, and
(ii) one or more C8-C30 fatty acid ester(s); and
(C) one or more oxidation dye(s), and preferably at least one oxidation
base and at least one oxidation coupler.
The oxidation dye(s) (C) that can be used according to the
invention is (or are) preferably chosen from oxidation bases and
oxidation couplers, and addition salts thereof.
By way of example, the oxidation bases that can be used are
chosen from para-phenylenediamines, bisphenylalkylenediamines, para-
aminophenols, bis-para-aminophenols, ortho-aminophenols and
heterocyclic bases, and addition salts thereof.
Among the para-phenylenediamines, mention may be made, by
way of example, of para-phenylenediamine, para-toluylenediamine,
2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine,
2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylene-
diamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-
phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-
para-phenylenediamine, 4-amino-N,N-diethyl-3 -methyl aniline, N,N-
bis(β-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(β-hydroxy-
ethyl)amino-2-methylaniline, 4-N,N-bis(β-hydroxyethyl)amino-2-
chloroaniline, 2-β-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-
phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(β-hydroxy-
propyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylene-
diamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N,N-( ethyl-

β-hydroxyethyl)-para-phenylenediamine, N-(β,γ-dihydroxypropyl)-
para-phenylenediamine, N-(4'-aminophenyl)-para-phenylenediamine,
N-pheny]-para-phenylenediamine, 2-β-hydroxyethyloxy-para-
phenylenediamine, 2-β-acetylaminoethyloxy-para-phenylenediamine,
N-(β-methoxyethyl)-para-phenylenediamine, 4-aminophenyl-
pyrrolidine, 2-thienyl-para-phenylenediamine, 2-β-hydroxyethylamino-
5-aminotoluene and 3-hydroxy-l-(4'-aminophenyl)pyrrolidine, and
addition salts thereof with an acid.
Among the para-phenylenediamines mentioned above, para-
phenylenediamine, para-toluylenediamine, 2-isopropyl-para-phenylene-
diamine, 2-β-hydroxyethyl-para-phenylenediamine, 2-β- hydroxy-
ethyloxy-para-phenylenediamine, 2,6-dimethyi-para-phenylenediamine,
2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylene-
diamine, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 2-chloro-
para-phenylenediamine and 2-β-acetylaminoethyloxy-para-phenylene-
diamine, and addition salts thereof with an acid, are particularly
preferred.
Among the bisphenylalkylenediamines, mention may, by way of
example, be made of N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-amino-
phenyl)-1,3-diaminopropanol, N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-
aminophenyl)ethylenediamine, N,N'-bis(4-aminophenyl)tetra-
methylenediamine, N,N'-bis(β-hydroxyethyl)-N,N'-bis(4-amino-
phenyl)tetramethylenediamine, N,N'-bis-(4-methylaminophenyl)tetra-
methylenediamine, N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methyl-
phenyl)ethylenediamine and 1,8-bis(2,5-diaminophenoxy)-3,6-dioxa-
octane and addition salts thereof with an acid.
Among the para-aminophenols, mention may be made, by way
of example of para-aminophenol, 4-amino-3-methylphenol, 4-amino-
3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methyl-
phenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-
phenol, 4-amino-2-aminomethylphenol, 4-amino-2-(β-hydroxy-
ethylaminomethyl)phenol and 4-amino-2-fluorophenol, and addition
salts thereof with an acid.
Among the ortho-aminophenols, mention may, by way of
example, be made of 2-aminophenol, 2-amino-5-methylphenol, 2-
amino-6-methylphenol and 5-acetamido-2-aminophenol, and addition

salts thereof with an acid.
Among the heterocyclic bases, mention may, by way of
example, be made of pyridine derivatives, pyrimidine derivatives,
pyrazole derivatives and pyrazolone derivatives, and addition salts
thereof.
Among the pyridine derivatives, mention may be made of the
compounds described, for example, in patents GB I 026 978 and
GB 1 153 196, such as 2,5-diaminopyridine, 2-(4-methoxy-
phenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine,
2-(β-methoxyethyl)amino-3-amino-6-methoxypyridine and 3,4-di-
aminopyridine, and addition salts thereof with an acid.
Other pyridine oxidation bases that can be used in the present
invention are the 3-aminopyrazolo[1,5-a]pyridine oxidation bases or
addition salts thereof described, for example, in patent application
FR 2801308. By way of example, mention may be made of
pyrazolo[1,5-a]pyridin-3-ylamine; 2-acetylaminopyrazolo-[1,5 -a]
pyridin-3-ylamine; 2-morpholin-4-ylpyrazolo[1,5-a]pyridin-3-ylamine;
3-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid; 2-methoxy-
pyrazolo[1,5-a]pyridin-3-ylamino; (3-aminopyrazolo[1,5-a]pyridin-7-
yl)methanol; 2-(3-aminopyrazolo[1,5-a]pyridin-5-yl)ethanol; 2-(3-
aminopyrazolo[1,5-a]pyridin-7-yl)ethanol; (3-aminopyrazolo[1,5-
a]pyridin-2-yl)methanol; 3,6-diaminopyrazolo[1,5-a]pyridine; 3,4-di-
aminopyrazolo[1,5-a]pyridine; pyrazolo[1,5-a]pyridine-3,7-diamine; 7-
morpholin-4-ylpyrazolo[1,5-a]pyridin-3-ylamine; pyrazolo[1,5-
a]pyridine-3,5-diamine; 5-morpholin-4-ylpyrazolo[1,5-a]pyridin~3-yl-
amine; 2-[(3-aminopyrazolo[1,5-a]pyridin-5-yl)(2-hydroxyethyl)-
amino]ethanol; 2-[(3-aminopyrazolo[1,5-a]pyridin-7-yl)(2-hydroxy-
ethyl)amino]ethanol; 3-aminopyrazolo[1,5-a]pyridin-5-ol; 3-amino-
pyrazolo[1,5-a]pyridin-4-ol; 3-aminopyrazolo[1,5-a]pyridin-6-ol;
3-aminopyrazolo[1,5-a]pyridin-7-ol; and also addition salts thereof
with an acid or with a base.
Among the pyrimidine derivatives, mention may be made of the
compounds described, for example, in Patents DE 2359399;
JP 88-169571; JP 05-63124; EP 0770375 or Patent Application
WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy~2,5,6-
triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine,

2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and
pyrazolopyrimidine derivatives such as those mentioned in Patent
Application FR-A-2 750 048 and among which mention may be made of
pyrazolo[1,5-a]pyrimidine-3,7-diamine; 2,5-dimethyl-
pyrazolo[1,5-a]pyrimidine-3,7-diamine; pyrazolo[1,5-a]pyrimidine-3,5-
diamine; 2,7-dimethylpyrazolo[l ,5-a]pyrimidine-3,5-diamine; 3-amino-
pyrazolof 1,5-a]pyrimidin-7-ol; 3-aminopyrazolo[1,5-a]pyrimidin-5-ol;
2-(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)ethanol, 2-(7-amino-
pyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol, 2-[(3-aminopyrazolo[1,5-
a]pyrimidin-7-yl)(2-hydroxyethyl)amino]ethanol, 2-[(7-amino-
pyrazolo[1,5-a]pyrirnidin-3-yl)(2-hydroxyethyl)amino]ethanol, 5,6-di-
methylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 2,6-dimethyl-
pyrazolo[1,5-a]pyrimidine-3,7-diamine, 2, 5, N7, N7-tetramethyl-
pyrazolo[1,5-a]pyrimidine-3,7-diamine, 3-amino-5-methyl-7-imidazol-
ylpropylaminopyrazolo[1,5-a]pyrimidine, and addition salts thereof
with an acid and tautomeric forms thereof when a tautomeric
equilibrium exists.
Among the pyrazole derivatives that can be used, mention may
be made, for example, of the compounds described in Patents DE-A-38
43 892, DE-A-41 33 957 and Patent Applications WO 94/08969,
WO 94/08970, FR-A-2 733 749 and DE-A-195 43 988, such as
4,5-diamino-1-methylpyrazole, 4,5-diamino-1-(β-hydroxy ethyl)-
pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4'-chlorobenzyl)-
pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-
phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-
dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methyl-
pyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino
tert-butyl-3-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)-3-methyl-
pyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-
3-(4'-methoxyphenyl)pyrazole, le 4,5-diamino-1-ethyl-3-hydroxy
methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-
diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-
1-isopropylpyrazole, 4-amino-5-(2'-aminoethyl)amino-1,3-dimethyl-
pyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole,
3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-
4-(β-hydroxyethyl)amino-1-methylpyrazole, and addition salts thereof.

Among the pyrazolone derivatives that can be used, mention
may, for example, be made of the following compounds and addition
salts thereof:
2,3-diaminodihydropyrazolone;
4,5-diamino-1,2-dimethyl-1,2-dihydropyrazol-3-one;
4-amino-5-methylamino-1,2-dimethyl-1,2-dihydropyrazol-3-one;
4-amino-5-dimethylamino-1,2-dimethyl-1,2-dihydropyrazol-3-one;
4-amino-5-(2-hydroxyethyl)amino-1,2-dimethyl-1,2-dihydropyrazol-3-
one;
4-amino-5-(pyrrolidin-1-yl)-1,2-dimethyl-1,2-dihydropyrazol-3-one;
4-amino-5-(piperidin-1-yl)-1,2-dimethyl-1,2-dihydropyrazol-3-one;
4,5-diamino-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-3-one:
4-amino-5-methylamino-1,2-di(2-hy droxy ethyl)-1,2-dihydropy razol-3-
one;
4-amino-5-dimethylamino-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazoI-
3-one;
4-amino-5-(2-hydroxyethyl)amino-1,2-di(2-hydroxyethyl)-1,2-
dihydropyrazol-3-one;
4-amino-5-(pyrrolidin-1-yl)-1,2-di(2-hydroxy ethyl)-1,2-
dihydropyrazol-3-one;
4-amino-5-(piperidin-1-yl)-1,2-di(2-hydroxyethyl)- 1,2-dihydropy razol-
3-one;
4,5-diamino-1,2-diethyl-1,2-dihydropyrazol-3-one;
4,5-diamino-1,2-diphenyl-1,2-dihydropyrazol-3-one;
4,5-diamino-1-ethyl-2-methyl-1,2-dihydropyrazol-3-one;
4,5-diamino-2-ethyl-1-methyl-1,2-dihydropyrazol-3-one;
4,5-diamino-1-phenyl-2-methyl-1,2-dihydropyrazol-3-one;
4,5-diamino-2-phenyl-1-methyl-1,2-dihydropyrazol-3-one;
4,5-diamino-1-(2-hydroxyethyl)-2-methyl-1,2-dihydropyrazol-3-one;
4,5-diamino-2-(2-hydroxyethyl)-1-methyl-1,2-dihydropyrazol-3-one;
2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,
2-amino-3-methylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-
one;
2-amino-3-dimethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-
1-one;
2-amino-3-ethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-

one;
2-amino-3-isopropylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-
1-one;
2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[l ,2-a]-
pyrazol-1-one;
2-amino-3-(2-hydroxypropyl)amino-6,7-dihydro-1H,5H-pyrazoloI 1,2-
a]pyrazol-1-one;
2-amino-3-bis(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-
a]pyrazol-1-one;
2-amino-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]~
pyrazol-1 -one;
2-amino-3-(3-hydroxypyrrolidin-1-yl)-6,7--dihydro-1H,5H-
pyrazolo[1,2-a]pyrazol-1-one;
2-amino-3-(piperidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-
1-one;
2,3-diamino-6-hydroxy-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-
one;
2,3-diamino-6-methyl-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-
one;
2,3-diamino-6,6-dimethyl-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-
1-one;
2,3-diamino-5,6,7,8-tetrahydro-1H,6H-pyridazino[1,2-a]pyrazol-1-one;
2,3-diamino-5,8-dihydro-1H,6H-pyridazino[1,2-a]pyrazol-1-one;
4-amino-5-dimethylamino-1,2-diethyl-1,2-dihydropyrazol-3-one;
4-amino-1,2-diethyl-5-ethylamino-1,2-dihydropyrazol-3-one;
4- amino -1,2-diethyl-5-isopropylamino-1,2-dihydropyrazol-3-one;
4- amino -1,2-diethyl-5-(2-hydroxyethylamino)-1,2-dihydropyrazol-3-
one;
4-amino-5-(2-dimethylaminoethylamino)-1,2-diethyl-1,2-dihydro-
pyrazol-3-one;
4-amino-5-[bis(2-hydroxyethyl)amino]-1,2-diethyl-1,2-dihydropyrazol-
3-one;
4-amino-1,2-diethyl-5-(3-imidazol-1-ylpropyl amino)-1,2-dihydro-
pyrazol-3-one;
4-amino-1,2-diethyl-5-(3-hydroxypyrrolidin-1-yl)-1,2-dihydropyrazol-
3-one;

4-amino-5-pyrrolidin-1-yl-1,2-diethyl-1,2-dihydropyrazol-3-one;
4-amino-5-(3-dimethylaminopyrrolidin-1-yl)-1,2-diethyl-1,2-dihydro-
pyrazol-3-one;
4-amino-1,2-diethyl-5-(4-methylpiperazin-1--yl)pyrazolidin-3-one.
The concentration of oxidation base(s) generally ranges from
0.001% to 20% by weight, preferably from 0.005% to 10% by weight.,
and even more preferably from 0.1% to 5% by weight, relative to the
total weight of the composition.
The oxidation coupler(s) present in the compositions of the
invention may be chosen from benzene couplers, heterocyclic couplers
and naphthalene couplers, and addition salts thereof.
By way of benzene couplers that can be used in the
compositions according to the invention, mention may be made of
meta-aminophenols, meta-phenylenediamines and meta-diphenols, and
also addition salts thereof.
Among the preferred couplers, mention may be made of
2-methyl-5-aminophenol, 5-N-(p-hydroxyethyl)amino-2-methylphenol,
6-chloro-2-methyl-5-aminophenol, 3-aminophenol, 1,3-dihydroxy-
benzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxy-
benzene, 2,4-diamino-1-(β-hydroxyethyloxy)benzene, 2--amino-4-(β-
hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis
(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido-1-dimethyl -
aminobenzene, sesamol, l-β-hydroxyethylamino-3,4-methylenedioxy-
benzene, a-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole,
4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxy-
pyridine, 6-hydroxybenzomorpholine 3,5-diamino-2,6-dimethoxy-
pyridine, l-N-(β-hydroxyethyl)amino-3,4-methylenedioxybenzene and
2,6-bis-(β-hydroxyethylamino)toluene, and addition salts thereof with
an acid.
The concentration of oxidation coupler(s) generally ranges from
0.001% to 20% by weight, preferably from 0.005% to 10% by weight,
and even more preferably from 0.01% to 5% by weight, relative to the
total weight of the composition.
In general, the addition salts of the oxidation bases and of
the couplers that can be used in the context of the invention are in
particular chosen from the addition salts with an acid, such as the

hydrochlorides, hydrobromides, sulphates, citrates, succinates,
tartrates, lactates, tosylates, benzenesulphonates, phosphates and
acetates, and the addition salts with a base, such as sodium hydroxide,
potassium hydroxide, aqueous ammonia, amines or alkanolamines
The dye composition in accordance with the invention may also
contain one or more direct dye(s) that may in particular be chosen from
nitrobenzene dyes, azo direct dyes, methine direct dyes, anthraquinone
dyes, xanthene dyes and triarylmethane dyes, and addition salts
thereof. These direct dyes may be nonionic, anionic or cationic in
nature.
The medium used in the compositions according to the present
invention is an aqueous medium or a medium containing water and at
least one organic solvent.
The organic solvent(s) used in the compositions according to
the invention may be chosen from monohydroxylated alcohols and
polyols.
By way of monohydroxylated alcohols that can be used,
mention may be made of C1-C4 lower alcohols such as ethanol,
isopropanol, tert-butanol or n-butanol, and mixtures thereof The
alcohol used is preferably ethanol.
By way of polyols that can be used, mention may be made of
propylene glycol, polyethylene glycols and glycerol. By way of organic
solvents, mention may also be made of polyol ethers such as
2-butoxyethanol, propylene glycol monomethyl ether, diethylene glycol
monoethyl ether and diethylene glycol monomethyl ether, and also
aromatic alcohols such as benzyl alcohol or phenoxyethanol, and
mixtures thereof.
The concentration of organic solvent(s) in the compositions
according to the present invention is preferably between 0 and 30%,
and more preferably between 0 and 20% by weight, relative to the total
weight of the composition.
The compositions according to the present application may also
contain one or more thickener(s), also referred to as "rheology-
adjusting agent(s)", different from the nonionic derivatives of cellulose
with hydrophobic substituent(s) of the invention.
The rheology-adjusting agent(s) may be chosen from mineral or

organic thickeners, and in particular polymeric associative thickeners,
fatty alcohols (oleyl alcohol), cellulosic derivatives other than the
nonionic derivatives of cellulose with hydrophobic substituent(s) (A)
according to the invention (hydroxyethylcellulose,
hydroxypropylcellulose, carboxymethylcellulose) and gums of
microbial origin (xanthan gum, scleroglucan gum).
The preferred rheology-adjusting agent(s) is (are) chosen from
fatty alcohols, in particular C20-C22 fatty alcohols, and cellulose
derivatives, other than the nonionic derivatives of cellulose with
hydrophobic substituent(s) (A) according to the invention.
The concentration of thickener(s) is preferably between 0.01%
and 20% by weight, and more preferably between 1% and 10% by
weight, relative to the total weight of the composition.
The dye composition in accordance with the invention may also
contain one or more adjuvant(s) conventionally used in compositions
for dyeing the hair.
The term "adjuvant(s)" is intended to mean one (or more)
additive(s) different from the abovementioned compounds, such as
anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or
mixtures thereof; nonionic, amphoteric, zwitterionic, anionic or
cationic polymers, other than the nonionic derivatives of cellulose with
hydrophobic substituent(s) (A) according to the invention, or mixtures
of said polymers; penetrating agents; sequestering agents; fragrances;
buffers; dispersants; conditioning agents such as, for example,
modified or unmodified, volatile or non-volatile silicones; film-
forming agents; ceramides other than the fatty acid amides (B) (i)
according to the invention; preservatives; opacifiers; vitamins; amino
acids; oligopeptides; peptides; modified or unmodified, hydrolysed or
nonhydrolysed proteins; enzymes; branched or unbranched fatty acids
and alcohols; animal, plant or mineral waxes; hydroxylated organic
acids; UV screens; antioxidants and free-radical scavengers;
antidandruff agents; seborrhoea-regulating agents; calmatives; mineral
oils; polyisobutenes and poly(α-olefins); pigments; acids, bases,
plasticizers, mineral fillers, pearlescent agents, flakes; antistatic agents
and reducing agents.
The adjuvant(s) above is (are), in general, present in an amount,

for each of them, of preferably between 0.01% and 40% by weight, and
more preferably between 0.1% and 25% by weight, relative to the total
weight of the composition.
Of course, those skilled in the art will take care to select this
(or these) possible additional compound(s) in such a way that the
advantageous properties intrinsically associated with the oxidation
dyeing composition in accordance with the invention are not, or not
substantially, impaired by the addition(s) envisaged.
The pH of the dye composition in accordance with the invention
generally ranges from 3 to 12 approximately, and preferably from 5 to
1 1 approximately. It may be adjusted to the desired value by means of
acidifying agent(s) or basifying agent(s) commonly used in the dyeing
of keratin fibres or alternatively using conventional buffer system(s).
Among the acidifying agents, mention may be made, by way of
example, of mineral or organic acids such as hydrochloric acid,
orthophosphoric acid, sulphuric acid, sulphonic acids and carboxylic
acids, for instance acetic acid, tartaric acid, citric acid and lactic acid.
Among the basifying agents, mention may, by way of example,
be made of aqueous ammonia, alkali metal carbonates, alkanolamines
such as mono-, di- and triethanolamines and derivatives thereof,
sodium hydroxide or potassium hydroxide and the compounds of
formula (I) below:
in which:
■ W is a propylene residue optionally substituted with a
hydroxyl group or a C1-C4 alkyl group;
■ Ra, Rb, Rc and Rd, which may be identical or different,
represent a hydrogen atom, a C1-C4 alkyl group or a C1-C4
hydroxyalkyl group.
The dye composition according to the invention may be in
various forms, such as in the form of creams or gels, or in any other
form suitable for dyeing keratin fibres, and in particular human hair.

The process for dyeing keratin fibres, of the present invention,
is a process in which the composition according to the present
invention as defined above is applied to the fibres, preferably in the
presence of at least one oxidizing agent for a period of time sufficient
to develop the desired colour. The colour may be revealed at acidic,
neutral or alkaline pH and the oxidizing agent(s) may be added to the
composition of the invention just at the time of use, or it (they) may be
used starting from an oxidizing composition containing it (them),
applied simultaneously with or sequentially to the composition of the
invention.
According to one particular embodiment, the composition
according to the present invention is a ready-to-use composition which
is mixed, preferably at the time of use, with a composition containing,
in a medium suitable for dyeing, at least one oxidizing agent, this
oxidizing agent (or these oxidizing agents) being present in a sufficient
amount to develop a colouration. The mixture obtained is subsequently
applied to the keratin fibres. After a leave-on time of approximately 3
to 50 minutes, preferably approximately 5 to 30 minutes, the keratin
fibres are rinsed, washed with shampoo, rinsed again, and then dried.
The oxidizing agents conventionally used for the oxidation
dyeing of keratin fibres are, for example, hydrogen peroxide, urea
peroxide, alkali metal bromates, persalts such as perborates and
persulphates, peracids and oxidase enzymes, among which mention may
be made of peroxidases, 2-electron oxidoreductases, such as uricases,
and 4-electron oxygenases, such as laccases, these oxidoreductases
being optionally combined with their customary cofactors, such as uric
acid for uricases. The preferred oxidizing agent is hydrogen peroxide.
The oxidizing composition may also contain various adjuvants
conventionally used in compositions for dyeing the hair, as defined
above.
The pH of the oxidizing composition containing the oxidizing
agent is such that, after mixing with the dye composition, the pH of the
resulting composition applied to the keratin fibres preferably ranges
from 3 to 12 approximately, and preferentially from 5 to 10. It may be
adjusted to the desired value by means of acidifying agent(s) or
basifying agent(s) normally used in the dyeing of keratin fibres, as

defined above.
The ready-to-use composition which is finally applied to the
keratin fibres may be in various forms, such as in the form of creams
or gels, or in any other form suitable for dyeing keratin fibres, and in
particular human keratin fibres such as the hair.
A subject of the invention is also a multicompartment dyeing
device or dyeing "kit", comprising at least a first compartment
containing the dye composition as defined above and at least a second
compartment containing an oxidizing composition. This device may be
equipped with a means for delivering the desired mixture to the hair,
such as the devices described in patent application FR-A-2 586 91 3.
The examples which follow serve to illustrate the invention
without, however, being limiting in nature.
EXAMPLES
EXAMPLE 1: Dye compositions according to the invention
The following compositions 1 and 2 were prepared.

Each composition 1 and 2 is diluted, extemporaneously, with
one and a half times its weight of an oxidizing composition having a
pH in the region of 3 (aqueous hydrogen peroxide at 20 volumes) (6%
by weight of H2O2). The mixture is easily prepared and has a good
viscosity; it is easily applied to grey hair, containing 90% white hairs,
at a rate of 10 g per 1 g of hair, for 30 minutes. The hair is then rinsed,
washed with a standard shampoo and dried.
The hair colouration is evaluated visually. The results obtained
on natural grey hair, containing 90% white hairs, after treatment, are
the following:
These colourations have good properties, in particular in terms
of selectivity and strength. The compositions obtained are stable over
time.
EXAMPLE 2: Comparative example
Composition 3 according to the invention and comparative
Composition 4 were prepared.



Application protocol
At the time of use, each of Compositions 3 and 4 is mixed with
one and a half times its weight of an oxidizing composition (aqueous
hydrogen peroxide at 20 volumes) (6% by weight of H2O2).
Dyeing properties
Each mixture is applied to natural (NW) and permanent-waved
(PW) locks of hair containing 90% white hairs, at a rate of 15 g of
mixture per gram of locks of hair. After a leave-on time of 30 minutes
at ambient temperature, the locks are rinsed, washed with a standard
shampoo, rinsed again and dried.
The colorimetric measurements are carried out using the Konica
Minolta CM-2600d spectrocolorimeter in the CIE L*a*b* system. In
the L*a*b* system, L* represents the strength of the colouring
obtained; the lower the value of L*, the stronger the colouring
obtained. The chromaticity is measured by the values a* and b*, a*
indicating the value along the green/red colour axis and b* indicating
the value along the blue/yellow colour axis.
For each composition, the selectivity of the colouring is
evaluated. The selectivity of the colouring is the variation in the colour

between natural hair and permanent-waved hair. The natural hair is
representative of the nature of the hair at the root, whereas the
permanent-waved hair is representative of the nature of the hair at the
end.
The selectivity is measured by AE, which is the variation in
colour between the natural hair and the permanent-waved hair, and is
obtained from the formula:

in which:
L*, a* and b* represent the parameters of the dyed permanent-
waved hair, and
L0*, a0* and bo* represent the parameters of the dyed natural hair.
The lower the value of AE, the lower the selectivity and
therefore the more uniform the colouring along the hair.
Results

The selectivity (AE) is lower for Composition 3 according to
the invention, thereby being representative of a more uniform
colouring along the fibre.

CLAIMS
1. Dye composition for keratin fibres, comprising, in a
medium suitable for dyeing:
(A) one or more nonionic derivative(s) of cellulose comprising one or
more hydrophobic substituent(s) containing from 8 to 30 carbon atoms;
(B) one or more C8-C30 fatty acid ester(s); and
(C) one or more oxidation dye(s).

2. Dye composition according to Claim 1, characterized in
that the nonionic derivative of cellulose (A) is a hydroxyethylcellulose
substituted with one or more hydrophobic substituent(s) containing
from 8 to 30 carbon atoms.
3. Dye composition according to either one of the preceding
claims, characterized in that the hydrophobic substituent is a C10-C22
alkyl group.
4. Dye composition according to any one of the preceding
claims, characterized in that the hydrophobic substituent is a cetyl
group.
5. Dye composition according to any one of the preceding
claims, characterized in that the degree of hydrophobic substitution
ranges from 0.1% to 10% by weight, preferably from 0.1% to 1% by
weight, and more preferably from 0.4% to 0.8% by weight, of the total
weight of the polymer.
6. Dye composition according to any one of the preceding
claims, characterized in that the concentration of nonionic
derivative(s) of cellulose (A) ranges from 0.01% to 10% by weight,
preferably from 0.05% to 3% by weight, and more preferably from
0.1% to 1% by weight, relative to the total weight of the composition.
7. Dye composition according to any one of the preceding
claims, characterized in that it also comprises one or more amide(s) of
an alkanolamine and of a C14-C30 fatty acid, preferably chosen from
the amides of a C2-C10 alkanolamine and of a C14-C30 fatty acid, and
more preferably from the amides of a C2-C6 alkanolamine and of a

C14-C22 fatty acid.
8. Dye composition according to Claim 7, characterized in
that the alkanolamine is a monoalkanolamine or dialkanolamine.
9. Dye composition according to Claim 7 or 8, characterized
in that the fatty acid amide (B) is chosen from the following
compounds:

- oleic acid diethanolamide,
- myristic acid monoethanolamide.
- soybean fatty acid diethanolamide,
- stearic acid ethanolamide,
- oleic acid monoisopropanolamide,
- linoleic acid diethanolamide,
- stearic acid monoethanolamide,
- behenic acid monoethanolamide,
- isostearic acid monoisopropanolamide,
- euric acid diethanolamide,
- ricinoleic acid monoethanolamide.

10. Dye composition according to any one of Claims 7 to 9,
characterized in that the concentration of fatty acid amide(s) (B)
ranges from 0.2% to 10% by weight, and more preferably from 0.5% to
6% by weight, relative to the total weight of the composition.
11. Dye composition according to any one of the preceding
claims, characterized in that the fatty acid ester (B) is chosen from the
monoesters, diesters and triesters derived from the reaction of linear
or branched, saturated or unsaturated, optionally hydroxylated
monoacids or diacids containing from 8 to 30 carbon atoms, with
saturated or unsaturated, linear, branched or cyclic monoalcohols or
polyols comprising from 2 to 100 carbon atoms and from 1 to 30
hydroxyl group(s).
12. Dye composition according to the preceding claim,
characterized in that the fatty acid ester (B) is chosen from isopropyl
myristate, stearyl stearate, myristate or palmitate, ethylene glycol
monostearate or distearate, polyethylene glycol monostearate or
distearate, sorbitan monopalmitate, glyceryl isostearate, propylene

glycol dipelargonate, 2-ethylhexyl palmitate, sorbitan tristearate,
di(2-ethylhexyl) sebacate, glyceryl trihydroxystearate, cetyl stearate,
palmitate or myristate, and myristyl stearate, palmitate or myristate
13. Dye composition according to any one of the preceding
claims, characterized in that the concentration of fatty acid ester(s)
(B) ranges from 0.01% to 10% by weight, preferably from 0.2% to
10% by weight, and more preferably from 0.5% to 6% by weight,
relative to the total weight of the composition.
14. Dye composition according to any one of the preceding
claims, characterized in that the oxidation dye (C) is chosen from
oxidation bases and oxidation couplers, and addition salts thereof.
15. Dye composition according to the preceding claim,
characterized in that the oxidation base is chosen from para-
phenylene diamines, bisphenylalkylenediamines, para-aminophenols,
bis-para-aminophenols, ortho-aminophenols and heterocyclic bases,
and addition salts thereof.
16. Dye composition according to any one of the preceding
claims, characterized in that the concentration of oxidation base(s)
ranges from 0.001% to 20% by weight, preferably from 0.005% to 10%
by weight, and even more preferably from 0.01% to 5% by weight,
relative to the total weight of the composition.

17 Dye composition according to Claim 14, characterized in
that the oxidation coupler is chosen from benzene couplers,
heterocyclic couplers and naphthalene couplers, and addition salts
thereof.
18 Dye composition according to the preceding claim,
characterized in that the benzene coupler is chosen from
meta-aminophenols, meta-phenylenediamines and meta-diphenols, and
addition salts thereof.
19. Dye composition according to any one of the preceding
claims, characterized in that the concentration of oxidation coupler(s)
ranges from 0.001% to 20% by weight, preferably from 0.005% to 10%
by weight, and even more preferably from 0.01% to 5% by weight,
relative to the total weight of the composition.

20. Dye composition according to any one of the preceding
claims, characterized in that it comprises one or more direct dye(s)
chosen from nitrobenzene dyes, azo direct dyes, methine direct dyes,
anthraquinone dyes, xanthene dyes and triarylmethane dyes, and
addition salts thereof.
21. Dye composition according to any one of the preceding
claims, characterized in that it comprises at least an oxidizing agent.
22. Process for the oxidation dyeing of keratin fibres,
characterized in that a dye composition as defined in any one of
Claims 1 to 20 is applied to the fibres, in the presence of at least one
oxidizing agent for a period of time sufficient to develop the desired
colour.
23. Multicompartment device, characterized in that it
comprises at least a first compartment containing a dye composition as
defined in any one of Claims 1 to 20 and at least a second
compartment containing at least one oxidizing agent.
24. Use of the composition defined in any one of Claims 1 to
21, for dyeing keratin fibres, in particular human keratin fibres such as
the hair.

The present invention relates to a dye composition for keratin
fibres, and in particular for human keratin fibres such as the hair,
comprising, in a medium suitable for dyeing:
(A) one or more nonionic derivative(s) of cellulose comprising one
or more hydrophobic substituent(s) containing from 8 to 30 carbon
atoms;
(B) one or more C8-C30 fatty acid ester(s); and
(C) one or more oxidation dye(s).
The present invention also relates to a process for dyeing
keratin fibres using such a composition; and also to the use of this
composition for dyeing keratinous fibres.