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 nonionic, nonhydrophobic polymer(s) of the
hydroxyalkylcellulose type, 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 oxichinon 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, especi especially in terms
of dyeing properties, in particular in terms of dyeing selectivity and
fastnesses. 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 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 nonionic, nonhydrophobic polymer(s) of the
hydroxyalkylcellulose type; 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 bydrophilic
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.
For the purpose of the present invention, the term
"nonhydrophobic polymer" is intended to mean a polymer which does
not comprise, in its structure, a fatty chain containing at least 8 carbon
atoms.
The nonionic, nonhydrophobic polymer(s) of the
hydroxyalkylcellulose type (B) that can be used according to the
invention is (are) prepared from cellulose of which all or some of the
hydroxyl functions are etherified, in a manner known to those skilled
in the art, with one or more alkyl or hydroxyalkyl group(s), which may
be identical or different, preferably containing from 1 to 4 carbon

atoms.
The nonionic, nonhyclrophobic polymer(s) of the
hydroxyalkylcellulose type (B) that can be used according 10 the
invention thus comprise one or more linear or branched, saturated or
unsaturated, alkyl or hydroxyalkyl group(s), which may be identical or
different, preferably containing from 1 to 4 carbon atoms.
By way of alkyl or hydroxyalkyl group(s) containing from 1 to
4 carbon atoms, that can be used, mention may be made of methyl,
ethyl, propyl, isopropyl, hydroxymethyl, hydroxyethyl, hydroxypropyl
and hydroxyisopropyl groups.
The nonionic, nonhydrophobic polymer o! the
hydroxyalkylcellulose type (B) according to the invention is preferably
chosen from:
hydroxypropylmethylcelluloses, such as those sold
under the name Methocel F4M by the company Dow Chemical,
hydroxyethylcelluloses, such as those sold under the
name Natrosol 250 HHR by the company Aqualon.
The nonionic, nonhydrophobic polymer of the
hydroxyalkylcellulose type (B) that is particularly preferred according
to the invention is hydroxypropylmethylcellulose.
The concentration of nonionic, nonhydrophobic polymer(s) of
the hydroxyalkylcellulose type (B) of the compositions according to
the invention preferably ranges from 0.01% to 5%, in particular from
0.05% to 2% by weight, and more preferably from 0.1% to 1% by
weight, relative to the total weight of the composition.
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-methylaniline, N,N-
bis(β-hydroxyethyl)-para-phetiylenediamine, 4-N,N-bis(β-hydroxy-
ethyl)amino-2-methylaniline, 4-N, N-bis(β-hydroxy ethyl )amino -2-
chloroaniline, 2-β-hydroxyetbyl-para-phenylenedi amine, 2-fluoro-para-
phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(β-hydroxy-
propyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylene-
diamine, N,N-dimethyl-3-met:hyl-para-phenylenediamine, N, N-(ethyl-
β-hydroxyethyl)-para-phenylenediamine, N-(β,γ-dihydroxypropyl)-
para-phenylenedi amine, N-('4'-aminopheny])-para-phenylenediamine,
N-phenyl-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-dimethyl-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 bisphenylalk)'lenediamines, mention may, by way of
example, be made of N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-amino-
phenyl)-l,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-methoxymethy]~
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 1 026 978 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-am in o-
pyrazolo[1,5-a]pyridin-4-ol; 3-aminopyrazolo[1,5-a]pyndin-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 n 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-dimethy1-
pyrazolo[1,5-a]pyrimidine-3,7-diamine; pyrazolo[1,5-a]pyrimidine-3,5-
diamine; 2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine; 3-amino-
pyrazolo[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]pyrimidin-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]pynmidine, 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-l-methylpyrazole, 4,5 -diamino-l-(β-hydroxy ethyl )-
pyrazole, 3,4-diaminopyrazole, 4,5-diamino-l-(4'-chlorobenzyl)-
pyrazole, 4,5-diamino-l,3-dimethylpyrazole, 4,5-diamino-3 -methyl-1 -
phenylpyrazole, 4,5-diamino-l-methyl-3-phenylpyrazole, 4-amino-1,3-
dimethyl-5-hydrazinopyrazole, l-benzyl-4,5-diamino-3-methyl-
pyrazole, 4,5-diamino-3-tert-butyl-l-methylpyrazole, 4,5-diamino-1 -

tert-butyl-3-methylpyrazole, 4!5-diamino-l-(β-hydroxyethyl)~3-methyl-
pyrazole, 4,5-diamino-l-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-l-methylpyrazole, 4,5-
diamino-3-hydroxymethyl-l-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-l-methyl-4-methylaminopyrazole and 3,5-diamino-
4-(β-hydroxyethyl)amino-l-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-l-yl)-1,2-dimethyl-1,2-dihydropyrazol-3-one;
4-amino-5-(piperidin-l-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-hydroxyethyl)-1,2-dihydropyrazol-3-
one;
4-amino-5-dimethylamino-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-
3-one;
4-amino-5-(2-hydroxyethyl)amino- 1,2-di(2-hydroxyethyl)-l ,2-
dihydropyrazol-3-one;
4-amino-5-(pyrrolidin- 1-yl)-1,2-di( 2-hydroxyethyl)-1,2-
dihydropyrazoI-3-one;
4-amino-5-(piperidin-l-yl)-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-
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-l-ethyl-2-methyl-1,2-dihydropyrazol-3-one;
4,5-diamino-2-ethyl-l-methyl-1,2-dihydropyrazol-3-one;
4,5-diamino-l-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-hydroxyethy[)-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-l~
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-] H,5H-pyrazolo[1,2-a]pyrazol
1-one;
2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[1 ,2-a]-
pyrazol-1-one;
2-amino-3-(2-hydroxypropyl)iimino-6,7-dihydro-1H,5H-pyrazolo[ 1,2-
a]pyrazol-1-one;
2-amino-3-bis(2-hydroxyethy].)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-l -
one;
2,3-diamino-6-methyl-6,7-dihydro-1H,5H-pyrazolo[1 ,2-a]pyrazol-l -
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-hydroxy ethyl) amino] -1,2 -die thy 1-1,2 -dihydropyrazo 1-
3-one;
4-amino-1,2-diethyl-5-(3-imidazol-l -ylpropylamino)-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-l -yl)-1 ,2-diethyl-1,2-dihydro-
pyrazol-3-one;
4-amino-1,2-diethyl-5-(4-methelpiperazin-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-(β-hydroxyethyl)amino-2-methylphenol,
6-chloro-2-methyl-5-aminophenol, 3-aminophenol, 1,3-dihydroxy-
benzene, l,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxy-
benzene, 2,4-diamino-l -(β-hydroxyethyloxy)benzene, 2-amino-4-(β-
hydroxyethylamino)-l -me thoxy benzene, 1,3-diaminobenzene, 1,3-bis
(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido-l dimethyl-
aminobenzene, sesamol, l-p-hydroxyethylamino-3,4-methylenedioxy-
benzene, a-naphthol, 2-nethyl-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-(p-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 13.01% to 5% by weight, relative to the
total weight of the composition.
According to one 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) one or more nonionic, nonhydrophobic polymer(s) of the
hydroxyalkylcellulose type; and
(C) one or more oxidation base(s) and one or more oxidation
coupler(s).
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 alkanolammes.
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 diethylere 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 l.) 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)
and the nonionic, nonhydrophobic polymers of the
hydroxyalkylcellulose type (B) according to the invention
(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) and the nonionic, nonhydrophobic
polymers of the hydroxyalkylcellulose type (B) 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) and the nonionic, nonhydrophobic
polymers of the hydroxyalkylcellulose type (B) 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, 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; animal, plant or mineral oils; polyisobutenes and poly(oc-
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
11 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 lime 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 colactors. 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-2 586 913.
The examples which follow serve to illustrate the invention
without, however, being limiting in nature.

Application protocol
Each composition 1 and 2 is diluted, extemporaneously, with
one and a half times its weight of an oxidizing composition (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 fastness. They also have a good strength. The
compositions obtained are stable over time.

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)
Rheological property
The measurements are carried out on compositions 3 and 4,
before and after mixing with said oxidizing composition under the
conditions described above.
The viscosity measurements are carried out using she Rheomat
RM180 rheometer (Mettler): rotation speed 200 rpm and temperature at
25°C with a different spindls according to viscosities (spindle No. 2, 3
or 4, noted respectively Ml. M2 or M3). The viscosities are measured
30 seconds after the spindle has begun to rotate.
Results


Before and after mixing with the oxidant, composition 3
according to the invention is thicker and therefore poses less risk of
running during application.
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 b0* 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

On natural hair and permanent-waved hair, the colouring
obtained with composition 3 according to the invention is stronger
(lower L* values) than the colouring obtained with composition 4.
The selectivity (AE) is lower for composition 3 according to the
invention, which is representative of a more uniform colouring along
the fibre.

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 nonionic, nonhydrophobic polymer(s) of the
hydroxyalkylcellulose type; 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 the nonionic, nonhydrophobic polymer of

the hydroxyalkylcellulose type (B) comprises one or more linear or
branched, saturated or unsaturated, alkyl or hydroxyalkyl group(s),
which may be identical or different, containing from 1 to 4 carbon
atoms.
8. Dye composition according to Claim 7, characterized in
that the nonionic, nonhydrophobic polymer of hydroxyalkylcellulose
type (B) is chosen from hydroxypropylmethylcelluloses and
hydroxyethylcelluloses.
9. Dye composition according to any one of the preceding
claims, characterized in that the concentration of nonionic,
nonhydrophobic polymer(s) of the hydroxyalkylcellulost.- type (B)
preferably ranges from 0.01% to 5%, in particular from 0.05% to 2%
by weight, and more preferably from 0.1% to 1% by weight, relative to
the total weight of the composition.
10. 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.

11. Dye composition according to the preceding claim,
characterized in that the oxidation base is chosen from para-
phenylenediamines, bisphenylalkylenediamines, para-aminophenols,
bis-para-aminophenols, ortho-aminophenols and heterocyclic bases,
and addition salts thereof.
12. 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.
13. Dye composition according to Claim 10, characterized in
that the oxidation coupler is chosen from benzene couplers,
heterocyclic couplers and naphthalene couplers, and addition salts
thereof.
14. 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.
15. 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.
16. 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, xanthens dyes and triarylmethane dyes, and
addition salts thereof.

17. Dye composition according to any one of the preceding
claims, characterized in that it comprises at least an oxidizing agent.
18. Process for the oxidation dyeing of keratin fibres,
characterized in that a dye composition as defined in any one of
Claims 1 to 16 is applied to the fibres, in the presence of at least one
oxidizing agent for a period or" time sufficient to develop the desired
colour.
19. 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 16 and at least a second
compartment containing at least one oxidizing agent.
20. Use of the composition defined in any one of Claims 1 to
17, for dyeing keratin fibres, in particular human keratin fibres such as
the hair.

The present invention lelates to a dye composition ior 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 nonionic, nonhydrophobic polymer(s) of the
hydroxyalkylcellulose type; 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.