The present invention relates to a composition for the oxidation
dyeing of keratin fibres, and in particular human keratin fibres such as
the hair, comprising one or more nonionic derivative(s) of cellulose
modified with one or more particular hydrophobic group(s), one or
more dye(s) of diaminodiazacyclopentene type and one or more
oxidation coupler(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 Theological 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 selectivity and fastness.
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 apply, which have good rheological properties and which
produce colorations that are strong and relatively nonselective and that
withstand the various attacks to which keratin fibres may be subjected.
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 oxidation base(s) chosen from diaminodiazacyclo
pentene derivatives, and addition salts thereof;
(C) one or more oxidation coupler(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 term "diaminodiazacyclopentene derivative(s)" is intended
to mean one (or more) compound(s) comprising in its (or their)
molecular structure the following substructure:


A denoting a carbonyl group or a carbon atom bearing a
hydrogen atom or another substituent.
Preferably, the diaminodiazacyclopentene derivative is a
diaminopyrazolone derivative or a diaminopyrazole derivative
The term "diaminopyrazolone derivative(s)" is intended to mean
one (or more) compound(s) comprising in its (or their) molecular
structure the following substructure:

The diaminopyrazolone derivatives are derivatives of
4,5-diaminopyrazol-3-one or 2,3-diaminopyrazol-l-one.
The diaminopyrazolone derivative(s) according to the invention
preferably correspond(s) to general formula (I) below:

in which:
■ R1, R2, R3 and R4, which may be identical or different,
represent, independently of one another:
- a hydrogen atom;
- a linear or branched C1-C10, preferably C1-C6, alkyl group
optionally substituted with one or more groups chosen from OR5,

NR6R7 or carboxyl groups, sulphonic, carboxamido CONR6R7 or
sulphonamido SO2NR6R7 groups, aliphatic heterocycles such as
piperidine, and aryls optionally substituted with one or more group(s)
chosen from C1-C4 alkyl, hydroxyl, C1-C2 alkoxy, amino and
(di)(C1-C2)alkylamino groups;
- an aryl group optionally substituted with one or more group(s)
chosen from C1-C4 alkyl, hydroxyl, C1-C2 alkoxy, amino and
(di)(C1-C2)alkylamino groups;
- a heteroaryl group comprising 5 or 6 ring members, optionally
substituted with one or more group(s) chosen from C1-C4 alkyl and
C1-C2 alkoxy groups;
■ R5, R6 and R7, which may be identical or different, represent:
- a hydrogen atom;
- a linear or branched C1-C4, preferably C1-C2, alkyl group
optionally substituted with one or more group(s) chosen from the
groups: hydroxyl, C1-C2 alkoxy, carboxamido CONR8R9, sulphonyl
SO2R8, and aryl optionally substituted with a C1-C4 alkyl, hydroxyl,
C1-C2 alkoxy, amino or (di)(C1-C2)alkylamino group;
- an aryl group optionally substituted with one or more group(s)
chosen from C1-C4 alkyl, hydroxyl, C1-C2 alkoxy, amino and
(di)(C1-C2)alkylamino groups;
- a carboxamido group CONR8R9;
- a sulphonyl group SO2R8;

■ R8 and R9, which may be identical or different, represent a
hydrogen atom; or a linear or branched C1-C4 alkyl group optionally
substituted with one or more group(s) chosen from hydroxyl and C1-C2
alkoxy groups;
■ R1 and R2, on the one hand, and R3 and R4, on the other hand,
may also form, together with the nitrogen atom(s) to which they are
attached, a saturated or unsaturated heterocycle comprising from 5 to 7
ring members, optionally substituted or N-substituted with one or more
group(s) chosen from halogen atoms, amino, (di)(C1-C4)alkylamino,
(di)hydroxy(C1-C2)alkylamino, hydroxyl, carboxyl, carboxamido,
(di)(C1-C2)alkylcarboxamido and C1-C2 alkoxy groups, and C1-C4 alkyl
groups optionally substituted with one or more groups chosen from
hydroxyl, amino, (di)alkylamino, alkoxy, carboxyl and sulphonyl

groups; it being possible for said heterocycles formed by R1 and R2, on
the one hand, and R3 and R4, on the other hand, with the nitrogen
atom(s) to which they are attached, to be identical or different, and it
being possible for the ring members forming said heterocycles to be
preferably chosen from carbon, nitrogen and oxygen atoms.
According to one particular embodiment, R1 and R2, which
may be identical or different, are chosen, independently of one another,
from:
- a C1-C6 alkyl group optionally substituted with one or more
group(s) chosen from hydroxyl, C1-C2 alkoxy, amino and (di)(C1-C2)-
alkylamino groups; and
- a phenyl, methoxyphenyl, ethoxyphenyl or benzyl group
Preferably, R1 and R2, which may be identical or different,
are chosen, independently of one another, from methyl, ethyl,
2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl and phenyl groups.
According to another embodiment, R1 and R2 form, together
with the nitrogen atoms to which they are attached, a saturated or
unsaturated, 5 or 6-membered ring optionally substituted with one or
more group(s), chosen from halogen atoms, amino, (di)(C1-C4.)alkyl-
amino, (di)hydroxy(C1-C2)alkylamino, hydroxyl, carboxyl,
carboxamido, (di)(C1-C2) alkylcarboxamido and C1-C2 alkoxy groups,
and C1-C4 alkyl groups optionally substituted with one or more
group(s) chosen from hydroxyl, amino, (di)alkylamino, alkoxy,
carboxyl and sulphonyl groups.
Preferably, R1 and R2 form, together with the nitrogen atoms
to which they are attached, a pyrazolidine or pyridazolidine ring
optionally substituted with one or more group(s) chosen from C1-C4
alkyl, hydroxyl, C1-C2 alkoxy, carboxyl, carboxamido, amino and
(di)(C1-C2)alkylamino groups.
Preferably, R1 and R2 form, together with the nitrogen atoms
to which they are attached, a pyrazolidine or pyridazolidine ring
optionally substituted with one or more groups chosen from C1-C4
alkyl, hydroxyl, C1-C2 alkoxy, carboxyl, carboxamido, amino and
(di)(C1-C2)alkylamino groups.
Even more advantageously, R1 and R2 form, together with the
nitrogen atoms to which they are attached, a pyrazolidine, pyridazoline

or pyridazolidine ring.
As regards R3 and R4, the latter, which may be identical or
different, are more particularly chosen from a hydrogen atom; a linear
or branched C1-C6 alkyl group, optionally substituted with one or more
group(s) chosen from hydroxyl, C1-C2 alkoxy, amino and (di)(C1-C2)-
alkylamino groups and aliphatic heterocycles such as piperidine, and a
phenyl group optionally substituted with one or more groups chosen
from hydroxyl, amino and C1-C2 alkoxy groups.
Preferably, R3 and R4, which may be identical or different,
are chosen from a hydrogen atom, and a methyl, ethyl, isopropyl,
2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-carboxyethyl.
2-dimethylaminoethyl, pyrrolidin-1-yl, 3-hydroxypyrrolidin-1 -yl,
4-piperidin-l-yl, 4-methylpiperidin-l-yl or 3-dimethylaminopiperidin-
1-yl group.
According to one particular embodiment, the R3 and R4
groups represent a hydrogen atom.
According to another embodiment, R3 and R4 form, together
with the nitrogen atom to which they are attached, a ring comprising
from 5 to 7 members chosen from the heterocycles pyrrolidine,
piperidine, homopiperidine, piperazine and homopiperazine; it being
possible for said ring to be substituted or N-substituted with one or
more group(s) chosen from the groups: hydroxyl, amino, (di)(C1-C2)-
alkylamino, (di)hydroxy(C1-C2)alkylamino, carboxyl, carboxamido,
(di)(C1-C2)alkylcarboxamido and C1-C4 alkyl optionally substituted
with one or more group(s) chosen from hydroxyl, amino and C1-C2
(di)alkylamino groups.
More particularly, R3 and R4 form, together with the nitrogen
atom to which they are attached, a ring comprising from 5 to 7
members, chosen from pyrrolidine, 2,5-dimethylpyrrolidine,
pyrrolidine-2-carboxylic acid, 3-hydroxypyrrolidine-2-carboxylic acid,
4-hydroxypyrrolidine-2-carboxylic acid, 2,4-dicarboxypyrrolidine,
3-hydroxy-2-hydroxymethylpyrrolidine, 2-carboxamidopyrrolidine,
3-hydroxy-2-carboxamidopyrrolidine, 2-(diethylcarboxamido)-
pyrrolidine, 2-hydroxymethylpyrrolidine, 3,4-dihydroxy-2-hydroxy-
methylpyrrolidine, 3-hydroxypyrrolidine, 3,4-dihydroxypyrrolidine,
3-aminopyrrolidine, 3-methylaminopyrrolidine, 3-dimethylamino-

pyrrolidine, 4-amino-3-hydroxypyrrolidine, 3-hydroxy-4-(2-hydroxy-
ethyl)aminopyrrolidine, piperidine, 2,6-dimethylpiperidine, 2-carboxy-
piperidine, 2-carboxamidopiperidine, 2-hydroxymethylpiperidine,
3-hydroxy-2-hydroxymethylpiperidine, 2-hydroxypiperidine,
3-hydroxypiperidine, 4-hydroxypiperidine, 3-hydroxymethylpiperidine,
homopiperidine, 2-carboxyhomopiperidine, 2-carboxamidohomo-
piperidine, homopiperazine, N-methylhomopiperazine and N-(2-
hydroxyethyl)homopiperazine.
Preferably, R3 and R4 form, together with the nitrogen atom
to which they are attached, a ring comprising from 5 to 7 members,
chosen from pyrrolidine, 3-hydroxypyrrolidine, 3-aminopyrrolidine,
3-dimethylaminopyrrolidine, pyrrolidine-2-carboxylic acid, 3-hydroxy-
pyrrolidine-2-carboxylic acid, piperidine, hydroxypiperidine,
homopiperidine, 1,4-diazepane, N-methylhomopiperazine and N-(3-
hydroxyethylhomopiperazine.
In accordance with an even more preferred embodiment of the
invention, R3 and R4 form, together with the nitrogen atom to which
they are attached, a 5-membered ring such as pyrrolidine, 3-hydroxy-
pyrrolidine, 3-aminopyrrolidine or 3-dimethylaminopyrrolidine.
The compounds of formula (I) may be optionally salified with
strong mineral acids such as, for example, HC1, HBr, HI, H2SO4 or
H3PO4, or organic acids such as, for example, acetic acid, lactic acid
tartaric acid, citric acid, succinic acid, benzenesulphonic acid, para-
toluenesulphonic acid, formic acid or methanesulphonic acid.
They may also be in the form of solvates, for example a
hydrate, or a solvate of a linear or branched alcohol, such as ethanol or
isopropanol.
By way of examples of derivatives of formula (I), mention
may be made of the compounds below and the addition salts thereof:
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-dihydropyrazoI-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)-1,2-
dihydropyrazol-3-one;
4-amino-5-(pyrrolidin-1-yl)-1,2-di-(2-hydroxyethyl)-1,2-
dihydropyrazol-3-one;
4-amino-5-(piperidin-1-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-1-ethyl-2-methyl-1,2-dihydropyrazol-3-one;
4,5-diamino-2-ethyl-1-methyl- l,2-dihydropyrazol-3-one;
4,5-diamino-1-phenyl-2-methyl-1,2-dihydropyrazol-3-one;
4,5-diarnino-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[1,2-a]-
pyrazol-1-one;
2-amino-3-(2-hydroxypropyl)amino-6,7-dihydro-1H,5H-pyrazolo-
[ 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-1 H,5H-pyrazolo-
[1,2-a]pyrazol-1-one;

2-amino-3-(3-hydroxy-pyrrolidin-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-yl-propylamino)-1,2-
dihydropyrazol-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-
dihydropyrazol-3-one;
4-amino-1,2-diethyl-5-(4-methylpiperazin-1-yl)pyrazolidin-3-one;
some of which appear below so as to illustrate the names with chemical
structures:

Among these compounds, the diaminopyrazolone derivatives of
formula (I) that are particularly preferred are the following:
2,3-diamino-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-I-
one;
2-amino-3-isopropylamino-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;
4,5-diamino-1,2-dimethyl-1,2-dihydropyrazol-3-one;
4,5-diamino-1,2-diethyl-1,2-dihydropyrazol-3-one;
4,5-diamino-1,2-di-(2-hydroxyethyl)-1,2-dihydropyrazol-3-one;
2-amino-3-(2-hydroxyethyl)amino-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;
2,3-diamino-5,6,7,8-tetrahydro-1H,6H-pyridazino[1,2-a]pyrazol-1-one
4-amino-1,2-diethyl-5-pyrrolidin-1-yl-1,2-dihydropyrazol-3-one;
4-amino-5-(3-dimethylamino-pyrrolidin-1-yl)-1,2-diethyl-1,2-dihydro-
pyrazol-3-one;
2,3-diamino-6-hydroxy-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-
one.
Even more particular preference is given to 2,3-diamino-6,7-

dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and salts thereof, .such as
2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one
dimethane sulphonate of formula:

The term "diaminopyrazole derivative(s)" is intended to mean
one (or more) compound(s) comprising in its (or their) molecular
structure the following substructure:

The diaminopyrazole derivative is therefore a derivative of
4,5-diaminopyrazole.
The diaminopyrazole derivative(s) according to the invention
preferably correspond(s) to general formula (II) below:

in which:
- R1, R2, R3, R4 and R5, which may be identical or different, represent a
hydrogen atom; a C1-C6 alkyl radical which is unsubstituted or
substituted with at least one substituent chosen from OR, NHR, NRR',
SR, SOR, SO2R, COR, COOH, CONH2, CONHR, CONRR', PO(OH)2,
SH, SO3X, a noncationic heterocycle, CI, Br or I, X denoting a
hydrogen atom, Na, K, or NH4, and R and R' ,which may be identical or

different, representing a C1-C4 alkyl or alkenyl; a C2-C4 hydroxyalkyl
radical; a C2-C4 aminoalkyl radical; a phenyl radical; a phenyl radical
substituted with a halogen atom or a C1-C4 alkyl, C1-C4 alkoxy, nitro,
trifluoromethyl, amino or C1-C4 alkylamino radical; a benzyl radical; a
benzyl radical substituted with a halogen atom or with a C1-C4 alkyl,
C1-C4 alkoxy, methylenedioxy or amino radical; a radical

in which m and n are integers, which may be identical or different,
between 0 and 3 inclusive, X represents an oxygen atom or else the
group NH, Y represents a hydrogen atom or else a C1-C4 alkyl radical,
and Z represents a methyl radical when n is equal to 0, or Z represents
a C1-C4 alkyl radical, or an OR or NR' ' Rgr'oup when n is greater than
or equal to 1, R' and R' ' which may be identical or different, denoting
a hydrogen atom or a C1-C4 alkyl radical; or R9 forms, with the
nitrogen atom of the NR7R8 group at position 5, a heterocycle
comprising at least 4 ring members,
- R6 represents a C1-C6 alkyl radical; a C1-C4 hydroxyalkyl radical; a
C1-C4 aminoalkyl radical; a (C1-C4)alkylamino(C1-C4)alkyl radical; a
di(C1-C4)alkylamino(C1-C4)alkyl radical; a hydroxy(C1-C4)alkylamino
(C1-C4)alkyl radical; a (C1-C4)alkoxymethyl radical; a phenyl radical; a
phenyl radical substituted with a halogen atom or with a (C1-C4)alkyl,
(C1-C4)alkoxy, nitro, trifluoromethyl, amino or (C1-C4)alkylamino
radical; a benzyl radical; a benzyl radical substituted with a halogen
atom or with a (C1-C4)alkyl, (C1-C4)alkoxy, nitro, trifluoromethyl,
amino or (C1-C4)alkylamino radical; a heterocycle chosen from
thiophene, furan and pyridine, or else a -(CH2)P-O-(CH2)q-OR' radical,
in which p and q are integers, which may be identical or different,
between 1 and 3 inclusive, and R' Is as defined above,
it being understood that:
at least one of the radicals R1, R2, R3 and R4 represents a hydrogen
atom.
The compounds of formula (II) may be optionally salified with
strong mineral acids such as, for example, HC1, HBr, HI, H2SO4 or
H3PO4, or organic acids such as, for example, acetic acid, lactic acid,

tartaric acid, citric acid, succinic acid, benzenesulphonic acid, para-
toluenesulphonic acid, formic acid or methanesulphonic acid.
They may also be in the form of solvates, for example, a
hydrate, or a solvate of a linear or branched alcohol, such as ethanol or
isopropanol.
By way of examples of derivatives of formula (II) that can be
used according to the invention, mention may be made 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, for instance 4,5-diamino-1-methylpyrazole,
4,5-diamino-l -(2-hydroxyethyl)pyrazole, 4,5-diamino-1-(4'-chloro-
benzyl)pyrazole, 4,5-diamino-l ,3-dimethylpyrazole, 4,5-diamino-3-
methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole,
4-amino-1,3-dimethyl-5-hydrazinopyrazole, l-benzyl-4,5-diamino-3-
methylpyrazole, 4,5-diamino-3-tert-butyl-l -methylpyrazole, 4,5-di-
amino-l -tert-butyl-3-methylpyrazole, 4,5-diamino-1-(P-hydroxyethyl)-
3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-
I-ethyl-3-(4'-methoxyphenyl)pyrazole, 4,5-diamino-l -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 and 4-amino-5-(2'-aminoethyl)amino-1,3-
dimethylpyrazole, and addition salts thereof.
Preference is even more particularly given to 4,5-diamino-1-(2-
hydroxyethyl)-1H-pyrazole and salts thereof, such as 4,5-diamino-1-(2-
hydroxyethyl)-1H-pyrazole sulphate, having the formula below:

The oxidation bases of diaminodiazacyclopentene type may be
present alone or as a mixture in the compositions of the invention.
The oxidation base(s) (B) of diaminodiazacyclopentene type is
(or are) in general present in concentrations ranging from 0.001% to
20% by weight, preferably from 0.005% to 10% by weight, and more

preferably from 0.01% to 5% by weight, relative to the total weight of
the composition.
The oxidation coupler(s) (C) 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
addition salts thereof.
Among the preferred couplers, mention may be made of
2-methyl-5-aminophenol, 5-N-(G-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-1-(B-hydroxyethyloxy)benzene, 2-amino-4-(B-
hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1.3-bis-
(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido-1-
dimethylaminobenzene, sesamol, l-B-hydroxyethylamino-3,4-
methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxy-
indole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-
hydroxypyridine, 6-hydroxybenzomorpholine 3,5-diamino-2,6-
dimethoxypyridine, l-N-(B-hydroxyethyl)amino-3,4-methylene
dioxybenzene and 2,6-bis-(B-hydroxyethylamino)toluene, and addition
salts thereof with an acid.
The concentration of oxidation coupler(s) (C) ranges from
0.001% to 20% by weight, preferably from 0.005% to 10% by weight,
even more preferably from 0.01% to 5% by weight, relative to the total
weight of the composition.
The compositions of the invention may also comprise one or
more additional oxidation base(s).
The term "additional oxidation base(s)" is intended to mean one
or more oxidation base(s) different from the oxidation basels) of
diaminodiazacyclopentene type (B) mentioned above.
By way of example, these additional oxidation bases are chosen
from para-phenylenediamines, bisphenylalkylenediamines, para-
aminophenols, bis-para-aminophenols, ortho-aminophenols and
heterocyclic bases other than the diaminodiazacyclopentene oxidation

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-hydroxyethyi)-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-
(3-hydroxyethyl)-para-phenylenediamine, N-(β,γ-dihydroxypropyl)-
para-phenylenediamine, N-(4'-aminophenyl)-para-phenylenedi amine,
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-1-(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 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 l,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 and pyrimidine 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-
methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxy-
pyridine, 2-(β-methoxyethyl)amino-3-amino-6-methoxypyridine and
3,4-diaminopyridine, 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-aminopyrazoio-
[1,5-a]pyridin-2-yl)methanol; 3,6-diaminopyrazolo[1,5-a]pyridine; 3,4-
diaminopyrazolo[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-di-
hydroxy-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-dimethylpyrazolo[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-aminopyrazolo-
[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-dimethylpyrazolo-
[1,5-a]pyrimidine-3,7-diamine, 2, 5, N7, N7-tetramethylpyrazolo-
[1,5-a]pyrimidine-3,7-diamine, 3-amino-5-methyl-7-imidazolylpropyl-
aminopyrazolo[1,5-a]pyrimidine, and addition salts thereof with an
acid and tautomeric forms thereof when a tautomeric equilibrium
exists.
The additional oxidation base(s) present in the composition of
the invention is (are) in general present in an amount of between
0.001% and 10% by weight approximately, of the total weight of the
dye composition, preferably between 0.005% and 6%.
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

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.
Particularly preferably, the additional oxidation bases used in
the compositions according to the invention are chosen from para-
phenylenediamines and para-aminophenols, and addition salts thereof.
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 triarylrnethane 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, hydroxypropyl-
cellulose, 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; 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,
plant or animal 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 (or 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 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 (III) 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 hydroxy-
alkyl 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 coloration. 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-2 586 913.
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.



Application protocol
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 coloration is evaluated visually. The results obtained
on natural grey hair, containing 90% white hairs, after treatment, are
the following:

These colorations have good properties, in particular in terms
of selectivity and fastness. They also have good 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).
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


Composition 3 according to the invention results in stronger
colouring on natural hair and also in lower selectivity.

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 oxidation base(s) chosen from diaminodiazacyclo-
pentene derivatives, and addition salts thereof;
(C) one or more oxidation coupler(s).

2. Dye composition according to Claim 1, characterized in
that the nonionic derivative of cellulose 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 i % 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 diaminodiazacyclopentene derivative
is a diaminopyrazolone derivative.
8. Dye composition according to Claim 7, characterized in

that the diaminopyrazolone derivative corresponds to formula (I)
below:
in which:
■ R1, R2, R3 and R4, which may be identical or different.
represent, independently of one another:
- a hydrogen atom;
- a linear or branched C1-C10, preferably C1-C6, alkyl group
optionally substituted with one or more groups chosen from OR5,
NR6R7 or carboxyl groups, sulphonic, carboxamido CONR6R7 or
sulphonamido SO2NR6R7 groups, aliphatic heterocycles such as
piperidine, and aryls optionally substituted with one or more group(s)
chosen from C1-C4 alkyl, hydroxyl, C1-C2 alkoxy, amino and
(di)(C1-C2)alkylamino groups;
- an aryl group optionally substituted with one or more
group(s) chosen from C1-C4 alkyl, hydroxyl, C1-C2 alkoxy, amino and
(di)(C1-C2)alkylamino groups;
- a heteroaryl group comprising 5 or 6 ring members, optionally
substituted with one or more group(s) chosen from C1-C4 alkyl and
C1-C2 alkoxy groups;
■ R5, R6 and R7, which may be identical or different, represent:
- a hydrogen atom;
- a linear or branched C1-C4, preferably C1-C2, alkyl group
optionally substituted with one or more group(s) chosen from the
groups: hydroxyl, C1-C2 alkoxy, carboxamido CONR8R9, sulphonyl
SO2R8, and aryl optionally substituted with a C1-C4 alkyl, hydroxyl,
C1-C2 alkoxy, amino or (di)(C1-C2)alkylamino group;
- an aryl group optionally substituted with one or more
group(s) chosen from C1-C4 alkyl, hydroxyl, C1-C2 alkoxy, amino and
(di)(C1-C2)alkylamino groups;
- a carboxamido group CONR8R9;

- a sulphonyl group SO2R8;
■ R8 and R9, which may be identical or different, represent a
hydrogen atom; or a linear or branched C1-C4 alkyl group optionally
substituted with one or more group(s) chosen from hydroxyl and C1-C2
alkoxy groups;
■ R1 and R2 on the one hand, and R3 and R4, on the other hand,
may also form, together with the nitrogen atom(s) to which they are
attached, a saturated or unsaturated heterocycle comprising from 5 to 7
ring members, optionally substituted or N-substituted with one or more
group(s) chosen from halogen atoms, amino, (di)(C1-C4)alkylamino.
(di)hydroxy(C1-C2)alkylamino, hydroxyl, carboxyl, carboxamido,
(di)(C1-C2)alkylcarboxamido and C1-C2 alkoxy groups, and C1-C4 alkyl
groups optionally substituted with one or more groups chosen from
hydroxyl, amino, (di)alkylamino, alkoxy, carboxyl and sulphonyl
groups; it being possible for said heterocycles formed by R1 and R2, on
the one hand, and R3 and R4, on the other hand, with the nitrogen
atom(s) to which they are attached, to be identical or different, and it
being possible for the ring members forming said heterocycles to be
preferably chosen from carbon, nitrogen and oxygen atoms.

9. Dye composition according to the preceding claim,
characterized in that the diaminopyrazolone derivative corresponding
to formula (I) is 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo-
[1,2-a]pyrazol-1-one or an addition salt thereof.
10. Dye composition according to any one of Claims 1 to 6,
characterized in that the diaminodiazacyclopentene derivative is a
diaminopyrazole derivative.
11. Dye composition according to Claim 10, characterized in
that the diaminopyrazole derivative corresponds to formula (II) below:


(II)
in which:
- R1, R2, R3, R4 and R5, which may be identical or different, represent a
hydrogen atom; a C1-C6 alkyl radical which is unsubstituted or substituted
with at least one substituent chosen from OR, NHR, NRR', SR, SOR,
SO2R, COR, COOH, CONH2, CONHR, CONRR', PO(OH)2, SH, SO3X, a
noncationic heterocycle, C1, Br or I, X denoting a hydrogen atom. Na, K.
or NH4, and R and R' ,which may be identical or different, representing a
C1-C4 alkyl or alkenyl; a C2-C4 hydroxyalkyl radical; a C2-C4 aminoalkyl
radical; a phenyl radical; a phenyl radical substituted with a halogen atom
or a C1-C4 alkyl, C1-C4 alkoxy, nitro, trifluoromethyl, amino or C1-C4
alkylamino radical; a benzyl radical; a benzyl radical substituted with a
halogen atom or with a C1-C4 alkyl, C1-C4 alkoxy, methylenedioxy or
amino radical; a radical

in which m and n are integers, which may be identical or different,
between 0 and 3 inclusive, X represents an oxygen atom or else the group
NH, Y represents a hydrogen atom or else a C1-C4 alkyl radical, and Z
represents a methyl radical when n is equal to 0, or Z represents a C1-C4
alkyl radical, or an OR or NR' ' R' ' ' group n is greater than or equal to
1, R' 'and R' ' which may be identical or different, denoting a hydrogen
atom or a C1-C4 alkyl radical; or R9 forms, with the nitrogen atom of the
NR7R8 group at position 5, a heterocycle comprising at least 4 ring
members,
- R6 represents a C1-C6 alkyl radical; a C1-C4 hydroxyalkyl radical; a C1-
C4 aminoalkyl radical; a (C1-C4)alkylamino(C1-C4)alkyl radical; a di(C1-
C4)alkylamino(C1-C4)alkyl radical; a hydroxy(C1-C4)alkylamino(C1-
C4)alkyl radical; a (C1-C4)alkoxymethyl radical; a phenyl radical; a phenyl
radical substituted with a halogen atom or with a (C1-C4)alkyl, (C1-
C4)alkoxy, nitro, trifluoromethyl, amino or (C1-C4)alkylamino radical; a
benzyl radical; a benzyl radical substituted with a halogen atom or with a
(C1-C4)alkyl, (C1-C4)alkoxy, nitro, trifluoromethyl, amino or (C1-
C4)alkylamino radical; a heterocycle chosen from thiophene, furan and
pyridine, or else a -(CH2)P-O-(CH2)q-OR' 'radical, in which p and q are

integers, which may be identical or different, between 1 and 3 inclusive,
and R' is as defined above,
it being understood that:
at least one of the radicals R1, R2, R3 and R4 represents a hydrogen atom.
12. Dye composition according to the preceding claim,
characterized in that the diaminopyrazole derivative corresponding to
formula (II) is 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole or an
addition salt thereof, such as the sulphate salt.
13. Dye composition according to any one of the preceding
claims, characterized in that the concentration of oxidation basels) (B)
ranges from 0.001% to 20% by weight, preferably from 0.005% to 10%
by weight, and more preferably from 0.01% to 5% 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 coupler (C) is chosen from
benzene couplers, heterocyclic couplers and naphthalene couplers, and
addition salts thereof.
15. Dye composition according to the preceding claim,
characterized in that the oxidation coupler (C) is a benzene coupler
chosen from meta-aminophenols, meta-phenylenediamines and meta-
diphenols, and addition salts thereof.
16. Dye composition according to any one of the preceding
claims, characterized in that the concentration of oxidation coupler(s)
(C) ranges from 0.005% to 15% by weight, preferably from 0.01% to
10% by weight, and even more preferably from 0.5% to 5% by weight,
relative to the total weight of the composition.
17. Dye composition according to any one of the preceding
claims, characterized in that it comprises one or more additional
oxidation base(s), other than the diaminodiazacyclopentene derivatives
(B), chosen from benzene oxidation bases and heterocyclic bases
18. Dye composition according to the preceding claim,
characterized in that the additional oxidation base is a benzene
oxidation base chosen from ortho- and para-phenylenediamines,
bisphenylalkylenediamines, para-aminophenols, bis-para-aminophenols
and ortho-aminophenols, and addition salts thereof.

19. 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.
20. Dye composition according to any one of the preceding
claims, characterized in that it comprises at least one oxidizing agent.
21. Process for the oxidation dyeing of keratin fibres,
characterized in that a dye composition as defined in any one of
Claims 1 to ] 9 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.
22. 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 19 and at least a second
compartment containing at least one oxidizing agent.
23. Use of the composition defined in one of Claims 1 to 20,
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 at
least one hydrophobic substituent containing from 8 to 30 carbon
atoms;
(B) one or more oxidation base(s) chosen from
diaminodiazacyclopentene derivatives;
(C) one or more oxidation coupler(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 keratin fibres.