Tri-aromatic azomethine direct dyes comprising at least one unit
derived from resorcinol, dyeing composition, method and use
The present invention relates to specific tri-aromatic
azomethine- type direct dyes comprising at least one unit derived from
resorcinol and their use for colouring keratin fibres, in particular
human keratin fibres such as the hair.
The invention also relates to a composition for dyeing keratin
fibres comprising, in a suitable medium for dyeing, such direct dyes
and a method for dyeing using said composition.
Lastly, the invention relates to precursors for these direct dyes,
their use for colouring fibres and a multi-compartment device
containing them.
The present invention relates to the field of dyeing keratin
fibres and more particularly to the field of hair dyeing.
It is known practice to dye keratin fibres, and in particular the
hair, with dyeing compositions containing one or more direct dyes,
according to a "direct dyeing" method.
The method conventionally used in direct dyeing consists in
applying to keratin fibres one or more direct dyes, or colouring
molecules, which have an affinity for the said fibres, leaving them to
take on the fibres, and then rinsing the fibres. The direct dyes used
hitherto are generally nitrobenzene dyes, anthraquinone dyes,
nitropyridine dyes, dyes of azo, xanthene, acridine or azine type or
triarylmethane-based dyes.
These direct dyes may also be applied to keratin fibres in the
presence of an oxidizing agent if the goal is to obtain a simultaneous
lightening effect for the fibres.
However, the resulting colours are temporary or semipermanent
since the nature of the interactions that bind the direct dyes
to the keratin fibre and their desorption from the surface and/or the
core of the fibre are responsible for their weak dyeing power and their
poor fastness with respect to washing, inclement weather or
perspiration.
Moreover, such direct dyes are generally sensitive to the action
of oxidizing agents, which makes them difficult to use in particular in
lightening direct dye compositions that are formulated from hydrogen
peroxide and an alkaline agent, which are similar to compositions used
for oxidation dyeing. In other words, direct dyes are generally not very
compatible with dyeing compositions intended to lighten fibres and,
consequently, using them in a lightening dyeing process as an
alternative to oxidation dyeing is not yet entirely satisfactory.
These dyes also have the drawback of lacking light stability,
because of the chromophore having low resistance to photochemical
attacks, which tends to lead to the colour of the keratin fibres fading
over time.
Therefore there is a real need for having direct dyes that not
only dye keratin fibres satisfactorily but that are also stable to light,
can lead to colours that resist the various attacks that fibres may be
subject to, such as inclement weather, washing and perspiration, and
further, that are sufficiently stable in the presence of oxidizing agents
such as hydrogen peroxide to be able to deliver simultaneous fibre
lightening with the benefits set out hereinbefore.
These aims are achieved with the present invention, which
particularly relates to azomethine-type direct dyes with a tri-aromatic
unit having the following formula (I):
(I)
and their organic or inorganic salts with an acid or a base, their
tautomeric forms, optical isomers, geometric isomers and/or their
solvates;
formula (I) in which:
• n denotes an integer equal to 0, 1, 2, 3 or 4;
• R denotes:
- a linear or branched C1-C4 alkyl radical, optionally
substituted by one or more radicals the same or different
chosen from hydroxyl or imidazolium, An radicals; An
designating an anion or a mixture of cosmetically acceptable
anions;
- a C1-C4 alkoxy radical;
- a halogen atom;
• Ri denotes:
- a hydrogen atom,
- a linear or branched C1-C9 alkyl radical, optionally
substituted by one or more hydroxyl radicals,
- a C1-C3 alkoxy radical;
• R2 denotes:
- a hydrogen atom,
- a linear or branched C3-C9 alkyl radical, optionally
substituted by one or more hydroxyl radicals,
- a C1-C3 alkoxy radicals,
- a Ci-C 2 alkyl radical when Ri is other than a hydrogen
atom;
• X denotes:
- a hydroxyl radical,
- a -NR 3R4 radical in which:
■ R 3 denotes a hydrogen atom or a linear or branched Ci-C
alkyl radical, optionally substituted by one or more
hydroxyl or C1-C4 alkoxy radicals;
■ R 4 denotes a hydrogen atom or a linear or branched Ci-C
alkyl radical, optionally substituted by one or more
hydroxyl or C1- C 4 alkoxy radicals;
• it being understood that when Ri and R2 denote a hydrogen
atom and n equals 0 then X does not denote a hydroxyl or amino -NH 2
radical.
A further subject of the present invention relates to the use of
one or more azomethine-type direct dyes of formula (I) as defined
previously for colouring keratin fibres, in particular human keratin
fibres such as the hair.
The present invention also relates to a composition for dyeing
keratin fibres, particularly human keratin fibres such as the hair,
comprising, in a suitable medium for dyeing, one or more azomethinetype
direct dyes of formula (I) as defined previously.
Specifically, the invention also relates to the use of said dyeing
composition for colouring keratin fibres, in particular human keratin
fibres such as the hair.
The invention further relates to a colouring method for keratin
fibres, particularly human keratin fibres such as the hair, in which said
dyeing composition according to the invention is applied to said fibres
for a long enough period to obtain the desired colour, after which the
fibres are rinsed, optionally washed with shampoo, rinsed again and
the resulting fibres are dried or left to dry.
In the same way, the invention relates more specifically to a
lightening method for keratin fibres, in particular human keratin fibres
such as the hair, in which (i) said dyeing composition free of oxidizing
agent and (ii) a cosmetic composition comprising one or more
oxidizing agents are applied to said fibres; compositions (i) and (ii)
being applied to said keratin fibres sequentially or simultaneously a
for long enough period to obtain the desired lightening, after which
the fibres are rinsed, optionally washed with shampoo, rinsed again
and the resulting fibres are dried or left to dry.
Accordingly, the invention also relates to a multi-compartment
device or dyeing kit comprising a first compartment containing one or
more direct dyes of formula (I) as defined previously and a second
compartment containing one or more oxidizing agents.
The azomethine-type direct dyes of formula (I) according to the
invention can thereby lead to colours that resist the various attacks
that keratin fibres can be subject to, such as inclement weather, light,
washing and perspiration.
What is more, the direct dyes according to the invention can
dye keratin fibres satisfactorily, in particular by leading to powerful,
chromatic and sparingly selective colours and can lead to an improved
uptake colouration.
The direct dyes according to the invention have the benefit of
being stable to light and may be used in the presence of an oxidizing
agent, which makes using them in lightening direct dye compositions
based upon oxidizing agents easier.
In other words, the direct dyes according to the present
invention lead to long-lasting colours and are compatible with dyeing
compositions that are intended to lighten keratin fibres.
Moreover, the invention relates to leuco-type colourless
compounds, which correspond to the reduced form of the azomethinetype
direct dyes according to the invention, having the following
formula (II):
and their organic or inorganic salts with an acid or a base, their
tautomeric forms, optical isomers, geometric isomers and/or their
solvates such as hydrates;
formula (II) in which n, R, Rl R2 and X have the same meanings as
indicated previously.
The leuco-type compounds according to the invention may
therefore lead in the presence of one or more oxidizing agents to
azomethine-type direct dyes of formula (I).
Accordingly, the invention also relates to the use of one or
more leuco-type compounds of formula (II) as precursors for direct
dyes of formula (I).
In particular, the invention relates to the use of one or more
leuco-type compounds of formula (II) in the presence of one or more
oxidizing agents for colouring keratin fibres, in particular human
keratin fibres such as the hair.
The invention also relates to a multi-compartment device or
dyeing kit containing a first compartment comprising one or more
leuco-type compounds of formula (II) such as defined hereinbefore and
a second compartment comprising one or more oxidizing agents.
The leuco-type compounds of formula (II) used under oxidizing
conditions thereby have the benefit of leading to colours that resist the
various attacks that keratin fibres can be subject to, such as inclement
weather, washing, light or perspiration.
Other features, aspects, subjects and benefits of the present
invention will emerge even more clearly on reading the description
and the examples that follow.
. Azomethine-type compound with a tri-aromatic unit
The direct dyes of formula (I) according to the present
invention comprise at least one unit derived from resorcinol (metadihydroxybenzene)
and an azomethine bond.
An designates an anion or a mixture of cosmetically
acceptable anions such as, for example, halides, such as chloride,
methosulfates, nitrates; alkylsulfonates: Alk-S(0) 20 such as
methylsulfonate or mesylate and ethylsulfonate; arylsulfonates: Ar-
S(0) 20 such as benzenesulfonate and toluenesulfonate or tosylate;
citrate; succinate; tartrate; lactate; alkyl sulfates: Alk-0-S(0)0 such
as methyl sulfate; aryl sulfates such as benzene sulfate and toluene
sulfate; phosphate; acetate; triflate; and borates such as
tetrafluoroborate.
Preferably, An is an anionic counter-ion chosen from bromide,
chloride, methyl sulfate, toluenesulfonate ions or a mixture of these
ions.
According to one embodiment, in formula (I) for azomethinetype
direct dyes according to the invention, considered in isolation or
in combination:
• n denotes an integer equal to 0, 1 or 2;
• R denotes:
- a C1-C2 alkyl radical, optionally substituted by one or
more hydroxyl or imidazolium, An radicals; An designating an
anion or a mixture of cosmetically acceptable anions;
- a C1-C2 alkoxy radical;
- a chlorine atom;
• P i denotes:
- a hydrogen atom,
- a linear or branched C1-C9 alkyl radical,
- a linear or branched C1-C3 alkyl radical, substituted by a
hydroxyl radical,
- a C1-C2 alkoxy radical;
• P 2 denotes:
- a hydrogen atom,
- a linear or branched C3-C9 alkyl radical,
- a C1-C2 alkoxy radical,
- a C1-C2 alkyl radical when Ri is other than a hydrogen
atom; and/or
• X denotes:
- a hydroxyl radical,
- a -NR 3R4 radical in which:
■ R3 denotes a hydrogen atom or a linear or branched -
C 3 alkyl radical, optionally substituted by one or more
hydroxyl or C1-C2 alkoxy radicals;
■ R4 denotes a hydrogen atom or a linear or branched -
C3 alkyl radical, optionally substituted by one or more
hydroxyl or C1-C2 alkoxy radicals;
• it being understood that when Ri and R2 denote a hydrogen
atom and n equals 0 then X does not denote a hydroxyl or amino -NH2
radical.
According to a specific embodiment, in formula (I) for
azomethine-type direct dyes according to the invention, considered in
isolation or in combination:
• n denotes an integer equal to 0, 1 or 2;
• R denotes:
- a methyl radical,
- a chlorine atom;
• Ri denotes:
- a hydrogen atom,
- a methyl, pentyl or heptyl radical,
- a methyl radical substituted by a hydroxyl radical,
- a methoxy radical;
• R2 denotes:
- a hydrogen atom,
- a propyl radical,
- a methoxy radical,
- a methyl radical when Ri is other than a hydrogen atom;
and/or
• X denotes:
- a hydroxyl radical,
- a -NR 3R4 radical in which:
■ R3 denotes a hydrogen atom or an ethyl or isopropyl
radical,
■ R 4 denotes a hydrogen atom or a linear or branched Ci-
C3 alkyl radical, optionally substituted by one or more
hydroxyl radicals;
• it being understood that when R and R2 denote a hydrogen
atom and n equals 0 then X does not denote a hydroxyl or amino -NH2
radical.
Preferably, n denotes an integer equal to 0, 1 or 2, in particular
1 or 2 . Preferably, n denotes an integer equal to 1.
Preferably, R denotes a linear or branched C1-C4 alkyl radical,
in particular a C -C2 alkyl radical. In particular, R denotes a methyl
radical.
Preferably, R denotes a hydrogen atom or a linear or branched
C1-C9 alkyl radical. In particular, R denotes a hydrogen atom or a
methyl radical.
In accordance with formula (I) for direct dyes according to the
invention, R2 denotes a C -C2 alkyl radical when R is other than a
hydrogen atom. In other words, when R denotes a hydrogen atom then
R2 is other than a C -C2 alkyl radical.
Preferably, R2 denotes a hydrogen atom.
According to one embodiment, R denotes a hydrogen atom or
a linear or branched C1-C9 alkyl radical, in particular a C alkyl
radical, and R2 denotes a hydrogen atom.
According to another embodiment, R denotes a hydrogen atom
and R2 denotes a C -C2 alkoxy radical.
According to another embodiment, R denotes a linear or
branched C1-C3 alkyl radical, substituted by a hydroxyl radical and R2
denotes a hydrogen atom.
According to another embodiment, R denotes a hydrogen atom
and R2 denotes a linear or branched C3-C9 alkyl radical, in particular a
C3 alkyl radical.
According to another embodiment, R denotes a linear or
branched C1-C9 alkyl radical, in particular C , and R2 denotes a C -C2
alkyl radical, in particular a C alkyl radical.
Preferably, X denotes a -NR 3R4 radical in which R 3 denotes a
hydrogen atom or a linear or branched C1-C 3 alkyl radical, optionally
substituted by a hydroxyl radical and R4 denotes a hydrogen atom or a
linear or branched C 1- C 3 alkyl radical, optionally substituted by a
hydroxyl radical.
According to a preferred embodiment, X denotes a -NR 3R4
radical in which R3 and R4 represent a hydrogen atom.
According to another preferred embodiment, X denotes a -
NR3R4 radical in which R3 and R4 are different from a hydrogen atom.
Preferably, the azomethine-type direct dyes of formula (I)
according to the invention are chosen from the following compounds
and their geometric or optical isomeric forms, their salts with an
organic or inorganic acid, or their solvates such as hydrates:
2-(4-Aminophenylamino)-4-[4-
aminophenylimino]-5-hydroxy-
3-methylcyclohexa-
2,5-dienone
Compound 4
5-Hydroxy-2-(4-hydroxyphenylamino)
-4-[4-hydroxyphenylimino]-3-
methylcyclohexa-2,5-dienone
Compound 5
2-(4-Amino-3 (or 2)-methylphenylamino)-
4-
[4-amino-3 (or 2)-methylphenylimino]-
5-hydroxy-3-methylcyclohexa-
2,5-dienone
Com ound 6
2-(3-Chloro-4-hydroxyphenylamino)-
4-[3-chloro-4-hydroxyphenylimino]-
5-hydroxy-3-
methylcyclohexa-2,5-dienone
Compound 7
2-(2-Chloro-4-hydroxyphenylamino)-
4-[2-chloro-4-hydroxyphenylimino]-
5-hydroxy-3-
methylcyclohexa-2,5-dienone
Compound 8
5-Hydroxy-2-[4-(6-hydroxyhexylamino)
phenylamino]-4-
[4-(6-hydroxyhexylamino)
phenylimino]-3-
methylcyclohexa-
2,5-dienone
Compound 9
2-[4-(Ethylisopropylamino)-
phenylamino]-
4-[4-(ethylisopropylamino)
phenylimino]-5-
hydroxycyclohexa-2,5-
dienone
Compound 10
2- {4-[Ethyl(2-hydroxyethyl)
amino]-2-methylphenylamino}
-4- {4- [ethylshydro
xyethyl) amino] -2-
methylphenylimino }-5-
hydroxycyclohexa-
2,5-dienone
Compound 11
2-(4-Amino-2,3-dimethylphenylamino)-
4-[4-amino-2,3-
dimethylphenylimino]-5-
hydroxy-3-methylcyclohexa-
2,5-dienone
Compound 12
2-(4-Amino -3-methy1-
phenylamino)-4-
[4-amino-3 (or 2)-methylphenylimino]-
5-hydroxycyclohexa-2,5-
Compound 13 dienone
2-(3-Chloro-4-hydroxyphenylamino)-
4-[3-chloro-4-hydroxyphenylimino]-
5-hydroxycyclohexa-
2,5-dienone
Compound 14
C I C I
2-(2-Chloro-4-hydroxyphenylamino)-
4-[2-chloro-4-hydroxyphenylimino]-
5-hydroxycyclohexa-
2,5-dienone
Compound 15
5-Hydroxy-2-[4-(6-hydroxy-
J H hexylamino)phenylamino]-4-
[4-(6-hydroxyhexylamino)
phenylimino]-
cyclohexa-2,5-dienone
OH
Compound 16
6-[4-(Ethylisopropylamino)-
phenylamino]-
4-[4-(ethylisopropylamino)
phenylimino]-3-
hydroxy-2-methoxycyclohexa-
2,5-dienone
Compound 17
2- (4-[Ethyl(2-hydroxyethyl)-
amino]-2-methyl-
HO N phenylamino} -4- {4-[ethyl(2-
hydro xyethyl) amino] -2-
methylphenylimino }-3-
OH hydroxy-2-methoxy-
Compound 18 cyclohexa-2,5-dienone
2-(4-Amino-2,3-dimethylphenylamino)-
4-[4-amino-2,3-
dimethylphenylimino]-3-
hydroxy-2-methoxycyclohexa-
/ ° 2,5-dienone
Compound 19
2-(4-Aminophenylamino)-4-[4-
aminophenylimino]-3-hydroxy-
2-methoxy-
/ ° cyclohexa-2,5-dienone
Compound 20
3-Hydroxy-2-(4-hydroxyphenylamino)
-4-[4-hydroxyphenylimino]-2-
/ ° methoxycyclohexa-2,5-dienone
Compound 21
2-(4-Amino-3 (or 2)-methylphenylamino)-
4-
[4-amino-3 (or 2)-methylphenylimino]-
/ 3-hydroxy-2-methoxycyclohexa- 2,5-dienone
Compound 22
2-(3-Chloro-4-hydroxyphenylamino)-
4-[3-chloro-4-hydroxyphenylimino]-
3-hydroxy-2-
methoxycyclohexa-2,5-dienone
Compound 23
C I
2-(2-Chloro-4-hydroxyphenylamino)-
4-[2-chloro-4-hydroxy-
/ ° phenylimino]-3-hydroxy-2-
methoxycyclohexa-2,5-dienone
Compound 24
3-Hydroxy-2-[4-(6-hydroxyhexylamino)
phenylamino]-4-
[4-(6-hydroxyhexylamino)
phenylimino]-2-
OH methoxy-
OH cyclohexa-2,5-dienone
Compound 25
2-[4-(Ethylisopropylamino)-
phenylamino]-
4-[4-(ethylisopropylamino)
phenylimino]-5-
hydroxy-3-pentylcyclohexak
2,5-dienone
Compound 26
2- (4-[Ethyl(2-hydroxyethyl)-
amino]-2-methylphenylamino}
-4- {4- [ethylshydro
xyethyl) amino] -2-
methylphenylimino }-5-
hydroxy-3-pentylcyclohexa-
2,5-dienone
Compound 27
2-(4-Amino-2,3-dimethylphenylamino)-
4-[4-amino-2,3-
dimethylphenylimino]-5-
hydroxy-3-pentylcyclohexa-
2,5-dienone
Compound 28
2-(4-Aminophenylamino)-4-[4-
aminophenylimino]-5-hydroxy-
3-pentylcyclohexa-
2,5-dienone
Compound 29
5-Hydroxy-2-(4-hydroxyphenylamino)
-4-[4-hydroxyphenylimino]-3-
pentylcyclohexa-2,5-dienone
Compound 30
2-(4-Amino-3 (or 2)-methylphenylamino)-
4-
[4-amino-3 (or 2)-methylphenylimino]-
5-hydroxy-3-pentylcyclohexa-
2,5-dienone
Compound 31
2-(3-Chloro-4-hydroxyphenylamino)-
4-[3-chloro-4-hydroxyphenylimino]-
5-hydroxy-3-
pentylcyclohexa-2,5-dienone
Compound 32
2-(2-Chloro-4-hydroxy-
C I C I phenylamino)-
4-[2-chloro-4-hydroxyphenylimino]-
5-hydroxy-3-
pentylcyclohexa-2,5-dienone
Compound 33
5-Hydroxy-2-[4-(6-hydroxyhexylamino)
phenylamino]-4-
J H [4-(6-hydroxyhexylamino)
phenylimino]-3-
pentylcyclohexa-
2,5-dienone
OH
Compound 34
2-[4-(Ethylisopropylamino)-
phenylamino]-
4-[4-(ethylisopropylamino)
phenylimino]-5-
hydroxy-3-hydroxymethylcyclohexa-
2,5-dienone
Compound 35
2- (4-[Ethyl(2-hydroxyethyl)-
amino]-2-methylphenylamino}
-4- {4- [ethylshydro
xyethyl) amino] -2-
methylphenylimino }-5-
hydroxy-3-hydroxymethylcyclohexa-
2,5-dienone
Compound 36
2-(4-Amino-2,3-dimethylphenylamino)-
4-[4-amino-2,3-
dimethylphenylimino]-5-
hydroxy-3-hydroxymethylcyclohexa-
2,5-dienone
Compound 37
2-(4-Aminophenylamino)-4-[4-
aminophenylimino]-5-hydroxy-
3-hydroxymethylcyclohexa-
2,5-dienone
Compound 38
5-Hydroxy-2-(4-hydroxyphenylamino)-
4-[4-hydroxyphenylimino]-3-
hydroxymethylcyclohexa-2,5-
dienone
Compound 39

6-[4-(Ethylisopropylamino)-
phenylamino]-
4-[4-(ethylisopropylamino)
phenylimino]-3-hydroxy-
2-propylcyclohexa-2,5-dienone
Compound 44
2- (4-[Ethyl(2-hydroxyethyl)-
amino]-2-methylphenylamino} -
4- (4-[ethyl(2-hydroxyethyl)-
amino]-2-methylphenylimino} -
3-hydroxy-2-propylcyclohexa-
2,5-dienone
Compound 45
2-(4-Amino-2,3-dimethylphenylamino)-
4-[4-amino-2,3-
dimethylphenylimino]-3-
hydroxy-2-propylcyclohexa-2,5-
dienone
Compound 46
2-(4-Aminophenylamino)-4-[4-
aminophenylimino]-3-hydroxy-
2-propylcyclohexa-
2,5-dienone
Compound 47
3-Hydroxy-2-(4-hydroxyphenylamino)-
4-[4-hydroxyphenylimino]-2-
propylcyclohexa-2,5-dienone
Compound 48
2-(4-Amino-3 (or 2)-methylphenylamino)-
4-
[4-amino-3 (or 2)-methylphenylimino]-
3-hydroxy-2-propylcyclohexa-
2,5-dienone
Compound 49
2-(3-Chloro-4-hydroxyphenylamino)-
4-[3-chloro-4-hydroxyphenylimino]-
3-hydroxy-2-
propylcyclohexa-2,5-dienone
Compound 50
C I C I
2-(2-Chloro-4-hydroxyphenylamino)-
4-[2-chloro-4-hydroxyphenylimino]-
3-hydroxy-2-
propylcyclohexa-2,5-dienone
Compound 51
3-Hydroxy-2-[4-(6-hydroxyhexylamino)
phenylamino]-4-[4-
(6-hydroxyhexylamino)
phenylimino]-2-
propyl-
OH cyclohexa-2,5-dienone
Compound 52
2-[4-(Ethylisopropylamino)-
phenylamino]-
4-[4-(ethylisopropylamino)
phenylimino]-5-
hydroxy-3,6-dimethylcyclohexa-
2,5-dienone
Compound 53
2- (4-[Ethyl(2-hydroxyethyl)-
amino]-2-methylphenylamino}
-4- {4- [ethylshydro
xyethyl) amino] -2-
methylphenylimino }-5-
hydroxy-3,6-dimethylcyclohexa-
2,5-dienone
Compound 54
2-(4-Amino-2,3-dimethylphenylamino)-
4-[4-amino-2,3-
dimethylphenylimino]-5-
hydroxy-3,6-dimethylcyclohexa-
2,5-dienone
Compound 55
2-(4-Aminophenylamino)-4-[4-
aminophenylimino]-5-hydroxy-
3,6-dimethylmethyl-cyclohexa-
2,5-dienone
Compound 56
5-Hydroxy-2-(4-hydroxyphenylamino)-
4-[4-hydroxyphenylimino]-3,6-
dimethylmethyl-cyclohexa-2,5-
dienone
Compound 57
2-(4-Amino-3 (or 2)-methylphenylamino)-
4-
[4-amino-3 (or 2)-methylphenylimino]-
5-hydroxy-3,6-dimethylmethylcyclohexa-
2,5-dienone
Compound 58
2-(3-Chloro-4-hydroxyphenylamino)-
4-[3-chloro-4-hydroxyphenylimino]-
5-hydroxy-3,6-
dimethylmethylcyclohexa-2,5-
dienone
Compound 59
2-(2-Chloro-4-hydroxyphenylamino)-
4-[2-chloro-4-hydroxyphenylimino]-
5-hydroxy-3,6-
dimethylmethylcyclohexa-2,5-
Compound dienone 60
5-Hydroxy-2-[4-(6-hydroxy-
J [ hexylamino)phenylamino]-4-
[4-(6-hydroxyhexylamino)
phenylimino]-3,6-
dimethylmethyl-cyclohexa-2,5-
OH dienone
Compound 61
Preferably, the direct dyes of formula (I) according to the
present invention are chosen from azomethine-type compounds 1, 2, 3,
12, 13, 17, 19, 26, 28, 35, 37, 44, 46, 53 and 55 .
More preferably, the direct dyes of formula (I) are chosen from
azomethine-type compounds 1, 2, 3 and 13.
The direct dyes of formula (I) may be obtained according to the
procedure described below:
The azomethine-type direct dyes corresponding to formula (I)
are generally obtained by reacting two equivalents of derivatives 1
with one equivalent of resorcinol 2 in a basic medium in the presence
of an oxidizing agent. The base used is preferably an aqueous solution
of ammonia and the oxidizing agent is preferably chosen from
hydrogen peroxide, air and ammonium persulfate.
Methods similar to this reaction scheme are described in Patent
Applications FR2234277, FR2047932, FR2 10666 1 and FR2 12 1101.
The invention also relates to the use of one or more
azomethine-type direct dyes of formula (I) as described previously for
colouring keratin fibres, in particular human keratin fibres such as the
hair.
. Dyeing composition
As indicated hereinbefore, the present invention also relates to
a composition for dyeing keratin fibres, particularly human keratin
fibres such as the hair, comprising, in a suitable medium for dyeing,
one or more direct dyes of formula (I) as defined previously.
Preferably, the dyeing composition comprises one or more
direct dyes of formula (I) chosen from azomethine-type compounds 1,
2, 3, 12, 13, 17, 19, 26, 28, 35, 37, 44, 46, 53 and 55 and their
mixtures.
More preferably, the dyeing composition comprises one or
more direct dyes of formula (I) chosen from azomethine-type
compounds 1, 2, 3 and 13 and their mixtures.
The direct dye(s) as defined previously may be present in the
dyeing composition according to the invention in a content ranging
from 0.00 1% to 10% by weight, preferably in a content ranging from
0.005% to 6%o by weight, relative to the total weight of the dyeing
composition.
In accordance with the present invention, the dyeing
composition contains one or more direct dyes of formula (I) as defined
previously and, optionally, one or more direct dyes having a structure
meeting formula (I) defined previously but in which when R i and R 2
denote a hydrogen atom, n equals 0, then X may denote a hydroxyl or
amino -NH 2 radical.
In other words, the condition defined in formula (I) indicating
that when R i and R 2 denote a hydrogen atom, n equals 0 then X does
not denote a hydroxyl or amino -NH 2 radical does not imply that the
dyeing composition according to the invention is free of any
azomethine direct dye whose formula (I) would meet the
abovementioned condition.
In other words, the abovementioned condition applies only to
direct dyes of formula (I) that are necessarily present in the dyeing
composition and not those that may be present optionally in said
composition.
The dyeing composition according to the invention may further
comprise one or more oxidation dyes.
The oxidation dyes are generally chosen from oxidation bases
optionally combined with one or more couplers.
By way of example, the oxidation bases are chosen from paraphenylenediamines,
bis(phenyl)alkylenediamines, /?ara-aminophenols,
r t/zo-aminophenols and heterocyclic bases, and their addition salts.
Among the /?ara-phenylenediamines that may be mentioned, for
example, are /?ara-phenylenediamine, /?ara-toluenediamine, 2-chloro-
/?ara-phenylenediamine, 2,3-dimethyl-/?ara-phenylenediamine, 2,6-
dimethyl-para-phenylenediamine, 2,6-diethyl-/?ara-phenylenediamine,
2,5-dimethyl-/?ara-phenylenediamine, N,N-dimethyl-/?araphenylenediamine,
N,N-diethyl-/?ara-phenylenediamine, N,Ndipropyl-
para-phenylenediamine, 4-amino-N,N-diethyl-3-
methylaniline, N,N-bis(P-hy droxyethyl) -para -phenylenediamine, 4-
N,N-bis(P-hydroxy ethyl) amino -2-methylaniline, 4-N,N-bis(Phydroxyethyl)
amino -2-chloro aniline, 2--hydroxyethyl-para -
phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-paraphenylenediamine,
N-(P-hydroxypropyl)-para-phenylenediamine, 2-
hydroxymethyl-para -phenylenediamine, N, -dimethyl- 3-methyl-para -
phenylenediamine, N,N- (ethyl- -hydroxyethyl)-paraphenylenediamine,
N-(P,Y-dihydroxypropyl)-para-phenylenediamine,
N-(4'-aminophenyl) -para -phenylenediamine, N-pheny1-paraphenylenediamine,
2--hydroxyethyloxy-para -phenylenediamine, 2--
acetylamino ethyloxy-para -phenylenediamine, N-(-metho xyethyl) -
para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thieny 1-paraphenylenediamine,
2-P-hydroxyethylamino-5-aminotoluene and 3-
hydroxy- 1-(4'-aminophenyl)pyrrolidine, and their addition salts with
an acid.
Among the /?ara-phenylenediamines mentioned above, paraphenylenediamine,
/?ara-toluenediamine, 2-isopropyl-paraphenylenediamine,
2-P-hydroxyethyl-para-phenylenediamine, 2--
hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-paraphenylenediamine,
2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-
/?ara-phenylenediamine, N,N-bis(P-hy droxyethyl)-paraphenylenediamine,
2-chloro-para-phenylenediamine and 2--
acetylaminoethyloxy-para-phenylenediamine, and their addition salts
with an acid, are particularly preferred.
Mention may be made, among bis(phenyl)alkylenediamines, by
way of example, of N,N'-bis(P-hydroxyethyl)-N,N'-bis(4'-
aminophenyl)- ,3-diaminopropanol, N,N'-bis(P-hydroxyethyl)-N,N'-
bis (4'-aminophenyl) ethylene diamine, N,N'-bis(4-
aminophenyl)tetramethylenediamine, N,N'-bis (P-hydroxyethyl) -N,N '-
bis(4- amino phenyl)tetramethylenediamine, N,N'-bis(4-
methylaminophenyl)tetramethylenediamine, N,N'-bis(ethyl)-N,N'-
bis(4'-amino-3'-methylphenyl)ethylenediamine, l ,8-bis(2,5-
diaminophenoxy)-3,6-dioxaoctane and their addition salts.
Mention may be made, among /?ara-aminophenols, by way of
example, of /?ara-aminophenol, 4-amino-3-methylphenol, 4-amino-3-
fluorophenol, 4-amino-3-chlorophenol, 4-amino-3-
(hydroxymethyl)phenol, 4-amino-2-methylphenol, 4-amino-2-
(hydroxymethyl)phenol, 4-amino-2-(methoxymethyl)phenol, 4-amino -
2-(aminomethyl)phenol, 4-amino -2- [(-
hydroxyethyl)aminomethyl]phenol, 4-amino-2-fluorophenol and their
addition salts with an acid.
Mention may be made, among r t/zo-aminophenols, by way of
example, of 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-
methylphenol, 5-acetamido-2-aminophenol and their addition salts.
Mention may be made, among heterocyclic bases, by way o f
example, of pyridine derivatives, pyrimidine derivatives and pyrazole
derivatives.
Mention may be made, among pyridine derivatives, o f 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, 3,4-diaminopyridine and their
addition salts.
Other pyridine oxidation bases o f use in the present invention
are the 3-aminopyrazolo[ 1,5-a]pyridine oxidation bases or their
addition salts described, for example, in Patent Application FR 2 80 1
308. Mention may be made, by way o f example, of pyrazolo[ 1,5-
a]pyrid-3-ylamine, 2-(acetylamino)pyrazolo[ 1,5-a]pyrid-3-ylamine, 2-
(morpholin-4-yl)pyrazolo[ 1,5-a]pyrid-3-ylamine, 3-
aminopyrazolo[ 1,5-a]pyridine-2-carboxylic acid, 2-
methoxypyrazolo[ 1,5-a]pyrid-3-ylamine, (3-aminopyrazolo[ 1,5-
a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[ 1,5-a]pyrid-5-yl)ethanol,
2-(3-aminopyrazolo[ 1,5-a]pyrid-7-yl)ethanol, (3-aminopyrazolo[ 1,5-
a]pyrid-2-yl)methanol, 3,6-diaminopyrazolo[ 1,5-a]pyridine, 3,4-
diaminopyrazolo[ l ,5-a]pyridine, pyrazolo[ l ,5-a]pyridine-3,7-diamine,
7-(morpholin-4-yl)pyrazolo[ l ,5-a]pyrid-3-ylamine, pyrazolo[ l ,5-
a]pyridine-3, 5-diamine, 5-(morpholin-4-yl)pyrazolo[ l ,5-a]pyrid-3-
ylamine, 2-[(3-aminopyrazolo[ 1,5-a]pyrid-5-yl)(2-
hydroxyethyl)amino]ethanol, 2-[(3-aminopyrazolo[ 1,5-a]pyrid-7-yl)(2-
hydroxyethyl)amino]ethanol, 3-aminopyrazolo[ 1,5-a]pyridin-5-ol, 3-
aminopyrazolo[ 1,5-a]pyridin-4-ol, 3-aminopyrazolo[ 1,5-a]pyridin-6-
ol, 3-aminopyrazolo[ 1,5-a]pyridin-7-ol and their addition salts.
Mention may be made, among pyrimidine derivatives, of the
compounds described, for example, in Patents DE 2359399, JP 88-
16957 1, JP 05-63 124 and EP 0 770 375 or Patent Application WO
96/1 5765 , 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 their
addition salts and their tautomeric forms, when a tautomeric
equilibrium exists.
Among the pyrazole derivatives that may be mentioned are the
compounds described in Patents DE 3843892, DE 4 133957 and Patent
Applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE
195 43 988, such as 4,5-diamino- 1-methylpyrazole, 4,5-diamino- 1-(-
hydroxyethyl)pyrazole, 3,4-diaminopyrazole, 4,5-diamino- 1-(4'-
chlorobenzyl)pyrazole, 4,5-diamino- 1,3-dimethylpyrazole, 4,5-
diamino-3-methyl- 1-phenylpyrazole, 4,5-diamino- 1-methyl-3-
phenylpyrazole, 4-amino - 1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-
4,5-diamino- 3-methylpyrazole, 4,5-diamino-3-tert-butyl- 1-
methylpyrazole, 4,5-diamino- 1-tert-butyl-3-methylpyrazole, 4,5-
diamino- 1-(P-hydroxyethyl)-3 -methylpyrazole, 4,5-diamino - 1-ethy 1-3-
methylpyrazole, 4,5-diamino - 1-ethy 1-3- (4'-methoxyphenyl)pyrazole,
4,5-diamino - 1-ethy 1-3 -hydro xymethylpyrazole, 4,5-diamino -3-
hydroxymethyl- 1-methylpyrazole, 4,5-diamino-3-hydroxymethyl- 1-
isopropylpyrazole, 4,5-diamino-3-methyl- 1-isopropylpyrazole, 4-
amino-5-(2'-aminoethyl)amino - 1,3-dimethylpyrazole, 3,4,5-triaminopyrazole,
1-methyl-3,4,5-triaminopyrazole, 3,5-diamino- 1-methy1-4-
methylaminopyrazole, 3,5-diamino-4-(P-hydroxyethyl)amino- 1-
methylpyrazole, and their addition salts. 4,5-Diamino- 1-(-
methoxyethyl)pyrazole may also be used.
Use will preferably be made of a 4,5-diaminopyrazole and
more preferably still of 4,5-diamino- 1-(P-hydroxyethyl)pyrazole
and/or one of its salts.
Mention may also be made, as pyrazole derivatives, of
diamino-N,N-dihydropyrazolopyrazolones and in particular those
described in Application FR-A-2 886 136, such as the following
compounds and their addition salts: 2,3-diamino-6,7-dihydro- lH,5Hpyrazolo[
1,2-a]pyrazol- 1-one, 2-amino-3-ethylamino-6,7-dihydrolH,
5H-pyrazolo[ 1,2-a]pyrazol- 1-one, 2-amino-3-isopropylamino-6,7-
dihydro- lH,5H-pyrazolo[ 1,2-a]pyrazol- 1-one, 2-amino-3-(pyrrolidinl
-yl)-6,7-dihydro- lH,5H-pyrazolo[ l ,2-a]pyrazol- l -one, 4,5-diamino-
1,2-dimethyl- l ,2-dihydropyrazol-3-one, 4,5-diamino- 1,2-diethyl- 1,2-
dihydropyrazol-3-one, 4,5-diamino- 1,2-di(2-hydroxy ethyl)- 1,2-
dihydropyrazol-3-one, 2-amino-3-(2-hydroxyethyl)amino-6,7-dihydrolH,
5H-pyrazolo[ 1,2-a]pyrazol- 1-one, 2-amino-3-dimethylamino-6,7-
dihydro- lH,5H-pyrazolo[ 1,2-a]pyrazol- 1-one, 2,3-diamino-5,6,7,8-
tetrahydro- lH,6H-pyridazino[ 1,2-a]pyrazol- 1-one, 4-amino -1,2-
diethyl-5-(pyrrolidin- l -yl)- l ,2-dihydropyrazol-3-one, 4-amino -5-(3-
dimethylaminopyrrolidin- 1-yl)- 1,2-diethyl- 1,2-dihydropyrazol-3-one
or 2,3-diamino-6-hydroxy-6,7-dihydro- lH,5H-pyrazolo[ 1,2-a]pyrazol-
1-one.
Use will preferably be made of 2,3-diamino-6,7-dihydrolH,
5H-pyrazolo[ l ,2-a]pyrazol- l -one and/or one of its salts.
Use will preferably be made, as heterocyclic bases, of 4,5-
diamino- 1-(P-hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-dihydrolH,
5H-pyrazolo[ l ,2-a]pyrazol- l -one and/or one of their salts.
The dyeing composition may optionally comprise one or more
couplers advantageously chosen from those conventionally used in
dyeing keratin fibres.
Mention may in particular be made, among these couplers, o f
ta-phenylenediamines, ta-aminophenols, ta-diphenols,
naphthalene couplers, heterocyclic couplers and their addition salts.
Mention may be made, for example, o f 1,3-dihydroxybenzene,
1,3-dihydroxy-2-methylbenzene, 4-chloro- 1,3-dihydroxybenzene, 2,4-
diamino- 1-(P-hydroxyethyloxy)benzene, -amino -4- (-
hydroxyethylamino)- 1-methoxybenzene, 1,3-diaminobenzene, 1,3-
bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido- l -
dimethylaminobenzene, sesamol, l -P-hydroxyethylamino-3,4-
methylenedioxybenzene, O -naphthol, 2-methyl- 1-naphthol, 6-
hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-
3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-
dimethoxypyridine, 1-N-(-hydroxy ethyl) amino -3,4-
methylenedioxybenzene, 2,6-bis (P-hydroxyethylamino)toluene, 6-
hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, l -H-3-
methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2,6-
dimethylpyrazolo[ 1,5-b]- l ,2,4-triazole, 2,6-dimethyl[3,2-c]- 1,2,4-
triazole and 6-methylpyrazolo[ 1,5-a]benzimidazole, their addition
salts with an acid, and their mixtures.
In general, the addition salts o f the oxidation bases and
couplers which can be used in the context of the invention are chosen
in particular from the addition salts with an acid, such as the
hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates,
lactates, tosylates, benzenesulfonates, phosphates and acetates.
The oxidation base(s) each advantageously represent from
0.00 1% to 10% by weight and preferably from 0.005% to 6% by
weight relative to the total weight of the composition.
The content of coupler(s), i f it is (they are) present, each
advantageously represent from 0.00 1% to 10% by weight relative to
the total weight of the composition, and preferably from 0.005% to 6%
by weight relative to the total weight of the dyeing composition.
The dyeing composition according to the invention may also
comprise one or more additional direct dyes other than the
azomethine-type direct dyes defined previously.
The additional direct dye(s) according to the invention are
chosen from neutral, acidic or cationic nitrobenzene dyes, neutral,
acidic or cationic azo direct dyes, neutral, acidic or cationic quinone
and in particular anthraquinone direct dyes, azine direct dyes,
triarylmethane direct dyes, azomethine direct dyes and natural direct
dyes.
Among the benzene direct dyes that may b e used according to
the invention, mention may b e made, in a non-limiting manner, of the
following compounds:
- 1,4-diamino-2-nitrobenzene
- 1-amino-2-nitro-4-B-hydroxyethylaminobenzene
- 1-amino-2-nitro-4-bis (P-hydroxyethyl)aminobenzene
- 1,4-bis(B-hydroxyethylamino)-2-nitrobenzene
- 1-B-hydroxyethylamino-2-nitro-4-bis ( -
hydroxyethylamino)benzene
- 1-B-hydroxyethylamino-2-nitro-4-aminobenzene
- 1-P-hydroxyethylamino-2-nitro-4-(ethyl)(Bhydroxyethyl)
aminobenzene
- 1-amino-3-methyl-4 -P-hydroxyethylamino-6-nitrobenzene
- 1-amino-2-nitro-4 -P-hydroxyethylamino-5-chlorobenzene
- 1,2-diamino-4-nitrobenzene
- 1-amino-2 -P-hydroxyethylamino-5-nitrobenzene
- 1,2-bis (P-hydroxyethylamino)-4-nitrobenzene
- 1-amino-2-tris(hydroxymethyl)methylamino-5-nitrobenzene
- 1-hydro xy-2- amino -5-nitrobenzene
- 1-hydroxy-2-amino-4-nitrobenzene
- 1-hydroxy- 3-nitro -4-amino benzene
- 1-hydro xy-2 -amino -4, 6-dinitrobenzene
- 1-P-hydroxyethyloxy-2-P-hydroxyethylamino-5-nitrobenzene
- 1-methoxy-2 -P-hydroxyethylamino-5-nitrobenzene
- 1-P-hydroxyethyloxy-3-methylamino-4-nitrobenzene
- 1-P,y-dihydroxypropyloxy-3-methylamino-4-nitrobenzene
- 1-P-hydroxyethylamino-4-P,y-dihydroxypropyloxy-2-
nitrobenzene
- 1-P,Y-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene
- 1-P-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene
- 1-P-hydroxyethylamino-3-methyl-2-nitrobenzene
- 1-P-aminoethylamino-5-methoxy-2-nitrobenzene
- 1-hydro xy-2-chloro-6-ethylamino-4-nitrobenzene
- 1-hydro xy-2-chloro-6-amino-4-nitrobenzene
- 1-hydroxy-6-bis (P-hydroxyethyl)amino-3-nitrobenzene
- 1-P-hydroxyethylamino-2-nitrobenzene and
- 1-hydroxy-4 -P-hydroxyethylamino-3-nitrobenzene.
Among the azo direct dyes that may b e used according to the
invention, mention may b e made of the cationic azo dyes described in
Patent Applications WO 95/1 5 144, WO-95/0 1772 and EP-7 14954, the
content of which forms an integral part of the invention.
Among these compounds, mention may b e made very
particularly of the following dyes:
- 1,3-dimethyl-2-[[4-(dimethylamino)phenyl]azo]- 1Himidazolium
chloride,
- 1,3-dimethyl-2-[(4-aminophenyl)azo]- lH-imidazolium
chloride,
- 1-methyl-4-[(methylphenylhydrazono)methyl]pyridinium
methyl sulfate.
Among the azo direct dyes that may also b e mentioned are the
following dyes, described in the Colour Index International, 3rd
edition: Disperse Red 17, Acid Yellow 9, Acid Black 1, Basic Red 22,
Basic Red 76, Basic Red 5 1, Basic Yellow 57, Basic Brown 16, Acid
Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 35, Basic Brown
17, Acid Yellow 23, Acid Orange 24, Disperse Black 9 .
Mention may also b e made of 1-(4 '-aminodiphenylazo)-2-
methyl-4-bis (P-hydroxyethyl)aminobenzene and 4-hydroxy-3-(2-
methoxyphenylazo)- 1-naphthalenesulfonic acid.
Among the quinone direct dyes, mention may b e made o f the
following dyes: Disperse Red 15, Solvent Violet 13 , Acid Violet 43,
Disperse Violet 1, Disperse Violet 4 , Disperse Blue 1, Disperse Violet
8, Disperse Blue 3, Disperse Red 11, Acid Blue 62, Disperse Blue 7,
Basic Blue 22, Disperse Violet 15, Basic Blue 99, and also the
following compounds:
- 1-N-methylmorpholiniumpropylamino-4-
hydroxyanthraquinone
- 1-aminopropylamino-4-methylaminoanthraquinone
- 1-aminopropylaminoanthraquinone
-5 -hydroxyethyl-1,4-diaminoanthraquinone
-2-aminoethylaminoanthraquinone
- 1,4-bis (P,y-dihydroxypropylamino)anthraquinone.
Among the azine dyes, mention may be made o f the following
compounds: Basic Blue 17 and Basic Red 2 .
Among the triarylmethane dyes that may b e used according to
the invention, mention may b e made of the following compounds:
Basic Green 1, Acid Blue 9, Basic Violet 3, Basic Violet 14, Basic
Blue 7, Acid Violet 49, Basic Blue 26 and Acid Blue 7 .
Among the azomethine dyes that can b e used according to the
invention, mention may b e made of the following compounds:
-2-P-hydroxyethylamino-5-[bis(P-4'-
hydroxyethyl)amino]anilino- 1,4-benzoquinone
-2-P-hydroxyethylamino-5-(2'-methoxy-4 ' -amino) anilino- 1,4-
benzoquinone
-3-N-(2'-chloro-4'-hydroxy)phenylacetylamino-6-methoxy- 1,4-
benzoquinoneimine
-3-N-(3 '-chloro-4'-methylamino)phenylureido-6-methyl- 1,4-
benzoquinoneimine
-3-[4'-N-(Ethylcarbamylmethyl)amino]phenylureido-6-methyl-
1,4-benzoquinoneimine
Among the natural direct dyes that may b e used according to
the invention, mention may b e made o f lawsone, juglone, alizarin,
purpurin, carminic acid, kermesic acid, purpurogallin,
protocatechaldehyde, indigo, isatin, curcumin, spinulosin and
apigenidin. Extracts or decoctions containing these natural dyes and in
particular cataplasms or henna-based extracts may also b e used.
The additional direct dye(s) may be present in the dyeing
composition in a content ranging from 0.00 1% to 10% by weight,
preferably in a content ranging from 0.005% to 6% by weight, relative
to the total weight of the composition.
Preferably, the dyeing composition comprises one or more
direct dyes of formula (I) such as those defined previously and one or
more additional azomethine direct dyes different from the direct dyes
of the present invention.
The medium that is suitable for dyeing, also known as the dye
support, is a cosmetic medium generally formed from water or a
mixture of water and of at least one organic solvent. Examples of
organic solvents that may be mentioned include C 1- C 4 lower alkanols,
such as ethanol and isopropanol; polyols and polyol ethers, for
instance 2-butoxyethanol, propylene glycol, propylene glycol
monomethyl ether, diethylene glycol monoethyl ether and monomethyl
ether, and also aromatic alcohols, for instance benzyl alcohol or
phenoxyethanol, and their mixtures.
When they are present, the solvents are present in proportions
preferably of between 1% and 99% by weight approximately and even
more preferentially between 5% and 95% by weight approximately
relative to the total weight of the dyeing composition.
The dyeing composition may also contain various adjuvants
conventionally used in hair dye compositions, such as anionic,
cationic, non-ionic, amphoteric surfactants or their mixtures, anionic,
cationic, non-ionic, amphoteric polymers or their mixtures, inorganic
or organic thickeners, and in particular anionic, cationic, non-ionic
and amphoteric polymeric associative thickeners, antioxidants,
penetrants, sequestrants, solubilizers, fragrances, buffers, dispersants,
conditioning agents, for instance volatile or non-volatile, modified or
unmodified silicones such as amino silicones, film-forming agents,
ceramides, preserving agents, opacifiers.
The above adjuvants are generally present in an amount, for
each of them, of between 0.0 1% and 20% by weight relative to the
weight of the composition.
Needless to say, a person skilled in the art will take care to
select this or these optional additional compound(s) such that the
advantageous properties intrinsically associated with the dyeing
composition in accordance with the invention are not, or are not
substantially, adversely affected by the envisaged addition(s).
The pH of the dyeing composition in accordance with the
invention is generally between 3 and 12 approximately, preferably
between 5 and 11 approximately and even more particularly from 6 to
8.5 . It may be adjusted to the desired value by means of acidifying or
alkalinizing agents customarily used in dyeing keratin fibres, or
alternatively using standard buffer systems.
Mention may be made, among the acidifying agents, by way of
example, of inorganic or organic acids, such as hydrochloric acid,
orthophosphoric acid, sulfuric acid, carboxylic acids, such as acetic
acid, tartaric acid, citric acid or lactic acid, or sulfonic acids.
Among the alkalinizing agents, mention made be made, by way
of example, of aqueous ammonia, alkali metal carbonates,
alkanolamines, such as mono-, di- and triethanolamines and their
derivatives, sodium hydroxide, potassium hydroxide and the
compounds of the following formula (III):
(III)
formula (III) in which W is a propylene residue optionally substituted
with a hydroxyl group or a C1-C4 alkyl radical; and Ra, Rb, Rc and Rd,
which may be identical or different, denote a hydrogen atom or a Ci-
C4 alkyl or C1-C4 hydroxyalkyl radical.
The dyeing composition according to the invention may be in
various forms, such as in the form of liquids, creams or gels, or in any
other form that is suitable for dyeing keratin fibres, and especially
human hair.
As indicated previously, the invention also relates to the use of
the dyeing composition as defined previously for colouring keratin
fibres, in particular human keratin fibres such as the hair.
III. Dyeing method
The dyeing method according to the present invention consists
in applying a dyeing composition as defined previously to keratin
fibres for a long enough period to obtain the desired colour, after
which the fibres are rinsed, optionally washed with shampoo, rinsed
again and the resulting fibres are dried or left to dry.
The dyeing composition is generally applied to keratin fibres at
room temperature, preferably between 25 and 55°C.
According to one embodiment, the dyeing composition
according to the invention is applied to the keratin fibres in the
presence of one or more oxidizing agents for a long enough period to
obtain the desired lightening.
The oxidizing agent may be present in the dyeing composition
or be used separately in a cosmetic composition.
Preferably, the oxidizing agent is used separately in a cosmetic
composition.
Accordingly, the present invention also relates to a lightening
method for keratin fibres, in particular human keratin fibres such as
the hair, in which (i) the dyeing composition as defined previously
free of oxidizing agent and (ii) a cosmetic composition comprising one
or more oxidizing agents are applied to said fibres; compositions (i)
and (ii) being applied to said keratin fibres sequentially or
simultaneously for a long enough period to obtain the desired
lightening, after which the fibres are rinsed, optionally washed with
shampoo, rinsed again and the resulting fibres are dried or left to dry.
In the sense of the present invention, "sequentially" is
understood to mean that the oxidizing composition is applied before or
after the dyeing composition, i.e. as a pre- or post-treatment.
The oxidizing agents used are chosen from hydrogen peroxide,
urea peroxide, alkali metal bromates, persalts such as perborates and
persulfates, peracids and oxidase enzymes (with their optional
cofactors), among which mention may be made of peroxidases, 2-
electron oxidoreductases such as uricases, and 4-electron oxygenases,
for instance laccases.
The oxidizing agent is preferably hydrogen peroxide.
The oxidizing composition may also contain various adjuvants
conventionally used in compositions for dyeing the hair and as defined
above.
The pH of the oxidizing composition containing the oxidizing
agent is such that, after mixing with the dyeing composition, the pH of
the resulting composition applied to the keratin fibres preferably
ranges between 3 and 12 approximately, more preferably still between
5 and 11, and better still between 6 and 9.5 . It may be adjusted to the
desired value by means of acidifying or alkalinizing agents usually
used in dyeing keratin fibres and as defined above.
V. Leuco-type compound
Moreover, the present invention relates to leuco-type
compounds having the following formula (II), their organic or
inorganic salts with an acid, their tautomeric forms, optical isomers,
geometric isomers and/or their solvates:
(II)
formula (II) in which n, R, Rl R2 and X have the same
meanings as indicated in formula (I).
In particular, the preferred variants for n, R, Rl R2 and X in
formula (II) for leuco-type compounds correspond to those indicated in
formula (I) for direct dyes.
The leuco-type compounds meeting formula (II) are obtained
generally by reacting the azomethine-type compounds of formula (I)
with a reducing agent according to the reaction scheme below:
Synthetic processes similar to this reaction scheme are
described in Patent Applications FR2056799, FR2047932, FR2 165965
and FR2262023 .
The leuco-type compounds of formula (II) are used as
precursors for direct dyes of formula (I).
Preferably, the leuco-type compounds of formula (II) are
chosen from compounds corresponding to the reduced form of
azomethine-type direct dyes 1 to 61 mentioned previously.
In other words, the leuco-type compounds of formula (II) are
chosen from precursors for azomethine-type direct dyes 1 to 61.
Even more preferably, the leuco-type compounds of formula
(II) are chosen from precursors for azomethine direct dyes 1, 2, 3, 12,
13, 17, 19, 26, 28, 35, 37, 44, 46, 53 and 55 .
More preferably, the leuco-type compounds of formula (II) are
chosen from precursors for direct dyes 1, 2, 3 and 13.
In particular, the invention relates to a cosmetic composition
comprising, in a cosmetically acceptable medium, one or more leucotype
compounds of formula (II) as defined previously.
The present invention also relates to a dyeing method in which
a cosmetic composition comprising one or more leuco-type compounds
of previously cited formula (II) in the presence of one or more
oxidizing agents is applied to keratin fibres for a long enough period
to develop the desired colour, after which the fibres are rinsed,
optionally washed with shampoo, rinsed again and the resulting fibres
are dried or left to dry.
The oxidizing agent may be oxygen from the air or be chosen
from previously cited oxidizing agents.
In particular, when the oxidizing agent is oxygen from the air,
simply exposing the keratin fibres treated with the composition
comprising the leuco-type compound(s) to air can generate the
colouring species and, consequently, colour the fibres.
According to one variant, the oxidizing agent(s) may be applied
to keratin fibres simultaneously or sequentially to the cosmetic
composition comprising the leuco-type compounds.
Accordingly, the cosmetic composition comprising the
oxidizing agent(s) may be applied to keratin fibres before,
simultaneously or after the cosmetic composition comprising the
leuco-type compounds of formula (II) according to the invention.
According to another variant, a ready-to-use composition is
applied to keratin fibres that results from mixing a cosmetic
composition comprising one or more leuco-type compounds having
previously cited formula (II) and a cosmetic composition comprising
one or more oxidizing agents.
The ready-to-use composition which is ultimately applied to
the keratin fibres may be in a variety of forms, such as in the form of
liquids, creams or gels or any other form appropriate for carrying out
dyeing of keratin fibres, and in particular of human hair.
The leave-on time for the composition(s) varies from 1 to 60
minutes, preferably from 5 to 40 minutes and even more preferably
from 10 to 30 minutes.
The cosmetic composition comprising such leuco-type
compounds is generally applied to keratin fibres at room temperature,
preferably between 25 and 55°C.
Accordingly, the invention relates also to a cosmetic
composition, particularly for dyeing human keratin fibres such as the
hair, comprising, in a cosmetically acceptable medium, one or more
leuco-type compounds of formula (II) as defined previously, optionally
in the presence of one or more oxidizing agents.
VI. Dyeing device
Lastly, the present invention relates to a multi-compartment
device or dyeing kit comprising a first compartment containing a
cosmetic composition comprising one or more direct dyes having
previously cited formula (I) or one or more leuco-type compounds
having previously cited formula (II), and optionally a second
compartment containing a cosmetic composition comprising one or
more oxidizing agents.
The device is suitable for dyeing keratin fibres.
In particular, the invention relates to a multi-compartment
device or dyeing kit comprising a first compartment containing a
cosmetic composition comprising one or more direct dyes having
previously cited formula (I) or one or more leuco-type compounds
having previously cited formula (II), and a second compartment
containing a cosmetic composition comprising one or more oxidizing
agents.
Accordingly, the invention relates to a multi-compartment
device or dyeing kit comprising a first compartment containing a
cosmetic composition comprising one or more direct dyes having
previously cited formula (I) free of oxidizing agent, and a second
compartment containing a cosmetic composition comprising one or
more oxidizing agents.
Moreover, the invention relates to a multi-compartment device
or dyeing kit comprising a first compartment containing a cosmetic
composition comprising one or more leuco-type compounds having
previously cited formula (II), and a second compartment containing a
cosmetic composition comprising one or more oxidizing agents.
According to a specific embodiment, the device comprises at
least one compartment containing a cosmetic composition comprising
one or more leuco-type compounds having previously cited formula
(II).
In this case, the composition comprising the leuco-type
compound(s) as defined hereinbefore is applied to keratin fibres that
are coloured when they are exposed to air.
The evaluation of the coloration can be done visually or read
on a spectrocolorimeter (such as Minolta CM3600d, illuminant D65,
angle 10°, SCI values) for the L*, a*, b* colorimetric measurements. In
this L*, a*, b* system, L* represents the intensity of the color, a*
indicates the green/red color axis and b* indicates the blue/yellow
color axis. The lower the value of L, the darker or more intense the
color is. The higher the value of a , the redder the shade is; the higher
the value of b , the yellower the shade is.
The variation in coloring between the colored locks of natural
white hair which is untreated (control) and after treatment or
coloration is defined by , corresponding to the colour uptake on
keratin fibers, according to the following equation:
* = - (L* —Lo
* )2 + (a * —a 0
* + ( * - b 0
*)2 (i)
In this equation, L*, a* and b* represent the values measured
after dyeing the natural hair comprising 90% of white hairs and L o ,
a o and b o represent the values measured for the untreated natural hair
comprising 90% of white hairs.
The greater the value of , the greater the difference in color
between the control locks and the dyed locks and the greater color
uptake is. Chromaticity in the CIE L*, a*, b * colorimetric system is
calculated according to the following equation:
The greater the value of C*, the greater the chromaticity is.
The examples that follow serve to illustrate the invention
without, however, being limiting in nature.
EXAMPLES
I . Examples of synthesis
Example 1: Synthesis of 2-[4-(ethylisopropylamino)-
phenylamino]-4-[4-(ethylisopropylamino)phenylimino]-5-hydroxy-3-
methylcyclohexa-2,5-dienone (compound 1)
To a solution of 0.002 mol (429 mg) of N-ethyl-N-isopropyl-4-
aminoaniline hydrochloride and 0.00 1 mol (124 mg) of orcinol in 2 ml
of water and 6 ml of ethanol brought to a pH of 9.5 with a solution of
20% aqueous ammonia, 0.002 mol (456 mg) of ammonium persulfate
dissolved in 1 ml of water is added dropwise. The temperature is held
below 30°C during the addition. At the end of the addition, the
precipitate formed is filtered and washed with water.
Thus 125 mg of a black powder corresponding to compound 1
is obtained.
The molecular ion 475 (ES+) is detected by mass.
Example 2: Synthesis of 2- {4-[ethyl(2-hydroxyethyl)-amino]-
2-methylphenylamino} -4- {4-[ethyl(2-hydroxyethyl)amino]-2-
methylphenylimino }-5-hydroxy-3-methylcyclohexa-2,5-dienone
(compound 2)
To a solution of 0.002 mol (573 mg) of 2-[(4-amino-3-
methylphenyl)ethylamino]ethanol sulfate and 0.00 1 mol (124 mg) of
orcinol in 2 ml of water and 2 ml of ethanol brought to a pH of 9.5
with a solution of 20% aqueous ammonia, 0.002 mol (456 mg) of
ammonium persulfate dissolved in 1 ml of water is added dropwise.
The temperature is held below 30°C. At the end of the addition, the
precipitate formed is filtered and washed with water.
108 mg of a black powder corresponding to compound 2 is
obtained.
The molecular ion 507 (ES+) is detected by mass.
Example 3: Synthesis of 2-(4-amino-3 (or 2)-methylphenylamino)-
4-[4-amino-3 (or 2)-methylphenylimino]-5-hydroxycyclohexa-
2,5-dienone (compound 13)
Air at room temperature is bubbled through a solution of
0.2 mol (39 g) of 2-methylbenzene- l ,4-diamine dihydrochloride, 0 .1
mol ( 11 g) of resorcinol in 500 ml of water and 50 ml of 20% aqueous
ammonia for 4 hours. After the precipitate is filtered, washed with
water and then ethanol, 190 mg of a black powder corresponding to
compound 13 is obtained.
The molecular ion 349 (ES+) is detected by mass.
Example 4 : Synthesis of 2-(4-amino-2,3-dimethylphenylamino)-
4-[(Z)-4-amino-2,3-dimethylphenylimino]-5-hydroxy-3-
methylcyclohexa-2,5-dienone (compound 3)
Compound 3
To a solution of 0.02 mol (4.23 g) of 2,3-dimethylbenzene- 1,4-
diamine dihydrochloride and 0.0 1 mol ( 1.24 g) of orcinol in 20 ml of
water and 30 ml of ethanol brought to a pH of 9.5 with a solution of
20% aqueous ammonia, 0.0 1 mol (2.28 g) of ammonium persulfate
dissolved in 10 ml of water is added dropwise. The temperature is held
below 30°C. At the end of the addition, the precipitate formed is
filtered and washed with water.
110 mg of a black powder corresponding to compound 3 is
obtained.
The molecular ion 39 1 (ES+) is detected by mass.
II. Dyeing evaluations of compounds synthesized
The following colouring base is prepared:
78.5 grams of water,
15 grams of ethanol,
5 grams of benzyl alcohol,
1.5 gram of oleocetyl dimethyl hydroxyethyl ammonium
chloride
The pH of the colouring base is adjusted to a value of 9.5 with
aqueous ammonia at 20% by weight. 6.25 mg of the dyes described in
synthesis examples 1, 2 and 4 are mixed.
Each of the compositions obtained is applied to 0.25 gram
tresses of grey hair with 90% whites. After 30 minutes leave-on time,
the tress is rinsed, washed with a standard shampoo, then rinsed again
and dried.
The results are collated in the following table:
Compound 1 Average orangey grey
Average orangey grey
Compound 2
Compound 3 Dark yellowish beige
CLAIMS
1.Azomethine-type direct dye with a tri-aromatic unit having
the following formula (I):
and its organic or inorganic salts with an acid or a base, its tautomeric
forms, optical isomers, geometric isomers and/or its solvates;
formula (I) in which:
• n denotes an integer equal to 0, 1, 2, 3 or 4;
• R denotes:
- a linear or branched C1-C4 alkyl radical, optionally substituted
by one or more radicals the same or different chosen from
hydroxyl or imidazolium, An radicals; An designating an anion
or a mixture of cosmetically acceptable anions;
- a C1-C4 alkoxy radical;
- a halogen atom;
• Ri denotes:
- a hydrogen atom,
- a linear or branched C1-C9 alkyl radical, optionally substituted
by one or more hydroxyl radicals,
- a C1-C3 alkoxy radical;
• R2 denotes:
- a hydrogen atom,
- a linear or branched C3-C9 alkyl radical, optionally substituted
by one or more hydroxyl radicals,
- a C1-C3 alkoxy radical,
- a Ci-C 2 alkyl radical when Ri is other than a hydrogen atom;
• X denotes:
- a hydroxyl radical,
- a -NR 3R4 radical in which:
■ R3 denotes a hydrogen atom or a linear or branched Ci-C
alkyl radical, optionally substituted by one or more Ci -
C4hydroxyl or alkoxy radicals;
■ 4 denotes a hydrogen atom or a linear or branched Ci-C
alkyl radical, optionally substituted by one or more
hydroxyl or C1-C 4 alkoxy radicals;
it being understood that when Ri and R2 denote a hydrogen atom and
n equals 0 then X does not denote a hydroxyl or amino -NH2 radical.
2 . Azomethine direct dye according to Claim 1, characterized
that in the formula (I), considered in isolation or in combination:
• n denotes an integer equal to 0, 1 or 2;
• R denotes:
- a Ci-C 2 alkyl radical, optionally substituted by one or
more hydroxyl or imidazolium, An radicals; An
designating an anion or a mixture of cosmetically
acceptable anions;
- a C1-C2 alkoxy radical;
- a chlorine atom;
• Ri denotes:
- a hydrogen atom,
- a linear or branched C1-C9 alkyl radical,
- a linear or branched C1-C3 alkyl radical, substituted by a
hydroxyl radical,
- a Ci-C 2 alkoxy radical;
• R2 denotes:
- a hydrogen atom,
- a linear or branched C3-C9 alkyl radical,
- a Ci-C 2 alkoxy radical,
- a Ci-C 2 alkyl radical when Ri is other than a hydrogen
atom;
• X denotes:
- a hydroxyl radical,
- a -NR 3R4 radical in which:
■ R3 denotes a hydrogen atom or a linear or branched -
C 3 alkyl radical, optionally substituted by one or more
Ci-C 2hydroxyl or alkoxy radicals;
■ R4 denotes a hydrogen atom or a linear or branched Ci-
C3 alkyl radical, optionally substituted by one or more
hydroxyl or Ci-C 2 alkoxy radicals;
• it being understood that when Ri and R2 denote a hydrogen
atom and n equals 0 then X does not denote a hydroxyl or amino -NH2
radical.
3. Azomethine direct dye according to Claim 1 or 2,
characterized in that Ri denotes a hydrogen atom or a linear or
branched C1- C 9 alkyl radical, and in particular, Ri denotes a hydrogen
atom or a methyl radical.
4 . Azomethine direct dye according to any one of Claims 1 to
3, characterized in that R2 denotes a hydrogen atom.
5. Azomethine direct dye according to any one of Claims 1 to
4, characterized in that X denotes an amino -NR 3R4 radical in which
R3 denotes a hydrogen atom or a linear or branched C1-C3 alkyl
radical, optionally substituted by a hydroxyl radical and R4 denotes a
hydrogen atom or a linear or branched C1-C3 alkyl radical, optionally
substituted by a hydroxyl radical.
6 . Azomethine direct dye according to any one of Claims 1 to
5, characterized in that it is chosen from the following compounds and
their geometric or optical isomeric forms, their salts with an organic
or inorganic acid, or their solvates such as hydrates:
2-[4-(Ethylisopropylamino)-
phenylamino]-
4-[4-(ethylisopropylamino)
phenylimino]-5-
hydroxy-3-methylcyclohexa-
2,5-dienone
2- (4-[Ethyl(2-hydroxyethyl)-
amino]-2-methylphenylamino}
-4- {4- [ethylshydro
xyethyl) -amino] -2-
methylphenylimino }-5-
hydroxy-3-methyl-
Compound 2 cyclohexa-2,5-dienone
2-(4-Amino-2,3-dimethylphenylamino)-
4-[4-amino-2,3-
dimethylphenylimino]-5-
hydroxy-3-methylcyclohexa-
2,5-dienone
Compound 3
2-(4-Aminophenylamino)-4-[4-
aminophenylimino]-5-hydroxy-
3-methylcyclohexa-
2,5-dienone
Compound 4
5-Hydroxy-2-(4-hydroxyphenylamino)
-4-[4-hydroxyphenylimino]-3-
methylcyclohexa-2,5-dienone
Compound 5
2-(4-Amino-3 (or 2)-methylphenylamino)-
4-
[4-amino-3 (or 2)-methylphenylimino]-
5-hydroxy-3-methylcyclohexa-
2,5-dienone
Compound 6
2-(3-Chloro-4-hydroxyphenylamino)-
4-[3-chloro-4-hydroxyphenylimino]-
5-hydroxy-3-
methylcyclohexa-2,5-dienone
Compound 7
2-(2-Chloro-4-hydroxyphenylamino)-
4-[2-chloro-4-hydroxyphenylimino]-
5-hydroxy-3-
methylcyclohexa-2,5-dienone
Compound 8
5-Hydroxy-2-[4-(6-hydroxyhexylamino)
phenylamino]-4-
[4-(6-hydroxyhexylamino)
phenylimino]-3-
methylcyclohexa-
2,5-dienone
OH
Compound 9
2-[4-(Ethylisopropylamino)-
phenylamino]-
4-[4-(ethylisopropylamino)
phenylimino]-5-
hydroxycyclohexa-2,5-
dienone
Compound 10
2- {4-[Ethyl(2-hydroxyethyl)
amino]-2-methylphenylamino}
-4- {4- [ethylshydro
xyethyl) amino] -2-
methylphenylimino }-5-
hydroxycyclohexa-
2,5-dienone
Compound 11
2-(4-Amino-2,3-dimethylphenylamino)-
4-[4-amino-2,3-
dimethylphenylimino]-5-
hydroxy-3-methylcyclohexa-
2,5-dienone
Compound 12
2-(4-Amino -3-methy1-
phenylamino)-4-
[4-amino-3 (or 2)-methylphenylimino]-
5-hydroxycyclohexa-2,5-
Compound 13 dienone
2-(3-Chloro-4-hydroxyphenylamino)-
4-[3-chloro-4-hydroxyphenylimino]-
5-hydroxycyclohexa-
2,5-dienone
Compound 14
C I C I
2-(2-Chloro-4-hydroxyphenylamino)-
4-[2-chloro-4-hydroxyphenylimino]-
5-hydroxycyclohexa-
2,5-dienone
Compound 15
5-Hydroxy-2-[4-(6-hydroxy-
J H hexylamino)phenylamino]-4-
[4-(6-hydroxyhexylamino)
phenylimino]-
cyclohexa-2,5-dienone
OH
Compound 16
6-[4-(Ethylisopropylamino)-
phenylamino]-
4-[4-(ethylisopropylamino)
phenylimino]-3-
hydroxy-2-methoxycyclohexa-
2,5-dienone
Compound 17
2- (4-[Ethyl(2-hydroxyethyl)-
amino]-2-methylphenylamino}
-4- {4- [ethylshydro
xyethyl) amino] -2-
methylphenylimino }-2-
hydroxy-2-methoxy-
Compound 18 cyclohexa-2,5-dienone
2-(4-Amino-2,3-dimethylphenylamino)-
4-[4-amino-2,3-
dimethylphenylimino]-3-
hydroxy-2-methoxycyclohexa-
2,5-dienone
Compound 19
2-(4-Aminophenylamino)-4-[4-
aminophenylimino]-3-hydroxy-2-
methoxycyclohexa-
2,5-dienone / °
Compound 20
3-Hydroxy-2-(4-hydroxyphenylamino)-
4-[4-hydroxyphenylimino]-2-
/ ° methoxycyclohexa-2,5-dienone
Compound 21
2-(4-Amino-3 (or 2)-methylphenylamino)-
4-
[4-amino-3 (or 2)-methylphenylimino]-
/ 3-hydroxy-2-methoxycyclohexa- 2,5-dienone
Compound 22
2-(3-Chloro-4-hydroxyphenylamino)-
4-[3-chloro-4-hydroxyphenylimino]-
3-hydroxy-2-
methoxycyclohexa-2,5-dienone
Compound 23
C I C I
2-(2-Chloro-4-hydroxyphenylamino)-
4-[2-chloro-4-hydroxyphenylimino]-
3-hydroxy-2-
/ ° methoxycyclohexa-2,5-dienone
Compound 24
3-Hydroxy-2-[4-(6-hydroxyhexylamino)
phenylamino]-4-
[4-(6-hydroxyhexylamino)
phenylimino]-2-
OH methoxy-
OH cyclohexa-2,5-dienone
Compound 25
2-[4-(Ethylisopropylamino)-
phenylamino]-
4-[4-(ethylisopropylamino)
phenylimino]-5-
hydroxy-3-pentylcyclohexa-
2,5-dienone
Compound 26
2- (4-[Ethyl(2-hydroxyethyl)-
amino]-2-methylphenylamino}
-4- {4- [ethylshydro
xyethyl) amino] -2-
methylphenylimino }-5-
hydroxy-3-pentylcyclohexa-
2,5-dienone
Compound 27
2-(4-Amino-2,3-dimethylphenylamino)-
4-[4-amino-2,3-
dimethylphenylimino]-5-
hydroxy-3-pentylcyclohexa-
2,5-dienone
Compound 28
2-(4-Aminophenylamino)-4-[4-
aminophenylimino]-5-hydroxy-
3-pentylcyclohexa-
2,5-dienone
Compound 29
5-Hydroxy-2-(4-hydroxyphenylamino)-
4-[4-hydroxyphenylimino]-3-
pentylcyclohexa-2,5-dienone
Compound 30
2-(4-Amino-3 (or 2)-methylphenylamino)-
4-
[4-amino-3 (or 2)-methylphenylimino]-
5-hydroxy-3-pentylcyclohexa-
2,5-dienone
Compound 31
2-(3-Chloro-4-hydroxyphenylamino)-
4-[3-chloro-4-hydroxyphenylimino]-
5-hydroxy-3-
pentylcyclohexa-2,5-dienone
Compound 32
2-(2-Chloro-4-hydroxy-
C I C I phenylamino)-
4-[2-chloro-4-hydroxyphenylimino]-
5-hydroxy-3-
pentylcyclohexa-2,5-dienone
Compound 33
5-Hydroxy-2-[4-(6-
hydroxyhexylamino)phenylami
no]-4-[4-(6-hydroxyhexylamino)
phenylimino]-3-
pentylcyclohexa-
2,5-dienone
Compound 34
2-[4-(Ethylisopropylamino)-
phenylamino]-
4-[4-(ethylisopropylamino)
phenylimino]-5-
hydroxy-3-hydroxymethylcyclohexa-
2,5-dienone
Compound 35
2- (4-[Ethyl(2-hydroxyethyl)-
amino]-2-methylphenylamino}
-4- {4- [ethylshydro
xyethyl) amino] -2-
methylphenylimino }-5-
hydroxy-3-hydroxymethylcyclohexa-
2,5-dienone
Compound 36
HO 2-(4-Amino-2,3-
dimethylphenylamino)-4-[4-
amino-2,3-
dimethylphenylimino]-5-
hydroxy-3-hydroxymethylcyclohexa-
2,5-dienone
Compound 37
2-(4-Aminophenylamino)-4-[4-
aminophenylimino]-5-hydroxy-
3-hydroxymethylcyclohexa-
2,5-dienone
Compound 38
5-Hydroxy-2-(4-hydroxyphenylamino)-
4-[4-hydroxyphenylimino]-3-
hydroxymethylcyclohexa-2,5-
dienone
Compound 39

6-[4-(Ethylisopropylamino)-
phenylamino]-
4-[4-(ethylisopropylamino)
phenylimino]-3-hydroxy-
2-propylcyclohexa-2,5-dienone
Compound 44
2- (4-[Ethyl(2-hydroxyethyl)-
amino]-2-methylphenylamino} -
4- (4-[ethyl(2-hydroxyethyl)-
amino]-2-methylphenylimino} -
3-hydroxy-2-propylcyclohexa-
2,5-dienone
Compound 45
2-(4-Amino-2,3-dimethylphenylamino)-
4-[4-amino-2,3-
dimethylphenylimino]-3-
hydroxy-2-propylcyclohexa-2,5-
dienone
Compound 46
2-(4-Aminophenylamino)-4-[4-
aminophenylimino]-3-hydroxy-
2-propylcyclohexa-
2,5-dienone
Compound 47
3-Hydroxy-2-(4-hydroxyphenylamino)-
4-[4-hydroxyphenylimino]-2-
propylcyclohexa-2,5-dienone
Compound 48
2-(4-Amino-3 (or 2)-methylphenylamino)-
4-
[4-amino-3 (or 2)-methylphenylimino]-
3-hydroxy-2-propylcyclohexa-
2,5-dienone
Compound 49
2-(3-Chloro-4-hydroxyphenylamino)-
4-[3-chloro-4-hydroxyphenylimino]-
3-hydroxy-2-
propylcyclohexa-2,5-dienone
Compound 50
2-(2-Chloro-4-hydroxyphenylamino)-
4-[2-chloro-4-hydroxyphenylimino]-
3-hydroxy-2-
propylcyclohexa-2,5-dienone
Compound 51
3-Hydroxy-2-[4-(6-hydroxyhexylamino)
phenylamino]-4-[4-
(6-hydroxyhexylamino)
phenylimino]-2-
propylcyclohexa-
2,5-dienone
Compound 52
2-[4-(Ethylisopropylamino)-
phenylamino]-
4-[4-(ethylisopropylamino)
phenylimino]-5- k hydroxy-3,6-dimethylcyclohexa-
2,5-dienone
Compound 53
2- (4-[Ethyl(2-hydroxyethyl)-
amino]-2-methylphenylamino}
-4- {4- [ethylshydro
xyethyl) amino] -2-
methylphenylimino }-5-
hydroxy-3,6-dimethyl-
Compound cyclohexa-2,5-dienone 54
2-(4-Amino-2,3-dimethylphenylamino)-
4-[4-amino-2,3-
dimethylphenylimino]-5-
hydroxy-3,6-dimethylcyclohexa-
2,5-dienone
Compound 55
2-(4-Aminophenylamino) -4- [4-
aminophenylimino]-5-hydroxy-
3,6-dimethylmethyl-cyclohexa-
2,5-dienone
Compound 56
5-Hydroxy-2-(4-hydroxyphenylamino)-
4-[4-hydroxyphenylimino]-3,6-
dimethylmethyl-cyclohexa-2,5-
dienone
Compound 57
2-(4-Amino-3 (or 2)-methylphenylamino)-
4-
[4-amino-3 (or 2)-methylphenylimino]-
5-hydroxy-3,6-dimethylmethylcyclohexa-
2,5-dienone
Compound 58
2-(3-Chloro-4-hydroxyphenylamino)-
4-[3-chloro-4-hydroxyphenylimino]-
5-hydroxy-3,6-
dimethylmethylcyclohexa-2,5-
dienone
Compound 59
2-(2-Chloro-4-hydroxyphenylamino)-
4-[2-chloro-4-hydroxyphenylimino]-
5-hydroxy-3,6-
dimethylmethylcyclohexa-2,5-
Compound dienone 60
5-Hydroxy-2-[4-(6-hydroxy-
J [ hexylamino)phenylamino]-4-
[4-(6-hydroxyhexylamino)
phenylimino]-3,6-
OH dimethylmethyl-cyclohexa-2,5-
OH dienone
Compound 61
7 . Use of one or more azomethine-type direct dyes of formula
(I) as defined according to any one of Claims 1 to 6, for colouring
keratin fibres, in particular human keratin fibres such as the hair.
8. Composition for dyeing keratin fibres, particularly human
keratin fibres such as the hair, characterized in that it comprises, in a
suitable medium for dyeing, one or more azomethine-type direct dyes
of formula (I) as defined according to any one of Claims 1 to 6 .
9 . Colouring method for keratin fibres, particularly human
keratin fibres such as the hair, in which a dyeing composition
comprising, in a suitable medium for dyeing, one or more azomethinetype
direct dyes of formula (I) as defined according to any one of
Claims 1 to 6 is applied to said fibres for a long enough period to
obtain the desired colour, after which the fibres are rinsed, optionally
washed with shampoo, rinsed again and the resulting fibres are dried
or left to dry.
10 . Lightening method for keratin fibres, in particular human
keratin fibres such as the hair, in which a dyeing composition
comprising, in a suitable medium for dyeing, (i) one or more
azomethine-type direct dyes of formula (I) as defined according to any
one of Claims 1 to 6 free of oxidizing agent and (ii) a cosmetic
composition comprising one or more oxidizing agents are applied to
said fibres; compositions (i) and (ii) being applied to said keratin
fibres sequentially or simultaneously for a long enough period to
obtain the desired lightening, after which the fibres are rinsed,
optionally washed with shampoo, rinsed again and the resulting fibres
are dried or left to dry.
11. Leuco-type compound having the following formula (II), its
organic or inorganic salts with an acid or a base, its tautomeric forms,
optical isomers, geometric isomers and/or its solvates:
formula (II) in which n, R, Rl R2 and X have the same meanings as
indicated according to any one of Claims 1 to 6 .
12. Use of one or more leuco-type compounds of formula (II)
as defined according to Claim 11 as precursors for azomethine-type
direct dyes of formula (I) as defined according to any one of Claims 1
to 6 .
13. Use of one or more leuco-type compounds of formula (II)
as defined according to Claim 11 in the presence of one or more
oxidizing agents for colouring keratin fibres, in particular human
keratin fibres such as the hair.
14. Cosmetic composition comprising, in a cosmetically
acceptable medium, one or more leuco-type compounds of formula (II)
as defined according to Claim 11, optionally in the presence of one or
more oxidizing agents.
15. Method for dyeing keratin fibres, particularly human
keratin fibres such as the hair, in which a cosmetic composition
comprising one or more leuco-type compounds of formula (II) as
defined in Claim 11 in the presence of one or more oxidizing agents is
applied to said fibres for a long enough period to develop the desired
colour, after which the fibres are rinsed, optionally washed with
shampoo, rinsed again and the resulting fibres are dried or left to dry.
16 . Multi-compartment device or kit comprising a first
compartment containing a composition comprising one or more
azomethine direct dyes of formula (I) as defined according to any one
of Claims 1 to 6 or one or more leuco-type compounds of formula (II)
as defined according to Claim 11, and a second compartment
comprising one or more oxidizing agents.