FIELD OF THE INVENTION
5 The present invention relates to a process for dyeing keratin fibers using a) one or more
direct dyes and b) one or more particular saccharinate salts.
BACKGROUND OF THE INVENTION
It is known practice to dye keratin fibers and in particular human hair with dye
10 compositions containing oxidation dye precursors, which are generally known as
oxidation bases, such as ortho- or para-phenylenediamines, ortho- or paraaminophenols
and heterocyclic compounds. These oxidation bases are generally
combined with couplers. These bases and couplers are colorless or weakly colored
compounds, which, when combined with oxidizing products, may give rise to colored
15 compounds by a process of oxidative condensation. This type of oxidation dyeing makes
it possible to obtain "permanent" colorings.
Moreover, it is known practice to dye keratin fibers and in particular human hair with dye
compositions containing direct dyes. The standard dyes that are used are, in particular,
dyes of the nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine or
20 triarylmethane type, or natural dyes. These dyes are colored or coloring molecules that
have affinity for keratin fibers.
Compositions containing one or more direct dyes are applied to the keratin fibers for a
time necessary to obtain the desired coloring, and are then rinsed out. The resulting
colorings are particularly chromatic colorings, but are, however, temporary or semi-
25 permanent since the nature of the interactions that bind the direct dyes to the keratin
fiber and their desorption from the surface and/or the core of the fiber are responsible for
their weaker dyeing power and their poorer persistence with respect to washing or
perspiration.
Direct dyeing products notably make it possible to modify the natural color of the hair, or
30 to cover white hairs. However, the intensity of the coloring obtained by using these
products is occasionally judged as being too weak relative to the expectations of users
on the day of application.
In addition, direct colorings have the drawback of fading out over time, in particular under
the action of UV, inclement weather and successive shampooing.
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There is therefore a real need to develop a process for dyeing keratin fibers using direct
dyes which makes it possible to obtain a better color build-up and intense and chromatic
colors.
The applicant has discovered, surprisingly, that all of these objectives can be achieved
5 by the process according to the present invention.
SUMMARY OF THE INVENTION
According to a first aspect, a subject of the present invention is a process for dyeing
keratin fibers using:
10 a) one or more direct dyes; and
b) one or more compounds of formula (A):
(A)
wherein:
• y+ represents a cationic counterion chosen from the compounds of formula (Ia), (lb),
15 (lc) or (ld) below:
R1
I+
R4/l''R3
R2
(Ia)
formula (Ia) wherein R1, R2, R3 and R4 represent independently of one another:
• a hydrogen atom;
• a linear or branched, saturated or unsaturated, C1-C12, preferably C1-C1o, hydrocarbon-
20 based group, optionally substituted with one or more group(s) chosen from: hydroxyl,
thiol, (C1-C5)alkylthio, amino, -NH3+, (C1-C5)dialkylamino, (C1-C5)alkylamino, (C1-
C4)alkoxyl, carboxyl, carboxylate, -S03H, -So3-, -C(O)NH2, -NHC(NH)-NH2, -
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C(O)ORa, -OC(O)-Ra, -C(O)NHRa, -NH-C(O)-Ra, phenyl, indolyl, phenol, furan,
guaiacol, imidazole or guanine and/or optionally interrupted by one or more group(s)
chosen from -C(O)-, -NRb-, -C(NRb)-, -OC(O)-, -C(O)O-, -C(O)NRb- or -NRbC(O)-;
- Ra representing a (C1-C4)alkyl group; and
5 - Rb representing a hydrogen atom or a (C1-C4)alkyl group, preferably a hydrogen atom;
it being understood that the overall charge of the compounds of formula (Ia) is positive;
(I b)
formula (lb) wherein:
• X represents an oxygen atom or an N Rb group;
10 • Rs, Rs and R1 represent independently of one another:
-a hydrogen atom;
- a carboxyl or carboxylate group;
-a -C (O)NH2 group;
-a linear or branched, saturated or unsaturated, C-C12, preferably C1-C1o, hydrocarbon-
15 based group, optionally substituted with one or more group(s) chosen from: hydroxyl,
thiol, (C1-C5)alkylthio, amino, -NH3+, (C1-C5)dialkylamino, (C1-C5)alkylamino, (C1-
C4)alkoxyl, carboxyl, carboxylate, -S03H, -So3-, -C(O)NH2, -NHC(NH)-NH2, -
C(O)ORa, -OC(O)-Ra, -C(O)NHRa, -NH-C(O)-Ra, phenyl, indolyl, phenol, furan,
guaiacol, imidazole or guanine and/or optionally interrupted by one or more group(s)
20 chosen from -C(O)-, -NRb-, -C(NRb)-, -OC(O)-, -C(O)O-, -C(O)NRb- or -NRbC(O)-;
Ra representing a (C1-C4)alkyl group; and
25
Rb representing a hydrogen atom or a (C1-C4)alkyl group, preferably a hydrogen atom;
it being understood that the overall charge of the compounds of formula (I b) is positive;
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formula (lc) wherein:
• Het represents a cationic saturated heterocyclic group comprising:
- from 5 to 10 ring members, preferably 5 or 6 ring members; and
- in addition to the ammonium bearing R'1 and R'2, optionally one or two atoms chosen
5 from nitrogen and/or oxygen atoms, preferably a nitrogen atom;
the heterocyclic group being optionally substituted with one or more group(s) R'3;
• R'1 and R'2, which may be identical or different, represent a hydrogen atom or a linear
or branched, saturated or unsaturated, C1-C12 hydrocarbon-based group, optionally
substituted with one or more group(s) chosen from: hydroxyl, amino, (C-
10 C6)dialkylamino, (C1-C5)alkylamino, carboxyl, carboxylate, carbamide, (C1-C4)alkoxyl,S03H,
-so3- or phenyl;
• R'3, which may be identical or different, represent a hydroxyl group, an amino group, a
-C(O)OR'4 group, an -OC(O)-R'4 group, a -C(O)NHR'4 group, an -NH-C(O)-R'4 group,
a linear or branched, saturated or unsaturated, C1-C12 hydrocarbon-based group,
15 optionally substituted with one or more group(s) chosen from: hydroxyl, amino, (C1-
C6)dialkylamino, (C1-C5)alkylamino, carboxyl, carboxylate, carbamide, (C1-C4)alkoxyl,S03H,
-so3- or phenyl;
• R'4 represents a hydrogen atom, a linear or branched, saturated or unsaturated, C-C12
hydrocarbon-based group, optionally substituted with one or more group(s) chosen from
20 hydroxyl, amino, (C1-C5)dialkylamino or (C1-C5)alkylamino;
it being understood that the overall charge of the compounds of formula (I c) is positive;
+ Rn -m 1
(I d)
formula (ld) wherein:
25 • Het' represents a cationic aromatic unsaturated heterocyclic group comprising:
- from 5 to 10 ring members, preferably 5 or 6 ring members; and
- in addition to the ammonium bearing R"1, optionally one or two atoms chosen from
nitrogen or oxygen atoms, preferably a nitrogen atom;
said heterocyclic group being optionally substituted with one or more group(s) R"2;
30
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• R"1 represents a linear or branched, saturated or unsaturated, C1-C12 hydrocarbonbased
group, optionally substituted with one or more group(s) chosen from hydroxyl,
amino, (C1-C5)dialkylamino, (C1-C5)alkylamino, carboxyl, carboxylate, carbamide, (C1-
C4)alkoxyl, -S03H, -So3- or phenyl; and
5 • R"2, which may be identical or different, represent a hydroxyl group, an amino group,
or a linear or branched, saturated or unsaturated, C1-C12 hydrocarbon-based group,
optionally substituted with one or more group(s) chosen from hydroxyl, amino, (C1-
C6)dialkylamino, (C1-C5)alkylamino, carboxyl, carboxylate, carbamide, (C1-C4)alkoxyl, -
S03H, -so3- or phenyl;
10 it being understood that the overall charge of the compounds of formula (I d) is positive;
· x is a stoichiometric coefficient chosen so as to ensure the electrical neutrality of the
compound of formula (A);
15
20
25
it being understood that the ingredients a) and b) are applied simultaneously or
sequentially to the keratin fibers, preferably simultaneously.
According to a second aspect, a subject of the present invention is a composition
comprising:
a) optionally one or more direct dyes; and
b) one or more compounds of formula (A) as defined above.
According to a third aspect, a subject of the present invention is a multicompartment
device or kit, comprising a first compartment which comprises one or more direct dyes
and a second compartment which comprises one or more compounds of formula (A) as
defined above.
Detailed description of the invention
For the purposes of the present invention and unless otherwise indicated:
• the term "keratin fibers" is intended to mean fibers of human or animal origin such as
head hair, bodily hair, the eyelashes, the eyebrows, wool, angora, cashmere or fur.
30 According to the present invention, the keratin fibers are preferably human keratin fibers,
more preferentially the hair;
• the term "direct dyes" is intended to mean natural and/or synthetic dyes, including in
the form of an extract or extracts, other than oxidation dyes. These are dyes that will
spread superficially on the fiber. They may be ionic or nonionic, i.e. anionic, cationic,
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neutral or nonionic. The direct dyes may be of the same types of ionicity or else as
mixtures.
• the direct dyes contain one or more chromophores, and these dyes are capable of
absorbing light at a wavelength Aabs ranging from 400 nm to 700 nm;
5 • the fluorescent direct dyes are dyes containing at least one fluorescent chromophore,
and these dyes are capable of absorbing in the visible range at a wavelength Aabs ranging
from 400 nm to 800 nm and of re-emitting in the visible range at a wavelength Aem longer
than that absorbed ranging from 400 nm to 800 nm.
The difference between the absorption and emission wavelengths, also known as the
10 Stoke's shift, is from 1 nm to 100 nm. Preferably, the fluorescent direct dyes are dyes
that are capable of absorbing at a wavelength Aabs ranging from 420 nm to 550 nm and
of re-emitting in the visible range at a wavelength Aem ranging from 470 to 600 nm;
• the term "alkyl group" is intended to mean a linear or branched, saturated hydrocarbonbased
radical;
15 • the term "(Cx-Cy)alkyl group" means an alkyl group comprising from x to y carbon atoms;
• the term "hydroxy(Cx-Cy)alkyl group" is intended to mean a (Cx-Cy)alkyl group, at least
one of the hydrogen atoms of which is replaced with a hydroxyl (-OH) group;
• the term "(hydroxy)(Cx-Cy)alkyl group" is intended to mean a hydroxy(Cx-Cy)alkyl group
or a (Cx-Cy)alkyl group;
20 • the term "alkoxy group" means an alkyl group bonded to an oxygen atom;
• the term "(Cx-Cy)alkoxy group" means an alkoxy group comprising from x to y carbon
atoms;
• the term "hydroxy(Cx-Cy)alkoxy group" is intended to mean a (Cx-Cy)alkoxy group, at
least one of the hydrogen atoms of which is replaced with a hydroxyl (-OH) group;
25 • the expression "optionally substituted" applied to an alkyl or alkoxy group implies that
the alkyl or alkoxy group may be substituted with one or more groups chosen from: i)
hydroxyl, ii) (C1-C4) alkoxy, iii) acylamino, iv) amino optionally substituted with one or two
identical or different (hydroxy)(C1-C4)alkyl groups, said alkyl groups possibly forming,
with the nitrogen atom that bears them, a heterocycle comprising from 5 to 7 ring
30 members, said heterocycle optionally comprising another nitrogen or non-nitrogen
heteroatom; v) a quaternary ammonium group -WR'R"R"', M- for which R', R" and R"',
which may be identical or different, represent a hydrogen atom or a (C1-C4)alkyl group,
or else R', R" and R"' form, with W, a heteroaryl such as imidazolium optionally
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substituted with a (C1-C4)alkyl group, and M- represents an anion, or a mixture of anions,
intended to ensure electrical neutrality;
• the term "alkylene group" is intended to mean a linear or branched C1-C10, particularly
C1-C6, more particularly C1-C2, acyclic hydrocarbon-based divalent chain, optionally
5 substituted with one or more groups, which may be identical or different, chosen from i)
hydroxyl, ii) (C1-C2)alcoxyl, iii) (poly)hydroxy(C2-C4)alcoxy(di)(C1-C2)(alkyl)amino, iv)
(poly)hydroxy(di)(C1-C2)(alkyl)amino, v) Ra-za-C(Zb)_zc-, vi) Ra'-C(Zb)_za_ and vii) Ra-za_
S(O)t-zc_ with za and zb, which may be identical or different, representing an oxygen or
sulfur atom, or a group NRa', zc, representing a bond, an oxygen or sulfur atom, or a
10 group NRa; Ra representing an alkali metal, a hydrogen atom or an alkyl group, or else
is absent if another part of the molecule is cationic, and Ra' representing a hydrogen
atom or an alkyl group and t is equal to 1 or 2; preferably the "alkylene group" represents
a -(CH2)p- group with p being an integer between 1 and 6, preferably between 1 and 4;
15 • the term "(hetero )aryl" is intended to mean an aryl group or a heteroaryl group;
• the term "aryl group" is intended to mean a monocyclic or fused or non-fused polycyclic
carbon-based group, comprising from 6 to 22 carbon atoms, at least one ring of which is
aromatic; preferentially, the aryl group is a phenyl, biphenyl, naphthyl, indenyl,
anthracenyl or tetrahydronaphthyl;
20 • the term "heteroaryl group" is intended to mean an optionally cationic, 5- to 22-
membered monocyclic or fused or non-fused polycyclic group, comprising from 1 to 6
heteroatoms chosen from nitrogen, oxygen, sulfur and selenium atoms, and at least one
ring of which is aromatic; preferentially, a heteroaryl group is chosen from acridinyl,
benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl,
25 benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl,
imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyl, naphthooxazolyl,
naphthopyrazolyl, oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl, phenoxazolyl,
pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl,
tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyl, thiopyrylyl, triazolyl,
30 xanthylyl and its ammonium salt;
• a (hetero)aryl group or the aryl or heteroaryl part of a group may optionally be
substituted with at least one group borne by a carbon atom, chosen from:
- a (C1-C10)alkyl, preferably (C1-Cs)alkyl, group, optionally substituted with at least one
group chosen from: hydroxyl, (C1-C2)alkoxy, hydroxy(C2-C4)alkoxy, acylamino, amino
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optionally substituted with one or two (C1-C4)alkyl groups, which may be identical or
different, optionally bearing at least one hydroxyl group, or the two (C1-C4)alkyl groups
possibly forming, with the nitrogen atom to which they are attached, a 5- to ?-membered
and preferably 5- or 6-membered heterocycle, said heterocycle being saturated or
5 unsaturated and optionally substituted and optionally comprising another nitrogen or
non-nitrogen heteroatom;
- a halogen atom;
- a hydroxyl group;
- a (C1-C2)alkoxy group;
10 - a hydroxy(C2-C4)alkoxy group;
- an amino group;
- a 5- or 6-membered heterocycloalkyl group;
- an optionally cationic 5- or 6-membered heteroaryl group, preferentially imidazolium,
optionally substituted with a (C1-C4)alkyl group, preferentially methyl;
15 - an amino group substituted with one or two identical or different (C1-C5)alkyl groups,
optionally bearing at least:
i) a hydroxyl group;
ii) an amino group optionally substituted with one or two optionally substituted (C1-
C3)alkyl groups, said alkyl groups possibly forming, with the nitrogen atom to which they
20 are attached, a saturated or unsaturated, optionally substituted 5- to ?-membered
heterocycle, optionally comprising at least one other nitrogen or non-nitrogen
heteroatom;
iii) a quaternary ammonium group -N+R'R"R"', M- for which R', R" and R"', which may
be identical or different, represent a hydrogen atom or a (C1-C4)alkyl group and M-
25 represents an anionic counterion;
iv) an optionally cationic 5- or 6-membered heteroaryl group, preferentially imidazolium,
optionally substituted with a (C1-C4)alkyl group, preferentially methyl;
v) an acylamino (-N(R)-C(O)-R') group wherein R represents a hydrogen atom or a
(hydroxy)(C1-C4)alkyl group and R' represents a (C1-C2)alkyl group;
30 - an acylamino (-N(R)-C(O)-R') group wherein R represents a hydrogen atom or a
(hydroxy)(C1-C4)alkyl group and R' represents a (C1-C2)alkyl group;
- a carbamoyl group ((R)2N-C(O)-) wherein R, which may be identical or different,
represent a hydrogen atom or a (hydroxy)(C1-C4)alkyl group;
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- an alkylsulfonylamino (R'-S(0)2-N(R)-) group wherein R represents a hydrogen atom
or a (hydroxy)(C1-C4)alkyl group and R' represents a (C1-C4)alkyl group or a phenyl
group;
-an aminosulfonyl ((R)2N-S(0)2-) group wherein R, which may be identical or different,
5 represent a hydrogen atom or a (hydroxy)(C1-C4)alkyl group;
- a carboxylic group in acid form or salified form (preferably salified with an alkali metal
or a substituted or unsubstituted ammonium);
- a cyano group;
- a nitro or nitroso group;
10 - a polyhaloalkyl group, preferentially trifluoromethyl;
- an ester group;
·the term "cationic heteroaryl group" is intended to mean a heteroaryl group as defined
above, which comprises an endocyclic or exocyclic quaternized cationic group;
- when the cationic charge is endocyclic, it is included in the electron delocalization via
15 the mesomeric effect, for example it is a pyridinium, imidazolium or indolinium group:
with R and R' being a heteroaryl substituent as defined above and particularly a
(hydroxy)(C1-Cs)alkyl group such as methyl;
20 -when the charge is exocyclic, for example, it is an ammonium substituent R+, such as
trimethylammonium or phosphonium, which is exterior to the heteroaryl such as pyridinyl,
indolyl, imidazolyl or naphthalimidyl in question;
with R a heteroaryl substituent as defined above and R+ an ammonium RaRbRcW-,
25 phosphonium RaRbRcP+- or ammonium RaRbRcW-(C1-C6)alkylamino group with Ra, Rb
and Rc, which may be identical or different, representing a hydrogen atom or a (C1-
Cs)alkyl group such as methyl;
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• the term "cationic aryl group bearing an exocyclic charge" is intended to mean an aryl
ring of which the quaternized cationic group is outside said ring; it is in particular an
ammonium substituent R+ such as trimethylammonium or phosphonium, which is outside
R~
the aryl such as phenyl or naphthyl:
5 ·the term "(hetero)cyclic group" is intended to mean a heterocyclic group or a carbocyclic
group;
• the term "heterocyclic group" is intended to mean a 5- to 22-membered monocyclic or
fused or non-fused polycyclic group that may contain one or two unsaturations but is
nonaromatic, comprising from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur
10 and selenium atoms;
• the term "heterocycloalkyl group" is intended to mean a saturated heterocyclic group
such as morpholinyl, piperazinyl or piperidinyl;
• the term "carbocyclic group" is intended to mean a 5- to 22-membered monocyclic or
fused or non-fused polycyclic group that may contain one or two unsaturations but is
15 nonaromatic, such as cyclobutyl, cyclopentyl or cyclohexyl;

CLAIMS
1. A process for dyeing keratin fibers using:
a) one or more direct dyes; and
b) one or more compounds of formula (A):
(A)
wherein:
• y+ represents a cationic counterion chosen from the compounds of formula (Ia), (lb),
(lc) or (ld) below:
(Ia)
10 formula (Ia) wherein R1, R2, R3 and R4 represent independently of one another:
• a hydrogen atom;
• a linear or branched, saturated or unsaturated, C1-C12, preferably C1-C1o, hydrocarbonbased
group, optionally substituted with one or more group(s) chosen from: hydroxyl,
thiol, (C1-C5)alkylthio, amino, -NH3+, (C1-C5)dialkylamino, (C1-C5)alkylamino, (C1-
15 C4)alkoxyl, carboxyl, carboxylate, -S03H, -So3-, -C(O)NH2, -NHC(NH)-NH2, -
C(O)ORa, -OC(O)-Ra, -C(O)NHRa, -NH-C(O)-Ra, phenyl, indolyl, phenol, furan,
guaiacol, imidazole or guanine and/or optionally interrupted by one or more group(s)
chosen from -C(O)-, -NRb-, -C(NRb)-, -OC(O)-, -C(O)O-, -C(O)NRb- or -NRbC(O)-;
- Ra representing a (C1-C4)alkyl group; and
20 - Rb representing a hydrogen atom or a (C1-C4)alkyl group, preferably a hydrogen atom;
it being understood that the overall charge of the compounds of formula (Ia) is positive;
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X
(I b)
formula (lb) wherein:
• X represents an oxygen atom or an N Rb group;
• Rs, Rs and R1 represent independently of one another:
5 -a hydrogen atom;
- a carboxyl or carboxylate group;
-a -C(O)NH2 group;
-a linear or branched, saturated or unsaturated, C-C12, preferably C1-C1o, hydrocarbonbased
group, optionally substituted with one or more group(s) chosen from: hydroxyl,
10 thiol, (C1-C5)alkylthio, amino, -NH3+, (C1-C5)dialkylamino, (C1-C5)alkylamino, (C1-
C4)alkoxyl, carboxyl, carboxylate, -S03H, -So3-, -C(O)NH2, -NHC(NH)-NH2, -
C(O)ORa, -OC(O)-Ra, -C(O)NHRa, -NH-C(O)-Ra, phenyl, indolyl, phenol, furan,
guaiacol, imidazole or guanine and/or optionally interrupted by one or more group(s)
chosen from -C(O)-, -NRb-, -C(NRb)-, -OC(O)-, -C(O)O-, -C(O)NRb- or -NRbC(O)-;
15 Ra representing a (C1-C4)alkyl group; and
Rb representing a hydrogen atom or a (C1-C4)alkyl group, preferably a hydrogen atom;
it being understood that the overall charge of the compounds of formula (I b) is positive;
{I c)
20 formula (lc) wherein:
• Het represents a cationic saturated heterocyclic group comprising:
- from 5 to 10 ring members, preferably 5 or 6 ring members; and
- in addition to the ammonium bearing R'1 and R'2, optionally one or two atoms chosen
from nitrogen and/or oxygen atoms, preferably a nitrogen atom;
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the heterocyclic group being optionally substituted with one or more group(s) R'3;
• R'1 and R'2, which may be identical or different, represent a hydrogen atom or a linear
or branched, saturated or unsaturated, C1-C12 hydrocarbon-based group, optionally
substituted with one or more group(s) chosen from: hydroxyl, amino, (C-
5 C6)dialkylamino, (C1-C5)alkylamino, carboxyl, carboxylate, carbamide, (C1-C4)alkoxyl, -
S03H, -so3- or phenyl;
• R'3, which may be identical or different, represent a hydroxyl group, an amino group, a
-C(O)OR'4 group, an -OC(O)-R'4 group, a -C(O)NHR'4 group, an -NH-C(O)-R'4 group,
a linear or branched, saturated or unsaturated, C1-C12 hydrocarbon-based group,
10 optionally substituted with one or more group(s) chosen from: hydroxyl, amino, (CC6)
dialkylamino, (C1-C5)alkylamino, carboxyl, carboxylate, carbamide, (C1-C4)alkoxyl,S03H,
-so3- or phenyl;
• R'4 represents a hydrogen atom, a linear or branched, saturated or unsaturated, C-C12
hydrocarbon-based group, optionally substituted with one or more group(s) chosen from
15 hydroxyl, amino, (C1-C5)dialkylamino or (C1-C5)alkylamino;
it being understood that the overall charge of the compounds of formula (I c) is positive;
Rll
- 1
(I d)
formula (ld) wherein:
20 • Het' represents a cationic aromatic unsaturated heterocyclic group comprising:
- from 5 to 10 ring members, preferably 5 or 6 ring members; and
25
- in addition to the ammonium bearing R"1, optionally one or two atoms chosen from
nitrogen or oxygen atoms, preferably a nitrogen atom;
said heterocyclic group being optionally substituted with one or more group(s) R"2;
• R"1 represents a linear or branched, saturated or unsaturated, C1-C12 hydrocarbonbased
group, optionally substituted with one or more group(s) chosen from hydroxyl,
amino, (C1-C5)dialkylamino, (C1-C5)alkylamino, carboxyl, carboxylate, carbamide, (C1-
C4)alkoxyl, -S03H, -So3- or phenyl; and
30 • R"2, which may be identical or different, represent a hydroxyl group, an amino group,
or a linear or branched, saturated or unsaturated, C1-C12 hydrocarbon-based group,
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optionally substituted with one or more group(s) chosen from hydroxyl, amino, (C1-
VS6)dialkylamino, (C1-VS6)alkylamino, carboxyl, carboxylate, carbamide, (C1-
VS4)alkoxyl, -S03H, -so3- or phenyl;
it being understood that the overall charge of the compounds of formula (ld) is positive;
5 • x is a stoichiometric coefficient chosen so as to ensure the electrical neutrality of the
compound of formula (A);
it being understood that the ingredients a) and b) are applied simultaneously or
sequentially to the keratin fibers, preferably simultaneously.
10 2. The process as claimed in the preceding claim, wherein y+ is chosen from the
compounds of formula (Ia), preferably from the compounds of formula (Ia) wherein R1,
R2 and R3 each represent a hydrogen atom and~ is as defined in the preceding claim.
3. The process as claimed in claim 1, wherein y+ is chosen from the compounds of
15 formula (lb), preferably from the compounds of formula (lb) wherein:
- Rs represents a hydrogen atom;
- Rs represents a linear or branched (C1-C4)alkyl group, optionally substituted with one
or more group(s) chosen from: hydroxyl, thiol, (C1-C5)alkylthio, amino, -NH3+, (C1-
C6)dialkylamino, (C1-C5)alkylamino, (C1-C4)alkoxyl, carboxyl, carboxylate, -S03H,-
20 SQ3-, -C(O)NH2, -NHC(NH)-NH2, -C(O)ORa, -OC(O)-Ra, -C(O)NHRa, -NH-C(O)-Ra,
phenyl, indolyl, phenol, furan, guaiacol, imidazole or guanine and/or optionally
interrupted by one or more group(s) chosen from -C(O)-, -NRb-, -C(NRb)-, -OC(O)-,
-C(O)O-, -C(O)NRb- or -NRbC(O)-;
Ra representing a (C1-C4)alkyl group; and
25 Rb representing a hydrogen atom or a (C1-C4)alkyl group, preferably a hydrogen atom;
- R1 represents a linear or branched (C1-C4)alkyl group, optionally substituted with one
or more hydroxyl group(s);
it being understood that the overall charge of the compounds of formula (lb) is positive.
30 4. The process as claimed in claim 1, wherein y+ is chosen from the compounds of
formula (lc), preferably from the compounds of formula (lc) wherein:
• Het is as defined in the preceding claim;
• R'1 and R'2, 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
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from: hydroxyl, amino, (C1-C5)dialkylamino, (C1-C5)alkylamino, carboxyl, carboxylate,
carbamide, (C1-C4)alkoxyl, -S03H, -So3- or phenyl;
• R'3, which may be identical or different, represent a group -C(O)OR'4, a group -OC(O)R'
4, a group -C(O)NHR'4 or a group -NH-C(O)-R'4;
5 R' 4 represents a (C1-C12)alkyl group, optionally substituted with one or more group(s)
chosen from hydroxyl, amino, (C1-C5)dialkylamino or (C1-C5)alkylamino;
it being understood that the overall charge of the compounds of formula (I c) is positive.
5. The process as claimed in claim 1, wherein y+ is chosen from the compounds of
10 formula (ld), preferably from the compounds of formula (ld) wherein:
• Het' is as defined in the preceding claim;
• R"1 represents a linear or branched, saturated or unsaturated, unsubstituted C1-C6,
preferably C1-C4, hydrocarbon-based group;
• R"2, which may be identical or different, represent a hydroxyl group or a linear or
15 branched, unsubstituted (C1-C5)alkyl group, preferably a linear or branched,
unsubstituted (C1-C4)alkyl group.
6. The process as claimed in claim 1, wherein y+ is chosen from the following compounds
1 to 69:
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R
1 2
R
5 6
R R
7 8 9
R R
10 11 12
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R
13 14 15
16 17
19 20 21
22 23 24
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25 27
OH H
28 29
31 32 33
34 35 36
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H H
37 39
41 42
H
H H
H
H
43 45
H
46 47 48
49 50 51
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53
H H
56
HO
0
I
58 59
H H
61 62 63
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H H
H
64
H
67 68 69
with R representing a (C1-C4)alkyl group optionally substituted with one or more hydroxyl
group(s) and X representing an oxygen atom or an NRb group, Rb representing a
hydrogen atom or a (C1-C4)alkyl group; preferably from the compounds 1, 5, 17 and 32
5 more preferentially from the compound 32 and the following compounds 1 a, Sa and 17a:
1a 5a 17a
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7. The process as claimed any one of the preceding claims, wherein the direct dye(s) a)
are neutral direct dyes, preferably chosen from the hydrazono dyes of formulae (lila) and
(lll'a), the azo and styryl dyes (IVa), the diazo and distyryl dyes (IV'a) and (IV"a), the
anthraquinone dyes (Va) and the azomethine dyes (VIa) and (VI'a) below, and mixtures
5 thereof:
Ar"-&{R3 )=N-N(Rb)-Ar Ar" -l:i{R11)-N=C{Rb)-Ar Ar-T=T' -Ar" Ar"-T=T' -Ar'-T'=T-Ar
lila
Ar-T=T'-L-T'=T-Ar
(IV" a)
Ar
(VIa)
formulae (lila), (lll'a), (IVa), (IV'a), (IV"a), (Va), (VIa) and (VI'a) wherein:
• Ar represents an aryl group, such as phenyl or naphthyl, substituted with at least one
electron-donating group such as i) optionally substituted (C1-Cs)alkyl, ii) optionally
10 substituted (C1-Cs)alkoxy, iii) (di)(C1-Cs)(alkyl)amino optionally substituted on the alkyl
group(s) with a hydroxyl group, iv) aryi(C1-Cs)alkylamino, v) optionally substituted N-(C1-
Cs)alkyi-N-aryi(C1-Cs)alkylamino or Ar represents a julolidine group;
• Ar' represents an optionally substituted divalent (hetero)arylene group such as
phenylene, particularly para-phenylene, or naphthalene, which is optionally substituted,
15 preferably with one or more (C1-Cs)alkyl, hydroxyl or (C1-Cs)alkoxy group(s);
• Ar" represents a (hetero)aryl group, which is optionally substituted, preferably with at
least i) an electron-withdrawing group such as nitro, nitroso, -C(X)-X'-R' or ii) a (di)(C1-
C6)(alkyl)amino group, iii) hydroxyl, iv) (C1-C5)alkoxy; (hetero)aryl is particularly chosen
from imidazolyl, triazolyl, indolyl or pyridyl or phenyl optionally substituted with at least
20 one group chosen from nitro, nitroso and amino, preferably substituted in the position
para to the phenyl group;
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• X, X' and X", which may be identical or different, represent an oxygen or sulfur atom,
or a group NR", preferably an oxygen atom;
• R1
, R2
, R3 and R4
, which may be identical or different, represent a hydrogen or halogen
atom, or a group chosen from hydroxyl, thiol, (C1-C4)alkyl, (C1-C4)alkoxy, (di)(C1-
5 C4)(alkyl)amino, nitro and nitroso;
• R' and R" represent a (C1-C4)alkyl group;
• Ra and Rb, which may be identical or different, represent a hydrogen atom or a (C1-
Cs)alkyl group, which is optionally substituted, preferably with a hydroxyl group;
or, as a variant, the substituent Ra with a substituent of Ar" and/or Rb with a substituent
10 of Ar and/or Ra with Rb form, together with the atoms that bear them, a (hetero)cycloalkyl;
in particular, Ra and Rb represent a hydrogen atom or a (C1-C4)alkyl group, which is
optionally substituted with a hydroxyl group;
• T and T', which may be identical or different, represent a group C(Ra) or N, preferably
N; and
15 • L represents a divalent group -ALK-, -C(X)-ALK-, -ALK-C(X)- or -C(X)-ALK-C(X')with
ALK representing a linear or branched (C1-C5)alkylene group, such as methylene,
and X and X' as defined above;
• R22, R23, R24, R2s, R2s and R21, which may be identical or different, represent a hydrogen
or halogen atom, or a group chosen from:
20 - (C1-C5)alkyl;
- hydroxyl, mercapto;
- (C1-C5)alkoxy, (C1-C5)alkylthio;
- aryloxy or arylthio;
- aryi(C1-C5)(alkyl)amino;
25 - (di)(C1-C5)(alkyl)amino;
- (di)(hydroxy(C1-C5)alkyl)amino;
• Z' represents a hydrogen atom or a group NR2sR29 with R2s and R29, which may be
identical or different, representing a hydrogen atom or a group chosen from:
- (C1-C5)alkyl;
30 - polyhydroxy(C1-C5)alkyl such as hydroxyethyl;
- aryl optionally substituted with one or more group(s), particularly i) (C1-C5)alkyl; iii) WC(
X)-X'-, W-X'-C(X)-, W-X'-C(X)-X"- with Ro representing a (C1-C5)alkyl group and X, X'
and X" as defined above; iv) a sulfonate;
- cycloalkyl; notably cyclohexyl;
5
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· Z represents a group chosen from hydroxyl and NR'2sR'29 with R'2s and R'29, which may
be identical or different, representing the same atoms or groups as R2s and R29 as
defined above;
the direct dyes of formula (IV"a) preferably having the formula (IV"' a):
formula (IV"'a) wherein:
R1 and R3
, which may be identical or different, preferably identical, represent a hydrogen
atom, a (C1-C4)alkyl group such as methyl or a sugar such as glucosyl, preferably a
hydrogen atom;
10 R2 and R4
, which may be identical or different, preferably identical, represent a hydrogen
atom, a (C1-C4)alkyl or (C1-C4)alkoxy group or an -0-sugar group such as -0-glucosyl,
preferably (C1-C4)alkoxy; such as methoxy;
• X, which may be identical or different, preferably identical, represents an oxygen or
sulfur atom or N-R with R representing a hydrogen atom or a group, preferably an oxygen
15 atom;
• ALK represents a (C1-C4)alkylene group such as methylene or ethylene, preferably
methylene.
8. The process as claimed in any one of the preceding claims, wherein the direct dye(s)
20 a) are neutral direct dyes chosen from the following compounds (A) to (G) and mixtures
thereof:
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H
H
H
G
preferably from the compounds (E), (F) and (G) and mixtures thereof, more
preferentially from the compounds (E) and (G) and mixtures thereof.
c
5 9. The process as claimed in any one of claims 1 to 6, wherein the direct dye(s) a) are
anionic direct dyes chosen from the dyes of formulae (Ill), (Ill'), (IV), (IV'), (V), (V'), (VI),
(VI'), (VII), (VIII), (IX) and (X) below and mixtures thereof:
a) the diaryl anionic azo dyes of formula (Ill) or (Ill'):
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(Ill}
(Ill')
formulae (Ill) and (Ill') wherein:
• R1, Rs, Rg, R1o, R'1, R's, R'g and R'1o, which may be identical or different, represent a
hydrogen atom or a group chosen from:
5 - (C1-C5)alkyl;
- (C1-C5)alkoxy, (C1-C5)alkylthio;
- hydroxyl, mercapto;
- nitro, nitroso;
- W-C(X)-X'-, W-X'-C(X)-, W-X'-C(X)-X"- with R0 representing a hydrogen atom or a
10 (C1-C5)alkyl or aryl group such as phenyl; X, X' and X", which may be identical or
different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen
atom or a (C1-C5)alkyl group;
- (0)28(0-)-, M+ with M+ representing a hydrogen atom or a cationic counterion;
- (O)CO--, M+ with M+ as defined above;
15 - R"-8(0)2-, with R" representing a hydrogen atom, an alkyl group, or an aryl, (di)(C1-
Cs)(alkyl)amino, or aryi(C1-C5)(alkyl)amino group; preferentially a phenylamino or
phenyl group;
- R"'-8(0)2-X'- with R"' representing a (C1-C5)alkyl group or an aryl group which is
optionally substituted, X' as defined above;
20 - (di)(C1-C5)(alkyl)amino;
- aryi(C1-C5)(alkyl)amino optionally substituted with one or more group(s) chosen from
i) nitro; ii) nitroso; iii) (0)28(0-)-, M+ and iv) (C1-C5)alkoxy with M+ as defined above;
-optionally substituted heteroaryl; preferentially a benzothiazolyl group;
- cycloalkyl; notably cyclohexyl;
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- Ar-N=N- with Ar representing an optionally substituted aryl group; preferentially a
phenyl optionally substituted with one or more alkyl, (0)2S(O-)-, M+ or phenylamino
group(s);
- or else two contiguous groups R1 with Rs or Rs with Rg or Rg with R1o together form a
5 fused benzo group A'; and R'1 with R's orR's with R'g or R'g with R'1o together form a
fused benzo group 8'; with A' and 8' optionally substituted with one or more group(s)
chosen from i) nitro; ii) nitroso; iii) (0)2S(O-)-, M+; iv) hydroxyl; v) mercapto; vi)
(di)(alkyl)amino; vii) W-C(X)-X'-; viii) W-X'-C(X)-; ix) W-X'-C(X)-X"-; x) Ar-N=N- and xi)
optionally substituted aryi(C1-C5)(alkyl)amino; with M+, R0
, X, X', X" and Ar as defined
10 above;
• W represents a sigma bond, an oxygen or sulfur atom, or a divalent group i) -NRwith
R as defined above, or ii) methylene -C(Ra)(Rb)- with Ra and Rb, which may be
identical or different, representing a hydrogen atom or an aryl group, or alternatively Ra
and Rb together form, with the carbon atom that bears them, a spiro cycloalkyl;
15 preferentially, W represents a sulfur atom or Ra and Rb together form a cyclohexyl;
it being understood that formulae (Ill) and (Ill') comprise, on one of the rings A, A', 8,
8' ore:
- at least one group (0)2S(O-)-, M'+ with M'+ representing a cationic counterion; or
- at least one group (O)CQ--, M'+ with M'+ representing a cationic counterion;
20 preferably at least one sodium sulfonate group;
b) the pyrazolone anionic azo dyes of formula (IV) or (IV'):
(IV)
formulae (IV) and (IV') wherein:
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R11, R12 and R13, which may be identical or different, represent a hydrogen or halogen
atom, a (C1-C5)alkyl group or -(0)2S(Ot M+ with M+ as defined above;
• R14 represents a hydrogen atom, a (C1-C5)alkyl group or a -C(O)Q-, M+ group with M+
as defined above;
5 • R1s represents a hydrogen atom;
• R1s represents an oxo group, in which case R'1s is absent, or else R1s with R1s
together form a double bond;
• R11 and R1s, which may be identical or different, represent a hydrogen atom or a
group chosen from:
10 - (0)2S(O-)-, M+ with M+ as defined above;
- Ar-O-S(0)2- with Ar representing an optionally substituted aryl group; preferentially a
phenyl optionally substituted with one or more alkyl group(s);
• R19 and R2o together form either a double bond, or a benzo group D', which is
optionally substituted;
15 • R'1s, R'19 and R'2o, which may be identical or different, represent a hydrogen atom or a
(C1-C5)alkyl group, or a hydroxyl group;
• R21 represents a hydrogen atom or a (C1-C5)alkyl or (C1-C5)alkoxy group;
• Ra and Rb, which may be identical or different, are as defined above; preferentially, Ra
represents a hydrogen atom and Rb represents an aryl group such as phenyl;
20 • Y represents either a hydroxyl group or an oxo group;
• __:__:_:__ represents a single bond when Y is an oxo group; and represents a double
bond when Y represents a hydroxyl group;
it being understood that formulae (IV) and (IV') comprise, on one of the rings D orE:
- at least one group (0)2S(O-)-, M'+ with M'+ representing a cationic counterion; or
25 - at least one group (O)CQ--, M'+ with M'+ representing a cationic counterion;
preferably at least one sodium sulfonate group.
c) the anthraquinone dyes of formulae (V) and (V'):
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(V}
formulae (V) and (V') wherein:
• R22, R23, R24, R2s, R2s and R21, which may be identical or different, represent a
hydrogen or halogen atom, or a group chosen from:
5 - (C1-C5)alkyl;
- hydroxyl, mercapto;
- (C1-C5)alkoxy, (C1-C5)alkylthio;
-optionally substituted aryloxy or arylthio, preferentially substituted with one or more
group(s) chosen from alkyl and (0)2S(O-)-, M+ with M+ as defined above;
10 - aryi(C1-C5)(alkyl)amino optionally substituted with one or more group(s) chosen from
alkyl and (0)2S(O-)-, M+ with M+ as defined above;
- (di)(C1-C5)(alkyl)amino;
- (di)(hydroxy(C1-C5)alkyl)amino;
- (0)2S(O-)-, M+ with M+ as defined above;
15 • Z' represents a hydrogen atom or a group NR2sR29 with R2s and R29, which may be
identical or different, representing a hydrogen atom or a group chosen from:
- (C1-C5)alkyl;
- polyhydroxy(C1-C5)alkyl such as hydroxyethyl;
-aryl optionally substituted with one or more group(s), particularly i) (C1-C5)alkyl such
20 as methyl, n-dodecyl, n-butyl; ii) (0)2S(O-)-, M+ with M+ as defined above; iii) W-C(X)X'-,
W-X'-C(X)-, W-X'-C(X)-X"- with R0
, X, X' and X" as defined above; preferentially
R0 represents a (C1-C5)alkyl group;
- cycloalkyl, notably cyclohexyl;
• Z represents a group chosen from hydroxyl and NR'2sR'29 with R'2s and R'29, which
25 may be identical or different, representing the same atoms or groups as R2s and R29 as
defined above;
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it being understood that formulae (V) and (V') comprise:
- at least one group (0)2S(O-)-, M'+ with M'+ representing a cationic counterion; or
- at least one group (O)CQ--, M'+ with M'+ representing a cationic counterion;
preferably at least one sodium sulfonate group.
5 d) the nitro dyes of formula (VI) or (VI'):
N02
formulae (VI) and (VI') wherein:
M"] u
(VI)
(VI')
• RJo, R31 and R32, which may be identical or different, represent a hydrogen or halogen
atom, or a group chosen from:
10 - (C1-C5)alkyl;
- (C1-C5)alkoxy optionally substituted with one or more hydroxyl group(s) or (C1-
C6)alkylthio optionally substituted with one or more hydroxyl group(s);
-hydroxyl, mercapto;
- nitro, nitroso;
15 - polyhalo(C1-C5)alkyl;
- W-C(X)-X'-, W-X'-C(X)-, W-X'-C(X)-X"- with R0
, X, X' and X" as defined above;
- (0)2S(O-)-, M+ with M+ as defined above;
- (O)CQ--, M+ with M+ as defined above;
- (di)(C1-C5)(alkyl)amino;
20 - (di)(hydroxy(C1-C5)alkyl)amino;
- heterocycloalkyl such as piperidine, piperazine or morpholino;
in particular, RJo, R31 and R32 represent a hydrogen atom;
• Rc and Rd, which may be identical or different, represent a hydrogen atom or a (C1-
C6)alkyl group;
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• W is as defined above; W particularly represents an N(H)- group;
• ALK represents a linear or branched divalent C1-C6 alkylene group; in particular, ALK
represents a -CH2-CH2- group;
• n is 1 or 2;
5 • p represents an integer ranging from 1 to 5;
• q represents an integer ranging from 1 to 4;
• u is 0 or 1;
• when n is 1, J represents a nitro or nitroso group; particularly nitro;
• when n is 2, J represents an oxygen or sulfur atom, or a divalent group -S(O)m- with
10 m representing an integer 1 or 2; preferentially, J represents an -SOr group;
• M" represents a hydrogen atom or a cationic counterion;
, which may be present or absent, represents a benzo group optionally
substituted with one or more groups RJo as defined above;
it being understood that formulae (VI) and (VI') comprise:
15 - at least one group (0)2S(O-)-, M'+ with M'+ representing a cationic counterion; or
- at least one group (O)CQ--, M'+ with M'+ representing a cationic counterion;
preferably at least one sodium sulfonate group.
e) the triarylmethane dyes of formula (VII):
(VII)
20 formula (VII) wherein:
• R33, R34, RJs and RJs, which may be identical or different, represent a hydrogen atom
or a group chosen from (C1-C5)alkyl, optionally substituted aryl and optionally
substituted aryi(C1-C5)alkyl; particularly a (C1-C5)alkyl group and benzyl optionally
substituted with an (O)mS(Q-)-, M+ group with M+ and m as defined above;
25 • R31, RJs, R39, R4o, R41, R42, R43 and R44, which may be identical or different, represent
a hydrogen atom or a group chosen from:
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- (C1-C5)alkyl;
- (C1-C5)alkoxy, (C1-C5)alkylthio;
- (di)(C1-C5)(alkyl)amino;
- hydroxyl, mercapto;
5 - nitro, nitroso;
- W-C(X)-X'-, W-X'-C(X)-, W-X'-C(X)-X"- with R0 representing a hydrogen atom or an
alkyl or aryl group; X, X' and X", which may be identical or different, representing an
oxygen or sulfur atom, or NR with R representing a hydrogen atom or a (C1-C5)alkyl
group;
10 - (0)2S(O-)-, M+ with M+ representing a hydrogen atom or a cationic counterion;
- (O)CQ--, M+ with M+ as defined above;
- or else two contiguous groups R41 with R42 or R42 with R43 or R43 with R44 together
form a fused benzo group optionally substituted with one or more group(s) chosen from
i) nitro; ii) nitroso; iii) (0)2S(O-)-, M+; iv) hydroxyl; v) mercapto; vi) (di)(C1-
15 C6)(alkyl)amino; vii) W-C(X)-X'-; viii) W-X'-C(X)-; ix) W-X'-C(X)-X"-; with M+, R0
, X, X'
and X" as defined above;
particularly, R31 to R4o represent a hydrogen atom, and R41 to R44, which may be
identical or different, represent a hydroxyl group or (0)2S(O-)-, M+ with M+ as defined
above; and when R43 with R44 together form a benzo group, it is preferentially
20 substituted with an (0)2S(O-)- group;
it being understood that at least one of the rings G, H or I comprises:
- at least one group (0)2S(O-)-, M'+ with M'+ representing a cationic counterion; or
- at least one group (O)CQ--, M'+ with M'+ representing a cationic counterion;
preferably at least one sodium sulfonate group.
25 f) the xanthene-based dyes of formula (VIII):
(VIII)
formula (VIII) wherein:
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• R4s, R4s, R41 and R4s, which may be identical or different, represent a hydrogen atom
or a halogen atom;
• R49, Rso, Rs1 and Rs2, which may be identical or different, represent a hydrogen or
halogen atom, or a group chosen from:
5 - (C1-C5)alkyl;
- (C1-C5)alkoxy, (C1-C5)alkylthio;
- hydroxyl, mercapto;
- nitro, nitroso;
- (0)2S(O-)-, M+ with M+ representing a hydrogen atom or a cationic counterion;
10 - (O)CQ--, M+ with M+ as defined above;
particularly, R4s, R4s, R41 and R4s represent a hydrogen or halogen atom;
· G represents an oxygen or sulfur atom or a group NRe with Re as defined above;
particularly, G represents an oxygen atom;
· L represents an alkoxide o-, M+; a thioalkoxide s-, M+ or a group NRt, with Rt
15 representing a hydrogen atom or a (C1-C5)alkyl group, and M+ as defined above; M+ is
particularly sodium or potassium;
• L' represents an oxygen or sulfur atom or an ammonium group: WRtR9, with Rt and
R9 , which may be identical or different, representing a hydrogen atom, a (C1-C5) alkyl
group or an optionally substituted aryl group; L' represents particularly an oxygen atom
20 or a phenylamino group optionally substituted with one or more alkyl or (O)mS(Q-)-, M+
group(s) with m and M+ as defined above;
• Q and Q', which may be identical or different, represent an oxygen or sulfur atom;
particularly Q and Q' represent an oxygen atom;
• M+ is as defined above;
25 g) the indole-based dyes of formula (IX):
(IX)
formula (IX) wherein:
• Rs3, Rs4, Rss, Rss, Rs1, Rss, Rsg and Rso, which may be identical or different, represent
a hydrogen atom or a group chosen from:
30 - (C1-C5)alkyl;
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- (C1-C5)alkoxy, (C1-C5)alkylthio;
- hydroxyl, mercapto;
- nitro, nitroso;
- W-C(X)-X'-, W-X'-C(X)-, W-X'-C(X)-X"- with R0 representing a hydrogen atom or an
5 alkyl or aryl group; X, X' and X", which may be identical or different, representing an
oxygen or sulfur atom, or NR with R representing a hydrogen atom or a (C1-C5)alkyl
group;
- (0)2S(O-)-, M+ with M+ representing a hydrogen atom or a cationic counterion;
- (O)CQ--, M+ with M+ as defined above;
10 • G represents an oxygen or sulfur atom or a group N Re with Re as defined above;
particularly, G represents an oxygen atom;
• Ri and Rh, which may be identical or different, represent a hydrogen atom or a (C1-
C6)alkyl group;
it being understood that formula (IX) comprises:
15 - at least one group (0)2S(O-)-, M'+ with M'+ representing a cationic counterion; or
- at least one group (O)CQ--, M'+ with M'+ representing a cationic counterion;
preferably at least one sodium sulfonate group.
h) the quinoline-based dyes of formula (X):
(X)
20 formula (X) wherein:
• Rs1 represents a hydrogen or halogen atom or a (C1-C5)alkyl group;
• Rs2, Rs3 and Rs4, which may be identical or different, represent a hydrogen atom or a
group (0)2S(O-)-, M+ with M+ representing a hydrogen atom or a cationic counterion; or
else Rs1 with Rs2, or Rs1 with Rs4, together form a benzo group optionally substituted
25 with one or more groups (0)2S(O-)-, M+ with M+ representing a hydrogen atom or a
cationic counterion;
it being understood that formula (X) comprises at least one group (0)2S(O-)-, M'+ with
M'+ representing a cationic counterion, preferably at least one sodium sulfonate group.
5
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10. The process as claimed in any one of the preceding claims, wherein the direct
dye(s) a) have a solubility in water at a temperature of 22oC and at atmospheric
pressure (760 mmHg, i.e. 1.013x 105 Pa) of less than 5% by weight, preferably less
than 1% by weight and more preferentially less than 0.5% by weight.
11. The process as claimed in any one of the preceding claims, comprising a step of
applying to the keratin fibers a composition, preferably an aqueous composition,
comprising:
a) one or more direct dyes as defined in any one of claims 1 or 7 to 1 0; and
10 b) one or more compounds of formula (A) as defined in any one of claims 1 to 6.
12. The process as claimed in any one of claims 1 to 10, comprising:
either
i) a first step of applying to the keratin fibers a composition, preferably an aqueous
15 composition, comprising a) one or more direct dyes as defined in any one of claims 1
or 7 to 10, then ii) a second step of applying to the keratin fibers a composition,
preferably an aqueous composition, comprising b) one or more compounds of formula
(A) as defined in any one of claims 1 to 6;
or
20 i) a first step of applying to the keratin fibers a composition, preferably an aqueous
composition, comprising b) one or more compounds of formula (A) as defined in any
one of claims 1 to 6, then ii) a second step of applying to the keratin fibers a
composition, preferably an aqueous composition, comprising a) one or more direct
dyes as defined in any one of claims 1 or 7 to 10.
25
13. The process as claimed in either one of claims 11 and 12, wherein the direct dye(s)
a) as defined in any one of claims 1 or 7 to 10 are present in the composition
comprising them in a content ranging from 0.001% to 10% by weight, preferably from
0.05% to 5% by weight, more preferentially from 0.3% to 3% by weight relative to the
30 total weight of the composition comprising them.
14. The process as claimed in any one of claims 11 to 13, wherein the compound(s) of
formula (A) as defined in any one of claims 1 to 6 are present in the composition
comprising them in a content ranging from 1% to 99.5% by weight, preferably from 3%
5
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to 90% by weight, more preferentially from 10% to 80% by weight, even more
preferentially from 20% to 60% by weight, most preferentially from 20% to 50% by
weight, and better still from 20% to 40% by weight relative to the total weight of the
composition comprising them.
15. The process as claimed in any one of claims 11 to 14, wherein the pH of the
composition(s) comprising the ingredients a) and/or b) is from 3 to 12, preferably from 5
to 10, more preferentially from 6 to 9.5.
10 16. A composition comprising:
a) optionally one or more direct dyes; and
b) one or more compounds of formula (A) as defined in any one of claims 1 to 6.
17. A multicompartment device or kit, comprising a first compartment which comprises
15 one or more direct dyes and a second compartment which comprises one or more
compounds of formula (A) as defined in any one of claims 1 to 6.