Hair dyeing process employing at least one dihydroxyflavanol, a
manganese or zinc salt, hydrogen peroxide, (bi)carbonate, an
alkaline agent and a magnesium, molybdenum or calcium salt
The present invention relates to a process for dyeing keratin
fibres, in particular human keratin fibres such as the hair, in which
said fibres are treated using one or more cosmetic compositions
comprising a) one or more dihydroxyflavanol derivative(s), b) one or
more manganese or zinc salt(s), c) hydrogen peroxide or one or more
hydrogen peroxide-generating system(s), d) one or more
(bi)carbonate(s) or one or more (bi)carbonate-generating system(s), e)
one or more alkalinizing agent(s) other than the (bi)carbonate(s) and f)
one or more metal salt(s) chosen from magnesium, molybdenum and
calcium salts, it being understood that the ingredient f) is applied
together, i.e. as co-treatment, with at least one of the other ingredients
a) to e).
It is known practice to obtain "permanent" colourations with
dyeing compositions containing oxidation dye precursors, which are
generally known as oxidation bases, such as ortho- or paraphenylenediamines,
ortho- or para-aminophenols and heterocyclic
compounds. These oxidation bases are colourless or weakly coloured
compounds, which, when combined with oxidizing products, may give
rise to coloured compounds by a process of oxidative condensation. It
is also known that the shades obtained may be varied by combining
these oxidation bases with couplers or colouration modifiers, the latter
being chosen especially from aromatic meta-diamines, metaaminophenols,
meta-diphenols and certain heterocyclic compounds
such as indole compounds. This oxidation dyeing process consists in
applying, to the keratin fibres, bases or a mixture of bases and
couplers with hydrogen peroxide (H20 2 or aqueous hydrogen peroxide
solution), as oxidizing agent, in leaving to diffuse, and in then rinsing
the fibres. The colourations resulting therefrom are permanent, strong
and resistant to external agents, especially to light, bad weather,
washing, perspiration and rubbing.
However, the commercial hair colourings which contain them
generally have the drawback of staining the clothing, of causing odour
and comfort problems, and of damaging the keratin fibres. This is
particularly the case with oxidation dyes.
However, the colourations obtained are not strong enough, and
are not very chromatic, in particular in the case of hair fibres.
Moreover, it is known practice to use metals at acid pH for
dyeing keratin fibres in amounts similar to those employed for dyes
using a mordanting process, which consists in preparing the fibres
before carrying out the dyeing in order to obtain persistent colours
(see, for example, Ullmann's Encyclopedia, "Metal and Dyes", 2005,
§ 5.1, p .8).
However, this process generally has the drawback of not
always respecting the cosmetic appearance of the keratin fibre.
Furthermore, the metals used, such as iron, result in neutral shades
that are not very chromatic. Generally, such metals do not make it
possible to obtain chromatic shades.
There thus exists a real need to develop dyeing processes
which make it possible to obtain strong, persistent and/or chromatic
colourations using dihydroxyflavanols and which are less aggressive
to keratin fibres. In particular, there exists a need to obtain
colourations which satisfactorily withstand external agents (light, bad
weather, shampooing) and which are persistent and homogeneous, i.e.
which have a weak colouration selectivity between the root and the
tip, while remaining strong and/or chromatic.
This aim is achieved by the present invention, a subject-matter
of which is a process for dyeing keratin fibres, in particular human
keratin fibres such as the hair, in which said fibres are treated, in one
or more steps, with one or more cosmetic compositions containing,
taken together or separately in said composition(s), the following
ingredients:
a) one or more dihydroxyflavanol derivative(s),
b) one or more manganese salt(s) or one or more zinc salt(s),
c) hydrogen peroxide or one or more hydrogen peroxidegenerating
system(s),
d) one or more (bi)carbonate(s) or one or more (bicarbonategenerating
system(s),
e) one or more alkalinizing agent(s) other than the
bicarbonate(s), and
f) one or more metal salt(s) chosen from magnesium,
molybdenum and calcium salts;
it being understood that:
- the pH of at least one of the compositions comprising at least
one of the ingredients a), b), d), e) and/or f) is alkaline, i.e. greater
than 7, and
- the ingredient f) is applied as co-treatment with at least one
of the other ingredients a) to e).
According to one particular embodiment of the dyeing process
according to the invention, the compound(s) d) and e) are found:
- either in a mixture with the compounds a), b) and c),
- or applied separately after application of a cosmetic
composition comprising the compound(s) a), b) and c),
- or applied together with the compound c) after application
of a cosmetic composition comprising the ingredients a) and b).
According to the dyeing process of the invention, the metal
salt(s) chosen from magnesium, molybdenum and calcium salts is(are)
applied with at least one of the ingredients a), b), c), d) and/or e).
Another subject-matter of the present invention is a cosmetic
composition for the dyeing of keratin fibres, comprising:
a) one or more dihydroxyflavanol derivative(s),
b) one or more manganese salt(s) or one or more zinc salt(s),
c) hydrogen peroxide or one or more hydrogen peroxidegenerating
system(s),
d) one or more (bi)carbonate(s) or one or more (bicarbonategenerating
system(s),
e) one or more alkalinizing agent(s) other than the
bicarbonate(s), and
f) one or more metal salt(s) chosen from magnesium,
molybdenum and calcium salts,
it being understood that the pH of the composition is alkaline,
i.e. greater than 7, and preferably between 8 and 12. It is in particular
between 8 and 10.5 .
The cosmetic composition is preferably aqueous.
Another subject-matter of the present invention relates to a
multicompartment device comprising:
a) one or more dihydroxyflavanol derivative(s),
b) one or more manganese salt(s) or one or more zinc salt(s),
c) hydrogen peroxide or one or more hydrogen peroxidegenerating
system(s),
d) one or more (bi)carbonate(s) or one or more (bicarbonategenerating
system(s),
e) one or more alkalinizing agent(s) other than the
bicarbonate(s), and
f) one or more metal salt(s) chosen from magnesium,
molybdenum and calcium salts,
it being understood that the pH of at least one of the
compositions comprising at least one of the ingredients a), b), d), e)
and/or f) is alkaline, i.e. greater than 7, and preferably between 8 and
12. It is in particular between 8 and 10.5 .
The multicompartment device or "kit" is suitable for
implementing the dyeing process according to the invention.
The process according to the invention has the advantage of
dyeing human keratin fibres, with persistent and, surprisingly,
chromatic dyeing results. In particular, the dyeing process according
to the invention makes it possible to produce colourations that are
resistant to washing, perspiration, sebum and light without
detrimentally modifying the fibres. Furthermore, the dyeing process
employed makes it possible to induce a satisfactory "uptake" of the
colouration.
Thus, another subject-matter of the invention is the use of one
or more metal salt(s) f) for improving the chromaticity of keratin
fibres, in particular human keratin fibres such as the hair, using one or
more dihydroxyflavanol derivative(s).
Other subject-matters, characteristics, aspects and advantages
of the present invention will emerge even more clearly on reading the
description and the examples that follow.
For the purposes of the present invention, and unless otherwise
indicated:
The "saturated or unsaturated, optionally fused rings" may also
be optionally substituted.
The "alkyl" radicals are saturated, linear or branched,
generally C1-C20 , particularly Ci-Cio, hydrocarbon radicals,
preferably Ci-C alkyl radicals, such as methyl, ethyl, propyl, butyl,
pentyl and hexyl.
The "alkenyl" radicals are unsaturated, linear or branched, C2-
C2o hydrocarbon radicals; preferably comprising at least one double
bond, such as ethylene, propylene, butylene, pentylene, 2-
methylpropylene and decylene.
The "aryl" radicals are monocyclic or fused or nonfused
polycyclic carbon-based radicals, preferentially comprising from 6 to
30 carbon atoms, at least one ring of which is aromatic; the choice is
preferably made, from the aryl radical, of a phenyl, biphenyl,
naphthyl, indenyl, anthracenyl and tetrahydronaphthyl.
The "alkoxy" radicals are alkyl-oxy radicals with alkyl as
defined previously, preferably a Ci-Cio alkyl, such as methoxy,
ethoxy, propoxy and butoxy.
The "alkylthio" radicals are alkyl-S- radicals with alkyl as
defined previously, preferably a Ci-Cio alkyl, such as methylthio,
ethylthio, propylthio and butylthio.
The "alkoxyalkyl" radicals are preferably (Ci-C2o)alkoxy(Ci-
C2o)alkyl radicals, such as methoxymethyl, ethoxymethyl,
methoxyethyl, ethoxyethyl, etc.
The "cycloalkyl" radicals are generally C 4- C cycloalkyl
radicals, preferably the cyclopentyl and cyclohexyl radicals. The
cycloalkyl radicals may be substituted cycloalkyl radicals, in
particular substituted by alkyl, alkoxy, carboxylic acid, hydroxyl,
amine and ketone groups.
The "alkyl" or "alkenyl" radicals, when they are "optionally
substituted", may be substituted by at least one substituent carried by
at least one carbon atom, chosen from:
- a halogen atom;
- a hydroxyl group;
- a C1-C2 alkoxy radical;
- a C1-C10 alkoxycarbonyl radical;
- a C2-C4 (poly)hydroxyalkoxy radical;
- an amino radical;
- a 5- or 6-membered heterocycloalkyl radical;
- an optionally cationic 5- or 6-membered heteroaryl radical,
preferentially imidazolium, optionally substituted by a (Ci-C 4)alkyl
radical, preferentially methyl;
- an amino radical substituted by one or two identical or
different Ci-C alkyl radicals, optionally carrying at least:
* one hydroxyl group,
* one amino group optionally substituted by one or two
optionally substituted C1- C 3 alkyl radicals, said alkyl radicals possibly
forming, with the nitrogen atom to which they are attached, a
saturated or unsaturated 5- to 7-membered heterocycle which is
optionally substituted and which optionally comprises at least one
other heteroatom identical to or different from nitrogen,
* 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 represents the
counterion of the corresponding organic acid, inorganic acid or halide,
* or an optionally cationic 5- or 6-membered heteroaryl
radical, preferentially imidazolium, optionally substituted by a (Ci-
C4)alkyl radical, preferentially methyl;
- an acylamino (-NR-COR') radical in which the R radical is a
hydrogen atom or a C1- C 4 alkyl radical optionally carrying at least one
hydroxyl group and the R' radical is a C1-C2 alkyl radical; a
carbamoyl ((R) 2N-CO-) radical in which the R radicals, which may be
identical or different, represent a hydrogen atom or a C1-C4 alkyl
radical optionally carrying at least one hydroxyl group; an
alkylsulfonylamino (R' S0 2-NR-) radical in which the R radical
represents a hydrogen atom or a C1-C4 alkyl radical optionally
carrying at least one hydroxyl group and the R' radical represents a
C1-C4 alkyl radical or a phenyl radical; an aminosulfonyl ((R) 2N-S0 2-)
radical in which the R radicals, which may be identical or different,
represent a hydrogen atom or a C1-C4 alkyl radical optionally carrying
at least one hydroxyl group;
- a carboxylic radical in acid or salified (preferably with an
alkali metal or a substituted or unsubstituted ammonium) form;
- a cyano group;
- a nitro group;
- a carboxyl or glycosylcarbonyl group;
- a phenylcarbonyloxy group optionally substituted by one or
more hydroxyl groups;
- a glycosyloxy group; and
- a phenyl group optionally substituted by one or more
hydroxyl groups.
The term "carboxylates" is understood to mean carboxylic acid
salt.
The term "carboxylic acid" is understood to mean a compound
comprising at least one carboxylic acid -C(0)-OH group, preferably
between 1 and 4 carboxylic acid groups, such as 1 or 2 . More
particularly, the carboxylic acid is chosen from: i) (Ci-Cio)alkyl-[C(0)-
OH] and ii) het-[C(0)-OH] , with n an integer between 1 and 4
inclusive, preferably between 1 and 2, het representing a heterocyclic
group, such as pyrrolidone, it being possible for the alkyl or het group
to be optionally substituted by one or more groups chosen in particular
from OH, and (di)(Ci- C 6)(alkyl)amino.
The "aryl" or "heterocyclic" radicals or the aryl or heterocyclic
part of the radicals, when they are optionally substituted, may be
substituted by at least one substituent carried by at least one carbon
atom, chosen from:
- a C i -C io, preferably C i -C , alkyl radical optionally
substituted by one or more radicals chosen from the hydroxyl radical,
C 1-C2 alkoxy radical, (poly)hydroxy(C2 -C4)alkoxy radical, acylamino
radical, amino radical substituted by two identical or different C 1-C4
alkyl radicals optionally carrying at least one hydroxyl group, or the
two radicals possibly forming, with the nitrogen atom to which they
are attached, a saturated or unsaturated and optionally substituted 5-
to 7-membered, preferably 5- or 6-membered, heterocycle optionally
comprising another heteroatom identical to or different from nitrogen;
- a halogen atom;
- a hydroxyl group;
- a C 1-C2 alkoxy radical;
- a C 1-C 10 alkoxycarbonyl radical;
- a (poly)hydroxy(C2 -C4)alkoxy radical;
- an amino radical;
- a 5- or 6-membered heterocycloalkyl radical;
- an optionally cationic 5- or 6-membered heteroaryl radical,
preferentially imidazolium, optionally substituted by a (C i -C4)alkyl
radical, preferentially methyl;
- an amino radical substituted by one or two identical or
different C i -C alkyl radicals, optionally carrying at least:
* one hydroxyl group,
* one amino group optionally substituted by one or two
optionally substituted C 1- C 3 alkyl radicals, said alkyl radicals possibly
forming, with the nitrogen atom to which they are attached, a
saturated or unsaturated and optionally substituted 5- to 7-membered
heterocycle optionally comprising at least one other heteroatom
identical to or different from nitrogen,
* one 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 C 1- C 4 alkyl group; and M represents the
counterion of the corresponding organic acid, inorganic acid or halide,
* or one optionally cationic 5- or 6-membered heteroaryl
radical, preferentially imidazolium, optionally substituted by a (Ci-
C4)alkyl radical, preferentially methyl;
- an acylamino (-NR-COR') radical in which the R radical is a
hydrogen atom or a Ci-C4 alkyl radical optionally carrying at least one
hydroxyl group and the R' radical is a Ci-C2 alkyl radical; a
carbamoyl ((R) 2N-CO-) radical in which the R radicals, which may be
identical or different, represent a hydrogen atom or a Ci-C4 alkyl
radical optionally carrying at least one hydroxyl group; an
alkylsulfonylamino (R' S0 2-NR-) radical in which the R radical
represents a hydrogen atom or a Ci-C4 alkyl radical optionally
carrying at least one hydroxyl group and the R' radical represents a
Ci-C4 alkyl radical or a phenyl radical; an aminosulfonyl ((R) 2N-S0 2-)
radical in which the R radicals, which may be identical or different,
represent a hydrogen atom or a Ci-C4 alkyl radical optionally carrying
at least one hydroxyl group,
- a carboxylic radical in acid or salified (preferably with an
alkali metal or a substituted or unsubstituted ammonium) form;
- a cyano group;
- a nitro group;
- a polyhaloalkyl group, preferentially trifluoromethyl;
- a carboxyl or glycosylcarbonyl group;
- a phenylcarbonyloxy group optionally substituted by one or
more hydroxyl groups;
- a glycosyloxy group; and
- a phenyl group optionally substituted by one or more
hydroxyl groups.
The radicals "containing one or more silicon atoms" are
preferably polydimethylsiloxane, polydiphenylsiloxane,
polydimethylphenylsiloxane or stearoxydimethicone radicals.
The "heterocyclic" radicals are generally radicals comprising,
in at least one ring, one or more heteroatoms chosen from O, N and S,
preferably O or N, optionally substituted by in particular one or more
alkyl, alkoxy, carboxylic acid, hydroxyl, amine or ketone groups.
These rings may contain one or more oxo groups on the carbon atoms
of the heterocycle.
Among the "heterocyclic" radicals that may be used, mention
may be made of the furyl, pyranyl, pyrrolyl, imidazolyl, pyrazolyl,
pyridyl and thienyl groups.
More preferably, the "heterocyclic" groups are fused groups,
such as benzofuryl, chromenyl, xanthenyl, indolyl, isoindolyl,
quinolyl, isoquinolyl, chromanyl, isochromanyl, indolinyl,
isoindolinyl, coumarinyl or isocoumarinyl groups, these groups
possibly being substituted, in particular by one or more OH groups.
The term "heterosides" or "glycosides" is understood to mean
any compound resulting from the condensation of monosaccharides
and non-glucide substances, also referred to as aglycones or genins.
The term "glycosyl radical" means a radical derived from a
monosaccharide or monosaccharide.
a) dihydroxyflavanol derivative
In accordance with the present invention, the dyeing process
employs one or more dihydroxyflavanol derivative(s).
The dihydroxyflavanol derivative(s) may be present in one or
more cosmetic compositions used during the dyeing process.
A specific form of the invention relates to dihydroxyflavanol
derivatives or mixtures of compounds.
More particularly, the dihydroxyflavanol derivatives a)
represent compounds of following formula (I) and also organic or
inorganic acid salts thereof, optical, geometric and tautomeric isomers
thereof, and solvates thereof such as the hydrates:
in which:
• R1, R2, R3, R4, R5, R6, R7, R8 and R9, which are identical or different,
represent:
- a hydrogen atom,
- a halogen atom,
- a hydroxyl group,
- a (Ci-C )alkyl group,
- a (Ci-C )alkoxy group,
- a (Ci-Ce)alkylthio group,
- a carboxyl group,
- an alkoxycarbonyl group,
- an optionally substituted amino group,
- an optionally substituted linear or branched alkenyl group,
- an optionally substituted cycloalkyl group,
- an aryl group,
- a substituted aryl group,
- a group containing one or more silicon atoms,
- a (di)((hydroxy)(Ci- C6)alkyl)amino group,
- an -O-sugar group, such as -O-glucoside,
- an R-Z-C(X)-Y- group with R representing a hydrogen atom
or a (Ci-C )alkyl group, Y and Z, which may be identical or different,
representing a bond, an oxygen or sulfur atom or an -N(R')- group
with R' representing a hydrogen atom or a (Ci-C )alkyl group, Y
possibly also representing a (Ci-Ce)alkylene group, and X representing
an oxygen or sulfur atom, or N-R" with R" representing a hydrogen
atom or a (Ci-C )alkyl group;
it being understood that at least two adjacent radicals chosen
from R1, R2, R3, R4, R5, R6, R7, R8 and R9 represent a hydroxyl group.
According to one embodiment, R6 and R7 represent a hydroxyl
group.
Preferably, R1, R , R5, R8 and R9 represent hydrogen atoms and
R2 and R4 represent a hydroxyl group.
The dihydroxyflavanol derivatives employed during the dyeing
process according to the invention can be natural or synthetic.
Among the natural dihydroxyflavanol derivatives are
compounds that may be present in nature and that are reproduced by
chemical (semi)synthesis. The salts of the dihydroxyflavanol
derivatives of the invention may be salts of acids or bases. The acids
may be inorganic or organic.
Preferably, the acid is hydrochloric acid, which results in
chlorides.
The bases may be inorganic or organic. In particular, the bases
are alkali metal hydroxides, such as sodium hydroxide, which results
in sodium salts.
According to a particular embodiment of the invention, the
composition comprises, as ingredient a), one or more synthetic
dihydroxyflavanol derivative(s) that do not exist in nature.
According to another preferred embodiment of the invention,
the composition of use in the process for dyeing keratin fibres
comprises, as ingredient a), one or more natural dihydroxyflavanol
derivative(s).
More particularly, the dihydroxyflavanol derivatives a) that
may be used in the dyeing process according to the invention are in
particular:
- dihydroxyflavanols such as catechin and epicatechin gallate,
their oligomers and polymers called proanthocyanidols or condensed
tannins such as theaflavin, theaflavin 3'-0-gallate, theaflavin 3,3'-0-
digallate, and proanthocyanidins Al , A2, Bl , B2, B3 and CI ;
- and mixtures of the preceding compounds.
More preferably still, the dihydroxyflavanol derivatives are
catechin and proanthocyanidins Al , A2, Bl , B2, B3 and CI .
When the dyeing precursors have D and L forms, the two forms
may be used in the compositions according to the invention, as may
the racemic mixtures.
According to one embodiment, the natural dihydroxyflavanol
derivatives are derived from extracts of animals, of bacteria, of fungi,
of algae, of plants and of fruits, used in their entirety or partially. In
particular regarding the plants, the extracts are derived from fruits,
including citrus fruits, from vegetables, from trees and from shrubs.
Mixtures of these extracts that are rich in dihydroxyflavanol
derivatives as defined previously may also be used.
Preferably, the natural dihydroxyflavanol derivative(s) of the
invention are derived from extracts of plants or plant parts.
For the purposes of the invention, these extracts will be put
into the same category as compounds a).
The extracts are obtained by extraction from various plant
parts, for instance the root, the wood, the bark, the leaf, the flower,
the fruit, the seed, the pod or the peel.
Among the plant extracts, mention may be made of extracts of
tea leaves and of rose.
Among the fruit extracts, mention may be made of extracts of
apple, of grape (in particular of grape seed) or extracts of cocoa beans
and/or pods.
Among the vegetable extracts, mention may be made of
extracts of potato or of onion peel.
Among the extracts of tree wood, mention may be made of
extracts of pine bark or extracts of logwood.
Mixtures of plant extracts may also be used.
According to a particular embodiment of the invention, the
dihydroxyflavanol derivative(s) are natural extracts, rich in
dihydroxyflavanol derivatives. According to a preferred form, the
dihydroxyflavanol derivative(s) are solely natural extracts.
The natural extracts according to the invention may be in the
form of powders or liquids. Preferably, the extracts of the invention
are in the form of powders.
According to the invention, the natural, synthetic
dihydroxyflavanol derivative(s) and/or the natural extract(s) used as
ingredient a) in one or more composition(s) of use in the process
according to the invention preferably represent(s) from 0.00 1% to 20%
by weight of the total weight of the composition(s) containing the
dihydroxyflavanol derivative(s) or the extract(s).
As regards the pure dihydroxyflavanol derivatives, the content
in the composition(s) containing them is preferably between 0.00 1%
and 5 % by weight of each of these compositions.
As regards the extracts, the content in the composition(s)
containing the extracts per se is preferably between 0.5% and 20% by
weight of each of these compositions.
Preferably, the dihydroxyflavanol derivative is catechin.
Additional ortho-diphenol derivative
According to a particular embodiment of the invention, the
dyeing process may use one or more ortho-diphenol derivative(s) other
than the dihydroxyflavanol derivative(s) a).
The ortho-diphenol derivative(s) may be present in one or more
cosmetic compositions used during the dyeing process.
A particular embodiment of the invention relates to orthodiphenol
derivatives or mixtures of compounds comprising one or
more aromatic rings, preferably a benzene ring, comprising at least
two hydroxyl (OH) groups carried by two adjacent carbon atoms of the
aromatic ring.
The aromatic ring may more particularly be a fused aryl or
fused heteroaromatic ring, i.e. optionally containing one or more
heteroatoms, such as benzene, naphthalene, tetrahydronaphthalene,
indane, indene, anthracene, phenanthrene, isoindole, indoline,
isoindoline, benzofuran, dihydrobenzofuran, chroman, isochroman,
chromene, isochromene, quinoline, tetrahydroquinoline and

- an aryl radical,
- a substituted aryl radical,
- a saturated or unsaturated heterocyclic radical, optionally
carrying a cationic or anionic charge, optionally substituted and/or
optionally fused with an aromatic ring, preferably a benzene ring, said
aromatic ring being optionally substituted, particularly by one or more
hydroxyl or glycosyloxy groups,
- a radical containing one or more silicon atoms,
- or two of the substituents carried by two adjacent carbon
atoms Ri - R2 , R2 - R or R - R4 form, together with the carbon atoms
which carry them, a saturated or unsaturated, aromatic or non-aromatic
ring, optionally containing one or more heteroatoms and optionally
fused with one or more saturated or unsaturated rings optionally
containing one or more heteroatoms. Particularly, R to R4 together
form from one to four rings.
A particular embodiment of the invention concerns orthodiphenol
derivatives of formula (II) in which two adjacent substituents
Ri - R2 , R2 - R or R - R4 cannot form, with the carbon atoms which
carry them, a pyrrolyl radical. More particularly, R2 and R cannot
form a pyrrolyl radical fused to the benzene ring carrying the two
hydroxyls.
The ortho-diphenols of use in the process of the invention may
be natural or synthetic. Among the natural ortho-diphenols are
compounds that may be present in nature and that are reproduced by
chemical (semi)synthesis.
The ortho-diphenol salts of the invention may be salts of acids
or bases. The acids may be inorganic or organic. Preferably, the acid is
hydrochloric acid, which results in chlorides.
The bases may be inorganic or organic. In particular, the bases
are alkali metal hydroxides, such as sodium hydroxide, which results
in sodium salts.
According to a particular embodiment of the invention, the
composition comprises one or more synthetic ortho-diphenol
derivative(s) that do not exist in nature.
According to another preferred embodiment of the invention,
the composition of use in the process for dyeing keratin fibres
comprises one or more natural ortho-diphenol derivative(s).
More particularly, the ortho-diphenols that may be used in the
process of the invention are in particular:
anthocyanidins, for instance cyanidin, delphinidin or
petunidin,
- anthocyanins or anthocyans, for instance myrtillin,
- ortho-hydroxybenzoates, for example gallic acid salts,
- hydroxystilbenes, for example 3,3',4,5'-tetrahydroxystilbene,
optionally oxylated (for example glucosylated),
- 3,4-dihydroxyphenylalanine and derivatives thereof,
- 2,3-dihydroxyphenylalanine and derivatives thereof,
- 4,5-dihydroxyphenylalanine and derivatives thereof,
- dihydroxycinnamates, such as caffeic acid and chlorogenic
acid,
- ortho-polyhydroxycoumarins,
- ortho-polyhydroxyisocoumarins,
- ortho-polyhydroxycoumarones,
- ortho-polyhydroxyisocoumarones,
- ortho-polyhydroxychalcones,
- ortho-polyhydroxychromones,
- quinones,
- hydroxyxanthones,
- 1,2-dihydroxybenzene and derivatives thereof,
- 1,2,4-trihydroxybenzene and derivatives thereof,
- 1,2,3-trihydroxybenzene and derivatives thereof,
- 2,4,5-trihydroxytoluene and derivatives thereof,
- proanthocyanidins and especially the proanthocyanidins Al ,
A2, Bl , B2, B3 and CI ,
- proanthocyanins,
- tannic acid,
- ellagic acid,
- and mixtures of the preceding compounds.
When the dyeing precursors have D and L forms, the two forms
may be used in the compositions according to the invention, as may
the racemic mixtures.
According to an embodiment, the natural ortho-diphenols are
derived from extracts of animals, of bacteria, of fungi, of algae, of
plants and of fruits, used in their entirety or partially. In particular
regarding the plants, the extracts are derived from fruits, including
citrus fruits, from vegetables, from trees and from shrubs. Mixtures of
these extracts that are rich in ortho-diphenols as defined previously
may also be used.
Preferably, the natural ortho-diphenol(s) of the invention are
derived from extracts of plants or plant parts.
For the purposes of the invention, these extracts will be put
into the same category as additional ortho-diphenol derivatives.
The extracts are obtained by extraction from various plant
parts, for instance the root, the wood, the bark, the leaf, the flower,
the fruit, the seed, the pod or the peel.
Among the plant extracts, mention may be made of extracts of
tea leaves and of rose.
Among the fruit extracts, mention may be made of extracts of
apple, of grape (in particular of grape seed) or extracts of cocoa beans
and/or pods.
Among the vegetable extracts, mention may be made of extracts
of potato or of onion peel.
Among the extracts of tree wood, mention may be made of
extracts of pine bark or extracts of logwood.
Mixtures of plant extracts may also be used.
According to a particular embodiment of the invention, the
ortho-diphenol derivative(s) are natural extracts, rich in orthodiphenols.
According to a preferred embodiment, the ortho-diphenol
derivative(s) are solely natural extracts.
Preferentially, the ortho-diphenol(s) according to the invention
are chosen from catechin, quercetin, haematein, haematoxylin,
brasilin, gallic acid, and natural extracts containing them chosen from
grape marc, pine bark, green tea, onion, cocoa bean, logwood, redwood
and oak gall.
More preferably still, the ortho-diphenol(s) used in one or more
compositions according to the invention are chosen from quercetin,
gallic acid and haematoxylin.
The natural extracts according to the invention may be in the
form of powders or liquids. Preferably, the extracts of the invention
are in the form of powders.
According to the invention, the natural and synthetic orthodiphenol
derivative(s) and/or the natural extract(s) used as ingredient
a) in one or more cosmetic composition(s) of use in the process
according to the invention preferably represent(s) from 0.00 1% to 20%
by weight of the total weight of the composition(s) containing the
ortho-diphenol(s) or the extract(s).
As regards the pure ortho-diphenols, the content in the
composition(s) containing them is preferably between 0.00 1% and 5%
by weight of each of these compositions.
As regards the extracts, the content in the composition(s)
containing the extracts per se is preferably between 0.5% and 20% by
weight of each of these compositions.
b) manganese or zinc salt
The dyeing process according to the invention uses one or
more manganese (Mn) salts or one or more zinc (Zn) salts. The
manganese or zinc salt(s) may be employed in one or more cosmetic
compositions used during the dyeing process.
For the purposes of the present invention, the term "manganese
or zinc salts" means the oxides of these metals, such as manganese
oxides, and the salts per se derived in particular from the action of an
acid on a metal.
Preferably, the salts are not oxides.
Among the salts, mention may be made of halides, such as
chlorides, fluorides and iodides; sulfates, phosphates; nitrates;
perchlorates and carboxylic acid salts and polymer salts, and also
mixtures thereof.
More particularly, the manganese salt is other than manganese
carbonate, manganese hydrogencarbonate or manganese
dihydrogencarbonate.
The carboxylic acid salts that may be used in the invention also
include salts of hydroxylated carboxylic acids such as gluconate.
As examples of polymer salts, mention may be made of
manganese pyrrolidonecarboxylate.
By way of example, mention may be made of manganese
chloride, manganese fluoride, manganese acetate tetrahydrate,
manganese lactate trihydrate, manganese phosphate, manganese
iodide, manganese nitrate trihydrate, manganese bromide, manganese
perchlorate tetrahydrate, manganese sulfate monohydrate and
manganese gluconate. The salts advantageously used are manganese
gluconate and manganese chloride.
Among the zinc salts, mention may be made of zinc sulfate,
zinc gluconate, zinc chloride, zinc lactate, zinc acetate, zinc glycinate
and zinc aspartate.
The manganese and zinc salts may be introduced in solid form
into the compositions or may be derived from a natural, mineral or
thermal water that is rich in these ions or alternatively from seawater
(especially the Dead Sea). They may also originate from mineral
compounds, for instance earths, ochres such as clays (for example
green clay), or even from a plant extract containing them (cf., for
example, patent document FR 2 814 943).
According to a preferred embodiment of the invention, the
manganese or zinc salt(s) used represent(s) from 0.00 1% to 0 .1% by
weight, approximately, of the total weight of the composition(s)
containing said metal salt(s), and even more preferentially from 0.05%
to 10% by weight approximately.
In particular, the manganese and zinc salts employed in the
invention are in oxidation state II, such as Mn(II) and Zn(II).
Preferably, the dyeing process of the invention employs one or
more manganese salts, in particular Mn(II) metal salts.
More preferentially still, the manganese salt(s) is (are) chosen
from carboxylic acid salts of manganese, in particular manganese
gluconate; more particularly manganese gluconate.
c) hydrogen peroxide or hydrogen peroxide-generating system
In the context of the present invention, the third constituent is
hydrogen peroxide or a hydrogen peroxide-generating system, such as:
a) urea hydrogen peroxide;
b) polymeric complexes that can release hydrogen peroxide,
such as polyvinylpyrrolidone/H202, in particular in the form of
powders, and the other polymeric complexes described in US 5 008
093, US 3 376 110 and US 5 183 90 1;
c) oxidases that produce hydrogen peroxide in the presence of
a suitable substrate (for example glucose in the case of glucose
oxidase or uric acid with uricase);
d) metal peroxides that generate hydrogen peroxide in water,
for instance calcium peroxide or magnesium peroxide;
e) perborates; or
f) percarbonates.
According to a preferred embodiment of the invention, the
composition contains one or more hydrogen peroxide-generating
system(s) chosen from a) urea hydrogen peroxide, b) polymeric
complexes that can release hydrogen peroxide chosen from
polyvinylpyrrolidone/H 202, c) oxidases, e) perborates and f)
percarbonates.
In particular, the third constituent is hydrogen peroxide.
Moreover, the composition(s) comprising hydrogen peroxide or
the hydrogen peroxide generator may also contain various adjuvants
conventionally used in hair dyeing compositions and as defined
hereinbelow.
According to a particular form of the invention, the hydrogen
peroxide used or the hydrogen peroxide-generating system(s) used
preferably represent(s) from 0.00 1% to 12% by weight of hydrogen
peroxide relative to the total weight of the composition(s) containing
it/them, and even more preferentially from 0.2% to 2.7% by weight.
d) (bi)carbonate(s) or (bi)carbonate-generating system
In accordance with the present invention, the dyeing process
uses one or more (bi)carbonates or one or more (bicarbonategenerating
systems.
The term "(bi)carbonate-generating system" means a system
which generates (bi)carbonate in situ, for instance carbon dioxide in
water or by buffering carbonate with an inorganic or organic acid. The
(bi)carbonate(s) or the (bi)carbonate-generating system(s) may be used
in one or more cosmetic compositions during the dyeing process.
The (bi)carbonate(s) is (are) chosen from:
a) carbonates of alkali metals (Met+
2C0 3 ) , of alkaline earth
metals (Met' +C0 3 ) , of ammonium ((R" 4N+)2C0 3 ) or of
phosphonium ((R" 4P+)2C0 3 ) with Met' representing an alkaline
earth metal and Met representing an alkali metal, and R" , which are
identical or different, representing a hydrogen atom or an optionally
substituted (Ci-C )alkyl group, such as hydroxyethyl,
b) bicarbonates, also known as hydrogencarbonates, of the
following formulae:
R' HC0 3 with R' representing a hydrogen atom, an alkali
metal, an ammonium group R" 4N - or a phosphonium group
R" 4P+- in which R" , which are identical or different,
represent a hydrogen atom or an optionally substituted (Ci-
C )alkyl group, such as hydroxyethyl, and, when R'
represents a hydrogen atom, the hydrogencarbonate is then
known as dihydrogencarbonate (C0 2, H20); and
Met' + (HC0 3 )2 with Met' representing an alkaline earth
metal.
More particularly, the (bi)carbonate(s) is (are) chosen from
alkali metal, alkaline earth metal or ammonium (bi)carbonates;
preferentially, alkali metal or ammonium (bi)carbonates.
Mention may be made of Na, K, Mg and Ca carbonates or
hydrogencarbonates and mixtures thereof, and in particular of sodium
hydrogencarbonate. These hydrogencarbonates may originate from a
natural water, for example spring water from the Vichy basin or from
La Roche-Posay or Badoit water (cf., for example, patent document FR
2 814 943). In particular, mention may be made of sodium carbonate
[497- 19-8] = Na2C0 3, sodium hydrogencarbonate or sodium
bicarbonate [144-55-8] = NaHC0 3, and sodium dihydrogencarbonate =
Na(HC0 3)2.
According to the invention, the (bi)carbonate agent(s) used
preferably represent(s) from 0.00 1% to 10% by weight of the total
weight of the composition(s) containing the (bi)carbonate agent(s) and
even more preferentially from 0.005% to 5% by weight.
Preferably, the ingredient d) is a (bi)carbonate. More
preferably, the (bi)carbonate used in the composition during the
dyeing process is ammonium (bi)carbonate or sodium bicarbonate.
e) alkalinizing agent(s) other than the bicarbonate(s)
The alkalinizing agent used in the dyeing process according to
the invention as fifth ingredient is different from the (bi)carbonate(s)
d) as defined previously. It is an agent which makes it possible to
increase the pH of the composition(s) in which it is present. The
alkalinizing agent is a Bronsted, Lowry or Lewis base. It may be
inorganic or organic.
In particular, said agent is chosen from i) aqueous ammonia, ii)
alkanolamines such as monoethanolamine, diethanolamine,
triethanolamine and derivatives thereof, iii) oxyethylenated and/or
oxypropylenated ethylenediamines, iv) inorganic or organic
hydroxides, v) alkali metal silicates such as sodium metasilicates, vi)
amino acids, preferably basic amino acids such as arginine, lysine,
ornithine, citrulline and histidine, and vii) the compounds of formula
(III) below:
in which:
- W is a divalent ( C i - C )alkylene group, preferably a propylene
group, optionally substituted in particular by a hydroxyl group or a C i -
C 4 alkyl radical;
- Ra, Rb, Rc and Rd, which are identical or different, represent
a hydrogen atom or a C 1- C 4 alkyl or C 1- C 4 hydroxyalkyl radical.
The inorganic or organic hydroxides are preferably chosen
from i) hydroxides of an alkali metal, ii) hydroxides of an alkaline
earth metal, for instance sodium hydroxide or potassium hydroxide,
iii) hydroxides of a transition metal, such as hydroxides of metals
from Groups III, IV, V and VI, and iv) hydroxides of lanthanides or of
actinides, quaternary ammonium hydroxides and guanidinium
hydroxide.
Preferentially, whether for the composition according to the
invention or the process implemented in the invention, the alkalinizing
agent is not sodium hydroxide NaOH. More generally and
preferentially, whether for the composition according to the invention
or the process implemented in the invention, the alkalinizing agent is
not an alkali metal hydroxide XOH, with X = alkali metal.
The hydroxide may be formed in situ, for instance guanidine
hydroxide, by reacting calcium hydroxide and guanidine carbonate.
The alkalinizing agent(s) e) as defined previously preferably
represent(s) from 0.00 1% to 10% by weight of the weight of the
composition(s) containing them, more particularly from 0.005% to 8%
by weight of the composition.
Preferably, the alkaline agent(s) is (are) chosen from
alkanolamines, in particular monoethanolamine.
f) magnesium, molybdenum or calcium salts
In accordance with the present invention, the dyeing process
according to the invention additionally employs one or more metal
salt(s) chosen from magnesium salts, molybdenum salts and calcium
salts.
The term "magnesium, molybdenum or calcium salt" is
understood to mean, within the meaning of the present invention, the
oxides of these metals and the salts properly speaking resulting in
particular from an acid with a metal.
Preferably, the salts of these metals are not oxides.
Among the salts of these metals, mention may be made of
hydroxides, halides, sulfates, phosphates, nitrates and carboxylic acid
salts and polymer salts, and also mixtures thereof.
The carboxylic acid salts that may be used in the invention also
include salts of hydroxylated carboxylic acids such as gluconate.
According to a particular embodiment of the invention, the
metal derivatives(s) is (are) magnesium (Mg) derivative(s).
Mention may be made, among magnesium salts, of hydroxides,
such as magnesium hydroxide, halides, sulfates, nitrates, such as
magnesium nitrate, or carboxylic acid salts.
In particular, the carboxylic acid salts of magnesium are
chosen from magnesium acetate, magnesium oxalate, magnesium
citrate, magnesium lactate, magnesium gluconate, magnesium
ascorbate, magnesium formate dihydrate or magnesium stearate.
In particular, the halides are chosen from magnesium chloride,
which may be hydrated or anhydrous, magnesium bromide or
magnesium iodide.
In particular, the sulfates are hydrated or anhydrous
magnesium sulfate.
In particular, the phosphates are magnesium phosphate,
magnesium hydrogenphosphate or tribasic magnesium phosphate
Mg3(P04)2 , which may be hydrated or anhydrous.
In particular, the magnesium salt is Dead Sea Salt [7647- 14-5]
obtained by evaporation of water from the Dead Sea, such as sold by
Tri Industries under the name "Dead Sea Salt" or by Sea Works Ltd
under the name "Dead Sea Bath Salt".
Preferably, the magnesium salts are chosen from magnesium
sulfates, carboxylic acid salts, in particular magnesium gluconate and
magnesium acetate, and Dead Sea salt.
In a preferred form of the invention, the amount in moles of
magnesium salts used in the process or in the composition is
equivalent in moles to that of the dyes.
The magnesium salt(s) is (are) present in the cosmetic
composition(s) used in the process according to the invention in a
content ranging from 0.00 1% to 20% by weight, relative to the total
weight of the composition(s) in which they are present.
According to a particular embodiment of the invention, the
metal derivative(s) is (are) molybdenum (Mo) derivative(s).
In particular, the molybdenum metal derivative(s) exhibit an
oxidation state ranging from (II) to (VI) and are as described in Kirk-
Othmer's Encyclopedia of Chemical Technology Copyright © 200 1 by
John Wiley & Sons Inc. Last updated: 17 Sep 2009, "Molybdenum
compounds", Edward I . Stieffel, pp. 87 1-895, or Ullmann 's
Encyclopedia; WILEY-VCH Verlag GmbH & Co. KGaA, 2000-2005,
"Molybdenum and Molybdenum Compounds".
More particularly:
a) binary molybdenum halides of oxidation states (II) to (VI),
hexacoordinated with 6 halogens of Mo(V), (IV) and (III), the
molybdenum atoms being bonded via halogen bonds such as Mo(II)
halide, containing [Mo6Hal ]4+ clusters bonded to halogen atoms to
give Mo Hali 2 with Hal, which are identical or different, representing
a halogen atom, and more particularly Hal represents CI;
b) molybdenum tetrahalides (Hal'^Mo with Hal' , which are
identical or different, representing a halogen atom, in particular
MoCl4;
c) molybdenum sulfur derivatives chosen from:
molybdenum disulfides [131 7-33-5], molybdenum(IV)
sulfides, MoS2;
- molybdenum sesquisulfide [1203 3-33-9]; dimolybdenum(III)
trisulfides, M02S3;
d) molybdenum acetate dimer [ 1422 1-06-8] .
In a preferred form of the invention, the amount in moles of
molybdenum salts used in the process or in the composition is
equivalent in moles to that of the dyes.
Preferably, the molybdenum metal derivative is chosen from
molybdenum acetate dimer.
The molybdenum salt(s) is (are) present in the cosmetic
composition(s) used in the process according to the invention in a
content ranging from 0.00 1% to 20% by weight, relative to the total
weight of the composition(s) in which they are present.
According to a particular embodiment of the invention, the
metal derivative(s) is (are) chosen from calcium salts and also the
hydrates thereof and supported forms thereof.
By way of example, mention may be made of the hydroxides,
sulfates, halides, carboxylates, phosphates, borates and carbonates.
In particular, the hydroxides are calcium hydroxide Ca(OH) 2.
In particular, the sulfates are chosen from calcium sulfate
Ca SC or gypsum.
In particular, the halides are chosen from calcium chloride,
calcium bromide or calcium iodide.
In particular, the carboxylates are chosen from calcium
oxalate, calcium diacetate, calcium citrate, tricalcium 2-
hydroxypropanoate- 1,2,3-tricarboxylate [8 13-94-5], calcium lactate,
calcium 2-hydroxypropanoate, hydrated or anhydrous calcium
gluconate, calcium ascorbate, calcium 2-ethylbutanoate, calcium
formate, calcium levulinate, calcium mesoxalate, calcium oleate,
calcium palmitate, calcium propionate, calcium saccharate, calcium
stearate, calcium stearoyl-2-lactylate, calcium succinate, calcium
tartrate and calcium pyrrolidonecarboxylate.
In particular, the calcium phosphates are chosen from calcium
phosphate Ca3(P04)2 , hydrated or anhydrous calcium
hydrogenphosphate CaHP0 4, calcium hydroxyphosphate
[Ca (OH)(P0 4)3] , hydrated or anhydrous calcium
bis(dihydrogenphosphate) Ca(H2P0 4 ) 2 , calcium pyrophosphate
Ca2P20 7, hydroxyapatite, calcium fluorophosphate and calcium
glycerophosphate.
In particular, the calcium derivative is calcium borate.
Preferentially, the calcium derivative is chosen from calcium
sulfate CaS0 4, gypsum, calcium diacetate, hydrated or anhydrous
calcium gluconate, calcium phosphate Ca3(P0 4)2, hydrated or
anhydrous calcium hydrogenphosphate CaHP0 4, hydrated or
anhydrous calcium bis(dihydrogenphosphate) Ca(H2P0 4)2, calcium
pyrrolidonecarboxylate and hydroxyapatite.
More preferably still, the calcium salts are chosen from
calcium carboxylates.
In particular, the calcium salts are chosen from calcium acetate
monohydrate, calcium gluconate hydrate and calcium
pyrrolidonecarboxylate.
In a preferred form of the invention, the amount in moles of
calcium salts used in the process or in the composition is equivalent in
moles to that of the dyes.
The calcium salt(s) is (are) present in the cosmetic
composition(s) used in the process according to the invention in a
content ranging from 0.00 1% to 20% by weight, relative to the total
weight of the composition(s) in which they are present.
Preferentially, the metal salts f) according to the invention are
soluble in water to a proportion of at least 0.000 1 g/1.
The metal salts f) according to the invention may be introduced
in solid form into the compositions or may originate from a natural,
mineral or thermal water that is rich in these ions, or alternatively
from seawater (in particular Dead Sea water). They may also originate
from inorganic compounds, such as plant extracts containing them
(cf., for example, patent document FR 2 814 943).
- water:
According to an embodiment of the invention, water is
preferably included in the process of the invention. It may originate
from the moistening of the keratin fibres and/or from the
composition(s) comprising compounds a) to f) as defined previously or
from one or more other compositions.
Preferably, the water originates at least from a composition
comprising at least one compound chosen from a) to f) as defined
previously.
- cosmetic compositions:
The cosmetic compositions according to the invention are
cosmetically acceptable, i.e. they comprise a dyeing support that
generally contains water or a mixture of water and of one or more
organic solvents or a mixture of organic solvents.
The term "organic solvent" means an organic substance that is
capable of dissolving or dispersing another substance without
chemically modifying it.
- organic solvents:
Examples of organic solvents that may be mentioned include
lower C 1- C 4 alkanols, such as ethanol and isopropanol; polyols and
polyol ethers such as 2-butoxyethanol, propylene glycol, propylene
glycol monomethyl ether, diethylene glycol monoethyl ether,
diethylene glycol monomethyl ether or hexylene glycol; and also
aromatic alcohols, for instance benzyl alcohol or phenoxyethanol.
The organic solvents are present in proportions preferably of
between 1% and 40% by weight approximately and more preferably
still between 5% and 30% by weight approximately relative to the
total weight of the dyeing composition.
- adjuvants:
The composition(s) of the dyeing process in accordance with
the invention may also contain various adjuvants conventionally used
in hair dyeing compositions, such as anionic, cationic, non-ionic,
amphoteric or zwitterionic surfactants or mixtures thereof, anionic,
cationic, non-ionic, amphoteric or zwitterionic polymers or mixtures
thereof, inorganic or organic thickeners, and in particular anionic,
cationic, non-ionic and amphoteric polymeric associative thickeners,
antioxidants, penetrating agents, sequestering agents, fragrances,
buffers, dispersing agents, conditioning agents, for instance volatile or
non-volatile and modified or unmodified silicones, film-forming
agents, ceramides, preservatives and opacifying agents.
Said adjuvants are preferably chosen from surfactants such as
anionic or non-ionic surfactants or mixtures thereof and inorganic or
organic thickeners.
The above adjuvants are generally present in an amount for
each of them of between 0.0 1% and 40% by weight relative to the
weight of the composition, and preferably between 0 .1% and 20%> by
weight relative to the weight of the composition.
Needless to say, those 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
composition(s) of use in the dyeing process in accordance with the
invention are not, or are not substantially, adversely affected by the
envisioned addition(s).
- additional dyes:
The dyeing process using the ingredients a) to f) as previously
defined may also use one or more additional direct dyes. These direct
dyes are chosen, for example, from those conventionally used in direct
dyeing, and among which mention may be made of any commonly used
aromatic and/or non-aromatic dye such as neutral, acidic or cationic
nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes,
natural direct dyes other than ortho-diphenols, neutral, acidic or
cationic quinone and in particular anthraquinone direct dyes, azine,
triarylmethane, indoamine, methine, styryl, porphyrin,
metalloporphyrin, phthalocyanine and methine cyanine direct dyes,
and fluorescent dyes.
Among the natural direct dyes, mention may be made of
lawsone, juglone, indigo, isatin, curcumin, spinulosin, apigenidin and
orceins. Extracts or decoctions containing these natural dyes and in
particular cataplasms or henna-based extracts may also be used.
According to the invention, the direct dye(s) used in the
composition according to the invention which comprises the
ingredients a) to f) as previously defined, or the composition(s) of the
dyeing process according to the invention, preferably represents from
0.00 1% to 10% by weight approximately of the total weight of the
composition(s) and even more preferentially from 0.05% to 5% by
weight approximately.
The composition according to the invention or the
composition(s) of the process using the ingredients a) to f) as
previously defined may also comprise one or more oxidation bases
and/or one or more couplers conventionally used for dyeing keratin
fibres.
Among the oxidation bases, mention may be made of paraphenylene
diamines, bis (phenyl) alkylene diamines, para-aminophenols,
bis-para-aminophenols, ortho-aminophenols and heterocyclic bases,
and the addition salts thereof.
Among these couplers, mention may be made especially of
meta-phenylenediamines, meta-aminophenols, meta-diphenols,
naphthalene couplers and heterocyclic couplers, and the addition salts
thereof.
The oxidation base(s) present in said composition(s) that is
(are) used in the process is (are) generally each present in an amount
of between 0.00 1% and 10% by weight of the total weight of the
composition(s) containing it or them.
The cosmetic composition(s) of the invention may be in
various formulation forms, such as a powder, a lotion, a mousse, a
cream or a gel, or in any other form that is suitable for dyeing keratin
fibres. They may also be packaged in a propellant-free pump-action
spray or under pressure in an aerosol container in the presence of a
propellant and form a foam.
- pH of the composition(s):
In accordance with the present invention, the pH of at least one
of the cosmetic compositions comprising at least one of the
ingredients a), b), d), e) and/or f) is alkaline, i.e. greater than 7, and
preferably between 8 and 12, and more particularly between 8 and 10 .
In other words, at least one of the cosmetic compositions used
during the dyeing process of the invention has an alkaline pH, i.e.
greater than 7 .
According to one embodiment, the pH of the cosmetic
composition(s) containing d) one or more (bi)carbonate(s) or one or
more (bi)carbonate-generating system(s) is alkaline, i.e. greater than
7, preferably between 8 and 12, and more particularly between 8 and
10 .
Preferably, the (bi)carbonate(s) or the (bi)carbonate-generating
system(s) is (are) used in a single cosmetic composition and the pH of
said composition is alkaline, i.e. greater than 7, preferably between 8
and 12, and more particularly between 8 and 10 .
According to a particular embodiment of the invention, the pH
of the cosmetic composition comprising d) one or more
(bi)carbonate(s) or one or more (bi)carbonate-generating system(s)
and e) one or more alkalinizing agent(s) other than the
(bi)carbonate(s) is alkaline, i.e. greater than 7, preferably between 8
and 12, and more particularly between 8 and 10 .
In other words, preferably, the (bi)carbonate(s) or the
(bi)carbonate-generating system(s) d) and the alkalinizing agent(s)
other than the (bi)carbonate(s) e) is (are) used in a single composition
and the pH of said composition is alkaline, i.e. greater than 7,
preferably between 8 and 12, and more particularly between 8 and 10,
in particular between 9 and 10 .
Even more preferentially, the (bi)carbonate(s) chosen from
ammonium bicarbonates and the alkalinizing agents chosen from
alkanolamines, in particular monoethanolamine, are used in a single
composition and the pH of said composition is alkaline, i.e. greater
than 7, preferably between 8 and 12, and more particularly between 8
and 10, in particular between 9 and 10 .
According to one embodiment, if one or more cosmetic
composition(s) used during the dyeing process do(es) not contain
(bi)carbonates, the pH of the composition(s) containing hydrogen
peroxide or a hydrogen peroxide-generating system is preferably less
than 7, more particularly between 1 and 5.
In particular, the cosmetic composition composed solely of
hydrogen peroxide exhibits a pH of less than 7 .
Preferably, the composition(s) containing the
dihydroxyflavanol derivative(s) and not containing (bi)carbonates has
(have) a pH of less than 7 and preferably of between 3 and 6.5 .
According to a particular embodiment of the invention, the
cosmetic composition(s) containing the manganese or zinc salt(s) b)
and not containing (bi)carbonates has (have) a pH of less than 7 and
preferably of between 3 and 6.5 .
According to a particular embodiment of the invention, the
cosmetic composition(s) containing the metal salt(s) f) and not
containing (bi)carbonates has (have) a pH of less than 7 and
preferably of between 3 and 6.5 .
The pH of these compositions may be adjusted to the desired
value by means of alkalinizing agents as defined previously in d) or
using acidifying agents usually used in the dyeing of keratin fibres, or
alternatively by means of standard buffer systems.
Among the acidifying agents for the compositions used in the
invention, examples that may be mentioned include inorganic or
organic acids, for instance hydrochloric acid, orthophosphoric acid,
sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid,
citric acid or lactic acid, or sulfonic acids.
Among the alkalinizing agents concerned are the agents as
defined previously under the heading "e) alkalinizing agent(s) " .
-dyeing process in one or more steps
A particular embodiment of the invention concerns processes
for dyeing in one or two steps.
According to one embodiment, the process for dyeing keratin
fibres is performed in a single step by applying, to the keratin fibres,
an aqueous dyeing composition, comprising:
a) one or more dihydroxyflavanol derivative(s),
b) one or more manganese salt(s) or one or more zinc salt(s),
c) hydrogen peroxide or one or more hydrogen peroxidegenerating
system(s),
d) one or more (bi)carbonate(s) or one or more (bicarbonategenerating
system(s),
e) one or more alkalinizing agent(s) other than the
(bi)carbonate(s), and
f) one or more metal salt(s) chosen from magnesium salts,
molybdenum salts and calcium salts.
The leave-on time after application is generally set at between
3 and 120 minutes, preferentially between 10 and 60 minutes and more
preferentially between 15 and 45 minutes.
In this embodiment, the cosmetic dyeing composition
comprising the ingredients a), b), c), d), e) and f) has an alkaline pH,
i.e. therefore greater than 7, preferably between 8 and 12, and more
particularly between 8 and 10 .
According to another embodiment, the process for dyeing
keratin fibres is performed in two steps.
In a first two-step variant of this process, the first step consists
in applying to the keratin fibres a dyeing composition comprising the
ingredients a), b), c) and f) as defined previously, and then, in a
second step, a composition comprising the ingredients d) and e) as
defined previously is applied to said keratin fibres, it being
understood that at least one of the two compositions is aqueous.
Preferably, the composition comprising the dihydroxyflavanol
derivative(s) is aqueous. Even more preferentially, the two
compositions used in this embodiment are aqueous.
In a second two-step variant of the process, the first step
consists in applying to said fibres a composition comprising the
ingredients a), b) and c) as defined previously, and then, in a second
step, a composition comprising the ingredients d), e) and f) as defined
previously is applied to said fibres, it being understood that at least
one of the two compositions is aqueous.
For the latter two processes, the leave-on time after application
for the first step is generally set at between 3 and 120 minutes,
preferentially between 10 and 60 minutes and more preferentially
between 15 and 45 minutes. The application time of the composition
used during the second step is generally set at between 3 and 120
minutes, preferentially between 3 and 60 minutes and more
preferentially between 5 and 30 minutes.
Preferably, the process for dyeing keratin fibres is carried out
in two steps.
Preferably, the metal salts f) chosen from magnesium salts,
molybdenum salts and/or calcium salts are employed during the dyeing
process with at least one of the ingredients a), b) and c).
More preferably, the metal salts f) are employed with the
dihydroxyflavanol derivative(s) and the manganese or zinc salts.
In other words, the metal salts f) are used in co-treatment of
the keratin fibres with the manganese or zinc salts.
In particular, the dyeing process is carried out in two steps by
applying to the keratin fibres:
i) a cosmetic composition comprising a) one or more
dihydroxyflavanol derivative(s), b) one or more manganese salt(s)
chosen from carboxylic acid salts of manganese, and c) hydrogen
peroxide, and
ii) a cosmetic composition comprising d) one or more
(bi)carbonate(s) chosen from ammonium bicarbonates and e) one or
more alkalinizing agent(s) chosen from alkanolamines,
it being understood that the composition comprising the
ingredients d) and e) exhibits an alkaline pH, i.e. of greater than 7,
and in particular of between 8 and 10 .
More particularly, the dihydroxyflavanol derivative employed
in the composition i) is catechin.
Irrespective of the application method, the application
temperature is generally between ambient temperature ( 15 to 25°C)
and 80°C and more particularly between 15 and 45°C. Thus, after
application of the composition according to the invention, the head of
hair may advantageously be subjected to a heat treatment by heating to
a temperature of between 30 and 60°C. In practice, this operation may
be performed using a styling hood, a hairdryer, an infrared ray
dispenser or other standard heating appliances.
Use may be made, both as means for heating and smoothing the
hair, of a heating iron at a temperature of between 60°C and 220°C
and preferably between 120°C and 200°C.
Irrespective of the application method, the keratin fibres may
optionally be mechanically wiped and/or dried between each step, in
particular before carrying out the step comprising the application of a
composition comprising the ingredient d), and in particular before
carrying out the final step comprising the application of a composition
containing the metal salt(s) f) as defined previously.
The steps of intermediate mechanical wiping and drying are
also known as "controlled leave-in" to distinguish from "standard
copious rinsing with water" and "leave-in" . The term "mechanical
wiping" of the fibres means rubbing an absorbent article on the fibres
and the physical removal, by means of the absorbent article, of the
excess ingredient(s) that have not penetrated into the fibres. The
absorbent article may be a piece of fabric such as a towel, particularly
a terry towel, a cloth or absorbent paper such as household roll towel.
According to a particularly advantageous process of the
invention, the mechanical wiping is performed without total drying of
the fibre, leaving the fibre moist.
The term "drying" means the action of evaporating the organic
solvents and/or water that are in one or more compositions used in the
process of the invention, comprising or not comprising one or more
ingredients a) to f) as defined previously. The drying may be
performed with a source of heat (convection, conduction or radiation)
by sending, for example, a stream of hot gas such as air necessary to
evaporate the solvent(s). Sources of heat that may be mentioned
include a hairdryer, a hairstyling hood, a hair-smoothing iron, an
infrared ray dispenser or other standard heating appliances.
A particular form of the invention concerns a dyeing process
that is performed at ambient temperature (25°C).
In all the particular and variant forms of the processes
previously described, the compositions mentioned are ready-for-use
compositions that may result from the extemporaneous mixing of two
or more compositions and in particular of compositions present in
dyeing kits.
- dyeing device or kit
Another subject-matter of the invention is a multicompartment
dyeing device or kit. Advantageously, this kit comprises from 2 to 7
compartments containing from 2 to 7 compositions in which are
distributed the ingredients a) one or more dihydroxyflavanol
derivative(s), b) one or more manganese salt(s) or one or more zinc
salt(s), c) hydrogen peroxide or one or more hydrogen peroxidegenerating
system(s), d) one or more (bi)carbonate(s) or one or more
bicarbonate-generating system(s), e) one or more alkalinizing agent(s)
other than the (bi)carbonate(s) and f) one or more metal salt(s) chosen
from magnesium salts, molybdenum salts or calcium salts, it being
possible for said compositions to be aqueous or pulverulent, with
particularly at least one of said compositions being aqueous.
According to a first variant, the kit comprises seven
compartments, the first six compartments comprising, respectively, the
powdered ingredients a), b), c), d), e) and f) as defined previously and
the seventh compartment containing an aqueous composition such as
water. In this case, the compound(s) c) are hydrogen peroxide
precursors.
Another variant concerns a seven-compartment kit, one of
which compartments contains an aqueous composition and the other
compartments of which comprise an ingredient a) to f) as defined
previously.
In another variant, the device comprises six compartments: a
first compartment comprising a composition containing a) one or more
dihydroxyflavanol derivative(s), a second compartment comprising b)
one or more manganese salt(s) or one or more zinc salt(s), a third
compartment comprising c) hydrogen peroxide or one or more
hydrogen peroxide-generating system(s), a fourth compartment
containing d) one or more (bi)carbonate(s) or one or more
(bi)carbonate-generating system(s), a fifth compartment containing e)
one or more alkalinizing agent(s) other than the (bi)carbonate(s) and a
sixth compartment containing f) one or more metal salt(s) chosen from
magnesium salts, molybdenum salts and calcium salts. Preferably, at
least one of these compositions is aqueous.
Another preferred embodiment concerns a device comprising
four compartments:
(I) a first compartment containing a composition including:
a) one or more dihydroxyflavanol derivative(s),
(II) a second compartment containing a composition including:
b) one or more manganese salt(s) or one or more zinc
salt(s),
c) hydrogen peroxide or one or more hydrogen peroxidegenerating
system(s),
(iii) a third compartment containing a composition including:
d) one or more (bi)carbonate(s) or one or more
(bi)carbonate-generating system(s), and
e) one or more alkalinizing agent(s) other than the
(bi)carbonate(s),
(iv) a fourth compartment containing a composition including:
f) one or more metal salt(s) chosen from magnesium salts,
molybdenum salts and calcium salts.
In this other embodiment, at least one of the four compositions
is aqueous and the dihydroxyflavanol derivative(s) may be in powder
form.
It is also possible to have a four-compartment kit, the first i)
containing a composition comprising a) one or more
dihydroxyflavanol derivative(s) and b) one or more manganese salt(s)
or one or more zinc salt(s), the second ii) containing a composition
comprising c) hydrogen peroxide or a hydrogen peroxide-generating
system, the third iii) containing a composition comprising d) the
(bi)carbonate agent and e) the alkalinizing agent other than the
(bi)carbonate, and the fourth iv) containing a composition comprising
f) one or more metal salt(s) chosen from magnesium salts,
molybdenum salts and calcium salts. In this other kit, at least one of
the compositions is preferentially aqueous. In addition, more
particularly, this composition contains hydrogen peroxide.
According to a specific form of the invention, the kit
comprises three compartments: a first compartment comprising a
composition containing a) one or more dihydroxyflavanol
derivative(s), b) one or more manganese salt(s) or one or more zinc
salt(s) and c) hydrogen peroxide or one or more hydrogen peroxidegenerating
system(s), a second compartment containing d) one or more
(bi)carbonate(s) and e) one or more alkalinizing agent(s) other than
the (bi)carbonate(s), and a third compartment containing f) one or
more metal salt(s) chosen from magnesium salts, molybdenum salts
and calcium salts.
Among the three-compartment kits, it is also possible to have
kits that contain, in a first compartment, a composition comprising a),
b), d) and e) as defined previously, in a second compartment, a
composition comprising c) as defined previously and, in a third
compartment, a composition comprising f) as defined previously.
In these two variants of three-compartment kits, the first
composition contained in the first compartment comprising either a),
b) and c) or a), b), d) and e) is in powder form and, preferably, the
second composition is aqueous.
According to one variant, the device according to the invention
also comprises an additional composition comprising one or more
treating agents.
The compositions of the device according to the invention are
packaged in separate compartments, optionally accompanied by
suitable application means, which may be identical or different, such
as fine brushes, coarse brushes or sponges.
The device mentioned above may also be equipped with a
means for dispensing the desired mixture on the hair, for instance the
devices described in Patent FR 2 586 913.
The present invention also relates to the use of one or more
metal salt(s) f) as defined previously for improving the chromaticity
of keratin fibres, in particular human keratin fibres such as the hair,
coloured using one or more dihydroxyflavanol derivative(s) as defined
previously.
In particular, the invention relates to the use of one or more
metal salt(s) f) in a dyeing composition comprising one or more
dihydroxyflavanol derivative(s) for improving the chromaticity of
keratin fibres.
The following examples serve to illustrate the invention
without, however, being limiting in nature.
I . Dyeing example
In the following example, the chromaticity C* was compared
between a dyeing process according to the invention and a dyeing
process which is identical but which does not involve the use of
magnesium salts.
1. Compositions tested
(*) 0 . 144 g of 167-volume aqueous hydrogen peroxide solution
( **) Dead Sea salt comprising 33% by weight of magnesium chloride
Composition B (developer) Amount
Sodium bicarbonate d) 2.6 g
Monoethanolamine e) g
Demineralized water q.s. for 100 g
2 . Procedure
Each composition Al, A2, A3 and A4 is applied to locks of
hair comprising 90% white hairs that have been permanent-waved, in a
proportion of 12 grams of composition per gram of hair. The
composition is then left to stand on the locks for 30 minutes at a
temperature of 50°C.
After this, the impregnated hair is wiped using an absorbent
paper towel to remove the excess composition.
The composition B is then applied to each of the locks in a
proportion of 4 grams of composition per gram of lock. The
composition B exhibits a pH = 9.5 . The leave-on time is 10 minutes at
ambient temperature. The hair is then rinsed with water, washed with a
conventional shampoo and dried under a hood.
3. Colorimetric results
The chromaticity C* is compared between a dyeing process
according to the invention and an identical process not employing the
magnesium salt.
The colour of the locks was evaluated in the CIE L* a * b *
system, using a Minolta Spectrophotometer CM2600D colorimeter. In
this L* a * b * system, the three parameters denote, respectively, the
colour intensity (L*), the green/red colour axis (a*) and the
blue/yellow colour axis (b*).
The chromaticity was measured by means of the values a * and
b*, and is obtained from the following formula:
The higher the C* value, the more chromatic is the colour
obtained.
The values of the chromaticity C* are given in the table below:
It is found that the dyeing process according to the invention
makes it possible to result in more chromatic colourations than the
comparative process devoid of metal salt f).
II. Dyeing example
In the following example, the chromaticity C* was compared
between a dyeing process according to the invention and a dyeing
process which is identical but which does not involve the use of a
molybdenum salt.
1. Compositions tested
2 . Procedure
The composition A 5 is applied to locks of hair comprising 90%
white hairs that have been permanent-waved, in a proportion of 12
grams of composition per gram of hair. The composition is then left to
stand on the locks for 30 minutes at a temperature of 50°C.
After this, the impregnated hair is wiped using an absorbent
paper towel to remove the excess composition.
The composition B is then applied to the locks in a proportion
of 4 grams of composition per gram of lock. The composition B
exhibits a pH = 9.5 . The leave-on time is 10 minutes at ambient
temperature. The hair is then rinsed with water, washed with a
conventional shampoo and dried under a hood.
3. Colorimetric results
The chromaticity C* is calculated in accordance with equation
(III) and its values are given in the table below:
It is found that the dyeing process according to the invention
makes it possible to result in more chromatic colourations than the
comparative process devoid of metal salt f).
III. Dyeing example
In the following example, the chromaticity C* was compared
between a dyeing process according to the invention and a dyeing
process which is identical but which does not involve the use of a
composition comprising magnesium salts.
1. Compositions tested
Composition B Developer
Ammonium bicarbonate d) 2.6 g
Monoethanolamine e) 2 g
Demineralized water q.s. for 100 g
2 . Procedure
Each composition A6, A 7 and A 8 is applied to locks of hair
comprising 90% white hairs that have been permanent-waved, in a
proportion of 12 grams of composition per gram of hair. The
composition is then left to stand on the locks for 30 minutes at a
temperature of 50°C.
After this, the impregnated hair is wiped using an absorbent
paper towel to remove the excess composition.
The composition B is then applied to each of the locks in a
proportion of 4 grams of composition per gram of lock. The
composition B exhibits a pH = 9.5 . The leave-on time is 10 minutes at
ambient temperature. The hair is then rinsed with water, washed with a
conventional shampoo and dried under a hood.
3. Colorimetric results
The chromaticity C* is calculated in accordance with equation
(III) and the values are given in the table below:
Results C*
Without calcium salts (comparative) 19.8
Calcium acetate
mono hydrate 23.7
(invention)
Calcium
pyrrolidonecarboxylate 21.2
(invention)
Calcium gluconate
(invention) 21.8
It is found that the dyeing process according to the invention
makes it possible to result in more chromatic colourations than the
comparative process devoid of metal salt f).

CLAIMS
1. Process for dyeing keratin fibres, in particular human keratin
fibres such as the hair, in which said fibres are treated with one or
more cosmetic compositions containing, taken together or separately in
said composition(s), the following ingredients:
a) one or more dihydroxyflavanol derivative(s),
b) one or more manganese salt(s) or one or more zinc salt(s),
c) hydrogen peroxide or one or more hydrogen peroxidegenerating
system(s),
d) one or more (bi)carbonate(s) or one or more (bicarbonategenerating
system(s),
e) one or more alkalinizing agent(s) other than the
bicarbonate(s), and
f) one or more metal salt(s) chosen from magnesium salts,
molybdenum salts and calcium salts;
it being understood that:
- the pH of at least one of the compositions comprising at least
one of the ingredients a), b), d), e) and/or f) is alkaline, i.e. greater
than 7, and
- the ingredient f) is applied as co-treatment with at least one
of the other ingredients a) to e).
2 . Dyeing process according to Claim 1, characterized in that
the dihydroxyflavanol derivative(s) is (are) chosen from natural
dihydroxyflavanol derivative(s).
3. Dyeing process according to Claim 1 or 2, characterized in
that the dihydroxyflavanol derivatives represent compounds of
following formula (I) and also organic or inorganic acid salts thereof,
optical, geometric and tautomeric isomers thereof, and solvates thereof
such as the hydrates:
in which:
• R1, R2, R3, R4, R5, R6, R7, R8 and R9, which are identical or different,
represent:
- a hydrogen atom,
- a halogen atom,
- a hydroxyl group,
- a (Ci-C )alkyl group,
- a (Ci-C )alkoxy group,
- a (Ci-Ce)alkylthio group,
- a carboxyl group,
- an alkoxycarbonyl group,
- an optionally substituted amino group,
- an optionally substituted linear or branched alkenyl group,
- an optionally substituted cycloalkyl group,
- an aryl group,
- a substituted aryl group,
- a group containing one or more silicon atoms,
- a (di)((hydroxy)(Ci- C 6)alkyl)amino group,
- an -O-sugar group, such as -O-glucoside,
- an R-Z-C(X)-Y- group with R representing a hydrogen atom or a
(Ci-C )alkyl group, Y and Z, which may be identical or different,
representing a bond, an oxygen or sulfur atom or an -N(R')- group
with R' representing a hydrogen atom or a (Ci-C )alkyl group, Y
possibly also representing a (Ci-Ce)alkylene group, and X representing
an oxygen or sulfur atom, or N-R" with R" representing a hydrogen
atom or a (Ci-C )alkyl group;
it being understood that at least two adjacent radicals chosen from R1,
R2, R3, R4, R5, R6, R7, R8 and R9 represent a hydroxyl group.
4 . Dyeing process according to any one of the preceding
claims, characterized in that the dihydroxyflavanol derivative(s) is
(are) chosen from:
- dihydroxyflavanols such as catechin and epicatechin gallate,
their oligomers and polymers called proanthocyanidols or condensed
tannins such as theaflavin, theaflavin 3'-0-gallate, theaflavin 3,3'-0-
digallate, and proanthocyanidins Al , A2, Bl , B2, B3 and CI ;
- and mixtures of the preceding compounds.
5. Dyeing process according to any one of Claims 2 to 4,
characterized in that the natural dihydroxyflavanol derivative(s) is
(are) chosen from extracts of animals, of bacteria, of fungi, of algae,
of plants and of fruits.
6 . Dyeing process according to any one of the preceding
claims, characterized in that:
- the manganese salts are chosen from:
i) manganese oxides and
ii) halides, sulfates, phosphates, nitrates and perchlorates,
carboxylic acid salts, such as gluconates, and also mixtures thereof,
and
- the zinc salts are chosen from zinc sulfate, zinc gluconate,
zinc chloride, zinc lactate, zinc acetate, zinc glycinate and zinc
aspartate;
and, more particularly, the salts b) are carboxylic acid salts of
manganese.
7 . Dyeing process according to any one of the preceding
claims, characterized in that the ingredient c) is hydrogen peroxide or
urea hyrogen peroxide.
8. Dyeing process according to any one of the preceding
claims, characterized in that the (bi)carbonate(s) is (are) alkali metal,
alkaline earth metal or ammonium (bi)carbonate(s).
9 . Dyeing process according to any one of the preceding
claims, characterized in that the alkaline agent(s) other than the
bicarbonate(s) is (are) chosen from:
aqueous ammonia,
alkanolamines,
oxyethylenated ethylenediamines,
oxypropylenated ethylenediamines,
inorganic or organic hydroxides,
alkali metal silicates,
amino acids, and
- the compounds of formula (III) below:
in which formula (III):
- W is a divalent (Ci-Cs )alkylene group, preferably a propylene
group, optionally substituted in particular by a hydroxyl group or a Ci-
C4 alkyl radical;
- Ra, Rb, Rc and Rd, which are identical or different, represent
a hydrogen atom or a Ci-C4 alkyl or Ci-C4 hydroxyalkyl radical;
preferably, the alkaline agent(s) e) is (are) chosen from
alkanolamines, in particular monoethanolamine.
10 . Dyeing process according to any one of the preceding
claims, characterized in that:
- the magnesium salts are chosen from magnesium hydroxides,
magnesium halides, magnesium sulfates, magnesium nitrates,
carboxylic acid salts of magnesium, and magnesium phosphates,
- the molybdenum salts are chosen from:
i) binary molybdenum halides of oxidation states (II) to (VI),
hexacoordinated with 6 halogens of Mo(V), (IV) and (III), the
molybdenum atoms being bonded via halogen bonds such as Mo(II)
halide, containing [Mo6Hals] 4+ clusters bonded to halogen atoms to
give Mo Hali 2 with Hal, which are identical or different, representing
a halogen atom, and more particularly Hal represents CI;
ii) molybdenum tetrahalides (Hal') 4Mo with Hal' , which are
identical or different, corresponding to a halogen atom;
iii) molybdenum sulfur derivatives chosen from:
molybdenum disulfides [131 7-33-5], molybdenum(IV)
sulfides, MoS2;
- molybdenum sesquisulfide [1203 3-33-9]; dimolybdenum(III)
trisulfides, M02S3;
iv) molybdenum acetate dimer [1422 1-06-8],
- the calcium salts are chosen from calcium hydroxides,
calcium sulfates, calcium halides, calcium carboxylates, calcium
phosphates, calcium borates and calcium carbonates.
11. Dyeing process according to any one of the preceding
claims, characterized in that it is performed in one step consisting in
applying, to the keratin fibres, an aqueous composition comprising a),
b), c), d), e) and f) as defined according to any one of the preceding
claims.
12. Dyeing process according to any one of Claims 1 to 10,
characterized in that the first step consists in applying to said fibres a
composition comprising the ingredients a), b), c) and f) as defined
according to any one of Claims 1 to 7 and 10, and then, in a second
step, a composition comprising the ingredients d) and e) as defined
according to Claims 8 and 9 is applied to said fibres, it being
understood that at least one of the two compositions is aqueous.
13. Process according to any one of Claims 1 to 10 and 12, in
which the keratin fibres are mechanically wiped and/or dried and/or
rinsed before carrying out the step comprising the application of a
composition comprising the ingredient d) and/or e) as defined
according to any one of Claims 1, 8 or 9 .
14. Cosmetic composition for the dyeing of keratin fibres
containing the compounds a), b), c), d), e) and f) as defined according
to any one of Claims 1 to 10, it being understood that the pH of the
composition is alkaline, i.e. greater than 7, and preferably between 8
and 12.
15. Multicompartment device, characterized in that it comprises
from 2 to 6 compartments containing from 2 to 6 compositions in
which are distributed the ingredients a), b), c), d), e) and f) as defined
according to any one of Claims 1 to 10, said compositions being
aqueous or pulverulent, with at least one of these compositions being
aqueous.
16 . Use of one or more metal salt(s) as defined according to
Claim 10 for improving the chromaticity of keratin fibres, in particular
human keratin fibres such as the hair, coloured using one or more
dihydroxyflavanol derivative(s) as defined according to any one of
Claims 1 to 5.