Hair dyeing process using at least one ortho-diphenol, a manganese
or zinc salt, hydrogen peroxide, (bi)carbonate, an alkaline agent
and a titanium or scandium salt
The present invention relates to a process for dyeing keratin
fibres, in particular human keratin fibres such as the hair, in which the
said fibres are treated using one or more cosmetic compositions
comprising a) one or more ortho-diphenol derivatives, b) one or more
manganese or zinc salts, c) hydrogen peroxide or one or more systems
for generating hydrogen peroxide, d) one or more (bi)carbonates or
one or more systems for generating (bi)carbonate(s), e) one or more
basifying agents other than the (bi)carbonate(s) and f) one or more
salts chosen from titanium salts and scandium salts.
It is known practice to obtain "permanent" colorations with dye
compositions containing oxidation dye precursors, which are generally
known as oxidation bases, such as ortho- or para-phenylenediamines,
ortho- or para-aminophenols and heterocyclic compounds. These
oxidation bases are colourless or weakly coloured compounds, which,
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 with these oxidation bases may be varied by
combining them with couplers or coloration modifiers, the latter being
chosen especially from aromatic meta-diamines, meta-aminophenols,
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 it to diffuse, and then in rinsing the fibres. The
colorations resulting therefrom are permanent, strong and resistant to
external agents, especially to light, bad weather, washing, perspiration
and rubbing.
However, the commercial hair dyes that contain them generally
have the drawback of staining clothing, of leading to odour and
comfort problems, and of degrading keratin fibres. This is particularly
the case with oxidation dyes.
In the field of dyeing, it is also known practice to dye keratin
materials such as the hair or the skin using ortho-diphenols in the
presence of a metal salt especially of manganese (Mn) and/or zinc
(Zn). In particular, patent applications FR 2 814 943, FR 2 814 945,
FR 2 814 946 and FR 2 814 947 propose compositions for dyeing the
skin or keratin fibres, comprising a dye precursor that contains at least
one ortho-diphenol, Mn and/or Zn oxides and salts, alkaline agents of
hydrogen carbonate type in a particular Mn, Zn/hydrogen carbonate
ratio and optionally an enzyme. According to these documents, it is
possible to obtain colorations on keratin materials with atmospheric
oxygen or any oxygen-generating system.
However, the colorations obtained are not strong enough and
are sparingly chromatic, especially in the case of hair fibres.
Moreover, it is known practice to use metals at acidic pH for
dyeing keratin fibres in amounts similar to those employed for dyes
using a mordanting process, which consists in preparing the fibres
before performing the dyeing operation in order to obtain fast shades
(Ullmann's Encyclopaedia "Metal and Dyes", 2005 § 5.1, p . 8).
However, this process generally has the drawback of not
always respecting the cosmeticity of the hair fibre. Furthermore, the
metals used, such as iron, lead to neutral and sparingly chromatic
shades. In general, such metals do not make it possible to obtain
chromatic shades.
There is thus a real need to develop dyeing processes for
obtaining strong, fast and/or chromatic colorations using orthodiphenols,
especially using natural extracts that are rich in orthodiphenols
and less aggressive to keratin fibres. In particular, there is a
need to obtain colorations that satisfactorily withstand external agents
(light, bad weather or shampooing), which are fast and homogeneous,
i.e. showing little coloration selectivity between the root and the end,
while at the same time remaining strong and/or chromatic.
This aim is achieved by the present invention, one subject of
which is a process for dyeing keratin fibres, in particular human
keratin fibres such as the hair, in which the said fibres are treated, in
one or more steps, with one or more cosmetic compositions
containing, taken together or separately in the said composition(s), the
following ingredients:
a) one or more ortho-diphenol derivatives,
b) one or more manganese salts or one or more zinc salts,
c) hydrogen peroxide or one or more systems that generate
hydrogen peroxide,
d) one or more (bi)carbonates or one or more systems that
generate (bi)carbonate(s),
e) one or more basifying agents other than the
(bi)carbonate(s), and
f) one or more salts chosen from titanium salts and scandium
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 that the composition
comprising the salt(s) chosen from titanium salts and scandium salts is
applied to the keratin fibres as a post-treatment, i.e. as the last step of
the dyeing process.
Thus, the keratin fibres are treated at the end of the dyeing
process with a composition comprising the titanium salt(s) or the
scandium salt(s).
In particular, the cosmetic composition comprising one or more
titanium salts or one or more scandium salts is applied to the keratin
fibres as a post-treatment.
According to one particular embodiment of the dyeing process
according to the invention, compound(s) d) and e) are:
- either in a mixture with ingredients a), b) and c),
- - or applied separately after application of a cosmetic
composition comprising compound(s) a), b) and c),
- - or applied together with compound c) after application of a
cosmetic composition comprising ingredients a) and b).
According to one particular embodiment of the dyeing process
of the invention, the salt(s) chosen from titanium salts and scandium
salts are applied separately after application of ingredients a) to e).
A subject of the present invention is also a cosmetic
composition for dyeing keratin fibres, comprising:
a) one or more ortho-diphenol derivatives,
b) one or more manganese salts or one or more zinc salts,
c) hydrogen peroxide or one or more systems that generate
hydrogen peroxide,
d) one or more (bi)carbonates or one or more systems that
generate (bi)carbonate(s),
e) one or more basifying agents other than the
(bi)carbonate(s), and
f) one or more salts chosen from titanium salts and scandium
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 particularly
between 8 and 10.5 .
The dye composition is preferably aqueous.
Another subject of the present invention concerns a mult i
compartment device comprising:
a) one or more ortho-diphenol derivatives,
b) one or more manganese salts or one or more zinc salts,
c) hydrogen peroxide or one or more systems that generate
hydrogen peroxide,
d) one or more (bi)carbonates or one or more systems that
generate (bi)carbonate(s),
e) one or more basifying agents other than the
(bi)carbonate(s), and
f) one or more salts chosen from titanium salts and scandium
salts;
it being understood that the pH of at least one of the
compositions comprising a), b), d), e) and/or f) is alkaline, i.e. greater
than 7, and preferably between 8 and 12. It is particularly between 8
and 10.5 .
The multi-compartment device or "kit" is suitable for
performing the dyeing process according to the invention.
The process according to the invention has the advantage of
dyeing human keratin fibres, with fast and surprisingly chromatic
dyeing results. In particular, the dyeing process according to the
invention leads to colorations that are resistant to washing,
perspiration, sebum and light, without impairing the fibres.
Furthermore, the dyeing process performed induces satisfactory
"build-up" of the coloration.
Thus, another subject of the invention is the use of one or more
titanium salts for improving the chromaticity and/or colour build-up of
keratin fibres, in particular of human keratin fibres such as the hair,
dyed with one or more ortho-diphenol derivatives.
Other subjects, characteristics, aspects and advantages of the
invention will emerge even more clearly on reading the description
and the examples that follow.
a) ortho-Diphenol derivative
In accordance with the present invention, the dyeing process
uses one or more ortho-diphenol derivatives.
The ortho-diphenol derivative(s) may be present in one or more
cosmetic compositions used in the course of the dyeing process.
One particular embodiment of the invention concerns orthodiphenol
derivatives or mixtures of compounds comprising one or
more aromatic rings, preferably a benzene ring, comprising at least
two hydroxyl groups (OH) borne by two adjacent carbon atoms of the
aromatic ring. Particularly, the ortho-diphenol derivative(s) according
to the invention are not self-oxidizable derivatives bearing an indole
unit. More particularly, they are not 5,6-dihydroxyindole.
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
isoquinoline, the said aromatic ring comprising at least two hydroxyl
groups borne by two adjacent carbon atoms of the aromatic ring.
Preferentially, the aromatic ring of the ortho-diphenol derivatives
according to the invention is a benzene ring.
The term "fused ring" means that at least two saturated or
unsaturated, heterocyclic or non-heterocyclic rings have a common
bond, i.e. at least one ring is fused to another ring.
The ortho-diphenols according to the invention may or may not
be salified. They may also be in aglycone form (without attached
sugar) or in the form of glycosylated compounds.
More particularly, the ortho-diphenol derivative a) represents a
compound of formula (I), or an oligomer thereof, in salified or nonsalified
form:
in which formula (I) the substituents:
• Ri to P 4 , which may be identical or different, represent:
a hydrogen atom;
a halogen atom,
a hydroxyl radical,
- a carboxyl radical,
an alkyl carboxylate or alkoxycarbonyl radical,
an optionally substituted amino radical,
an optionally substituted linear or branched alkyl radical,
an optionally substituted linear or branched alkenyl radical,
an optionally substituted cycloalkyl radical,
an alkoxy radical,
an alkoxyalkyl radical,
an alkoxyaryl radical, the aryl group possibly being optionally
substituted,
an aryl radical,
a substituted aryl radical,
a saturated or unsaturated heterocyclic radical, optionally
bearing a cationic or anionic charge, optionally substituted
and/or optionally fused with an aromatic ring, preferably a
benzene ring, the said aromatic ring being optionally
substituted particularly with one or more hydroxyl or
glycosyloxy groups,
a radical containing one or more silicon atoms,
• in which two of the substituents borne by two adjacent
carbon atoms Ri - R2, R2 - R3 or R3 - R4 form, together with the
carbon atoms that bear 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, Ri to R4
together form from one to four rings.
One particular embodiment of the invention concerns orthodiphenol
derivatives of formula (I), of which two adjacent substituents
Ri - R2, R2 - R3 or R3 - R4 cannot form with the carbon atoms that bear
them a pyrrolyl radical. More particularly, R2 and R 3 cannot form a
pyrrolyl radical fused to the benzene ring bearing the two hydroxyl
groups.
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 linear or branched, saturated
hydrocarbon-based radicals, generally of C1-C20 , particularly of CiCio,
preferably Ci -C alkyl radicals, such as methyl, ethyl, propyl,
butyl, pentyl and hexyl.
The alkenyl radicals are linear or branched, unsaturated C2-C20
hydrocarbon-based radicals; preferably comprising at least one double
bond, such as ethylene, propylene, butylene, pentylene, 2-
methylpropylene and decylene.
The aryl radicals are fused or nonfused monocyclic or
polycyclic carbon-based radicals, preferentially comprising from 6 to
30 carbon atoms, and of which at least one ring is aromatic; the aryl
radical is preferentially chosen from phenyl, biphenyl, naphthyl,
indenyl, anthracenyl and tetrahydronaphthyl.
The alkoxy radicals are alkyl-oxy radicals with alkyl as
defined previously, preferably of C1-C10 such as methoxy, ethoxy,
propoxy and butoxy.
The alkoxyalkyl radicals are preferably (Ci -C2o)alkoxy( Ci -
C2o)alkyl radicals, such as methoxymethyl, ethoxymethyl,
methoxyethyl, ethoxyethyl, etc.
The cycloalkyl radicals are generally C4- C cycloalkyl
radicals, preferably cyclopentyl and cyclohexyl radicals. The
cycloalkyl radicals may be substituted cycloalkyl radicals, in
particular substituted with alkyl, alkoxy, carboxylic acid, hydroxyl,
amine and ketone groups.
The alkyl or alkenyl radicals, when they are optionally
substituted, may be substituted with at least one substituent borne by
at least one carbon atom, chosen from:
- a halogen atom;
- a hydroxyl group;
- a Ci -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 with a (Ci -C4)alkyl
radical, preferentially methyl;
- an amino radical substituted with one or two identical or
different C -C alkyl radicals, optionally bearing at least:
* one hydroxyl group,
* one amino group optionally substituted with one or two
optionally substituted C1-C 3 alkyl radicals, the said alkyl radicals
possibly forming with the nitrogen atom to which they are attached a
saturated or unsaturated, optionally substituted 5- to 7-membered
heterocycle, optionally comprising 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 organic or mineral acid or of the corresponding
halide;
* or an optionally cationic 5- or 6-membered heteroaryl
radical, preferentially imidazolium, optionally substituted with a (C -
C4)alkyl radical, preferentially methyl;
- an acylamino radical (-NR-COR') in which the radical R is a
hydrogen atom, a C1-C4 alkyl radical optionally bearing at least one
hydroxyl group and the radical R' is a C1-C2 alkyl radical; a
carbamoyl radical ((R) 2N-CO-) in which the radicals R, which may be
identical or different, represent a hydrogen atom, a C1-C4 alkyl radical
optionally bearing at least one hydroxyl group; an alkylsulfonylamino
radical (R' S0 2-NR-) in which the radical R represents a hydrogen
atom, a C1-C4 alkyl radical optionally bearing at least one hydroxyl
group and the radical R' represents a C1-C4 alkyl radical or a phenyl
radical; an aminosulfonyl radical ((R) 2N-S02-) in which the radicals
R, which may be identical or different, represent a hydrogen atom or a
C1-C4 alkyl radical optionally bearing 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 with one or
more hydroxyl groups;
- a glycosyloxy group; and
- a phenyl group optionally substituted with one or more
hydroxyl groups.
The aryl or heterocyclic radicals or the aryl or heterocyclic
part of the radicals, when they are optionally substituted, may be
substituted with at least one substituent borne by at least one carbon
atom, chosen from:
- a Ci -Cio and preferably Ci -C alkyl radical optionally
substituted with one or more radicals chosen from hydroxyl, Ci -C2
alkoxy, C2 -C4 (poly)hydroxyalkoxy, acylamino, amino substituted
with two Ci -C4 alkyl radicals, which may be identical or different,
optionally bearing at least one hydroxyl group, or the two radicals
possibly forming, with the nitrogen atom to which they are attached, a
saturated or unsaturated, optionally substituted 5- to 7-membered and
preferably 5- or 6-membered heterocycle optionally comprising
another heteroatom identical to or different from nitrogen;
- a halogen atom;
- a hydroxyl group;
- a Ci -C2 alkoxy radical;
- a Ci -Cio 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 with a (Ci -C4)alkyl
radical, preferentially methyl;
- an amino radical substituted with one or two identical or
different Ci -C alkyl radicals, optionally bearing at least:
* one hydroxyl group,
* one amino group optionally substituted with one or two
optionally substituted C1- C 3 alkyl radicals, the said alkyl radicals
possibly forming with the nitrogen atom to which they are attached a
saturated or unsaturated, optionally substituted 5- to 7-membered
heterocycle, optionally comprising 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- C 4 alkyl group; and M represents the
counterion of the organic or mineral acid or of the corresponding
halide;
* or an optionally cationic 5- or 6-membered heteroaryl
radical, preferentially imidazolium, optionally substituted with a (Ci-
C4)alkyl radical, preferentially methyl;
- an acylamino radical (-NR-COR') in which the radical R is a
hydrogen atom, a C1-C4 alkyl radical optionally bearing at least one
hydroxyl group and the radical R' is a C1-C2 alkyl radical; a
carbamoyl radical ((R) 2N-CO-) in which the radicals R, which may be
identical or different, represent a hydrogen atom, a C1-C4 alkyl radical
optionally bearing at least one hydroxyl group; an alkylsulfonylamino
radical (R' S0 2-NR-) in which the radical R represents a hydrogen
atom, a C1-C4 alkyl radical optionally bearing at least one hydroxyl
group and the radical R' represents a C1-C4 alkyl radical or a phenyl
radical; an aminosulfonyl radical ((R) 2N-S0 2-) in which the radicals
R, which may be identical or different, represent a hydrogen atom or a
C1-C4 alkyl radical optionally bearing at least one hydroxyl group;
- a carboxylic radical in acid or salified form (preferably with
an alkali metal or a substituted or unsubstituted ammonium);
- a cyano group;
- a nitro group;
- a polyhaloalkyl group, preferentially trifluoromethyl;
- a carboxyl or glycosylcarbonyl group;
- a phenylcarbonyloxy group optionally substituted with one or
more hydroxyl groups;
- a glycosyloxy group; and
- a phenyl group optionally substituted with one or more
hydroxyl groups.
For the purposes of the present invention, the term "glycosyl
radical" means a radical derived from a monosaccharide or
polysaccharide.
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 especially with 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 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 with one or more OH groups.
The ortho-diphenols that are useful in the process of the
invention may be natural or synthetic. Among the natural orthodiphenols
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 mineral or organic. Preferably, the acid is
hydrochloric acid, which results in chlorides.
The bases may be mineral or organic. In particular, the bases
are alkali metal hydroxides such as sodium hydroxide, which leads to
sodium salts.
According to one particular embodiment of the invention, the
composition comprises as ingredient a) one or more synthetic orthodiphenol
derivatives that do not exist in nature.
According to another preferred embodiment of the invention,
the composition that is useful in the process for dyeing keratin fibres
comprises as ingredient a) one or more natural ortho-diphenol
derivatives.
More particularly, the ortho-diphenols that may be used in the
process of the invention according to a) are in particular:
- flavanols, for instance catechin and epicatechin gallate,
- flavonols, such as quercetin,
- anthocyanidins, for instance cyanidin, delphinidin and
petunidin,
- anthocyanins or anthocyans, for instance myrtillin,
- ortho-hydroxybenzoates, for example gallic acid salts,
- flavones, such as luteolin,
- hydroxystilbenes, for example tetrahydroxy-3,3', 4,5'-
stilbene, 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 ,
- proathocyanins,
- tannic acid,
- ellagic acid,
- and mixtures of the preceding compounds,
particularly catechin, quercetin, braziline, hematin,
hematoxylin, chlorogenic acid, caffeic acid, gallic acid, catechol,
gallic acid, L-DOPA, pelargonidin, cyanidin, (-)-epicatechin, (-)-
epigallocatechin, (-)-epigallocatechin 3-gallate (EGCG), (+)-catechin,
isoquercetin, pomiferin, esculetin, 6,7-dihydroxy-3-(3-hydroxy-2,4-
dimethoxyphenyl)coumarin, santalin AC, mangiferin, butein,
maritimetin, sulfuretin, robtein, betanidin, pericampylinone A,
theaflavin, proanthocyanidin A2, proanthocyanidin B2,
proanthocyanidin CI , procyanidins DP 4-8, tannic acid, purpurogallin,
5,6-dihydroxy-2-methyl- l ,4-naphthoquinone, alizarin, wedelo lactone,
variegatic acid, gomphidic acid, xerocomic acid, carnosol, and natural
extracts containing them.
The term "carboxylate" means a carboxylic acid salt.
The term "carboxylic acid" means a compound comprising at
least one carboxylic acid group-C(0)-OH, 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 being an integer between 1 and 4 inclusively
and preferably between 1 and 2, het representing a heterocyclic group
such as pyrrolidone, the alkyl or het group possibly being optionally
substituted with one or more groups, chosen especially from OH and
(di)(Ci-C 6)(alkyl)amino.
When the dye precursors have D and L forms, the two forms
may be used in the compositions according to the invention, as may
the racemic mixtures.
Preferentially, the ortho-diphenol(s) according to the invention
are chosen from flavanols, flavonols, ortho-hydroxybenzoates,
isoflavones and neoflavones.
According to one embodiment, the natural ortho-diphenols are
derived from extracts of animals, bacteria, fungi, algae, plants and
fruit, used in their entirety or partially. In particular concerning
plants, the extracts are obtained from fruit including citrus fruit,
legumes, trees and 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
assimilated as compound a).
The extracts are obtained by extraction of various plant parts,
for instance the root, the wood, the bark, the leaf, the flower, the fruit,
the seed, the clove 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 legume 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 and extracts of campeachy wood;
Mixtures of plant extracts may also be used.
According to one particular embodiment of the invention, the
ortho-diphenol derivative(s) are natural extracts, rich in orthodiphenols.
According to one preferred mode, the ortho-diphenol
derivative(s) are solely natural extracts.
Preferentially, the ortho-diphenol(s) according to the invention
are chosen from catechin, quercetin, haematin, haematoxylin, brasilin,
gallic acid, and natural extracts containing them chosen from grape
marc, pine bark, green tea, onion, cocoa bean, logwood, redwood and
gall nut.
Even more preferentially, the ortho-diphenol(s) used in one or
more compositions according to the invention are chosen from
catechin, 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, synthetic orthodiphenol
derivative(s), and/or the natural extract(s) used as ingredient
a) in one or more cosmetic compositions that are useful in the process
according to the invention preferably represent from 0.00 1% to 20%
by weight relative to 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 in the course of the dyeing process.
For the purposes of the present invention, the term "salts"
means the oxides of these metals and salts per se derived especially
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 polymeric salts, and also
mixtures thereof.
More particularly, manganese salt is other than manganese
carbonate, manganese hydrogen carbonate or manganese dihydrogen
carbonate.
The carboxylic acid salts that may be used in the invention also
include salts of hydroxylated carboxylic acids such as gluconate.
As examples of polymeric 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
spring 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 FR 2 814 943).
According to one preferred embodiment of the invention, the
manganese or zinc salt(s) used represent from 0.00 1% to 0 .1% by
weight approximately relative to the total weight of the composition(s)
containing the said metal salt(s), and even more preferentially from
0 .05% to 10%o by weight approximately.
Particularly, the metal salts of the invention are in oxidation
state 2, such as Mn (II) and Zn (II).
Preferably, the dyeing process of the invention uses a cosmetic
composition comprising one or more manganese salts, in particular
Mn(II) metal salts.
Even more preferentially, the manganese salt(s) are chosen
from manganese carboxylic acid salts, especially manganese
gluconate, and manganese halides such as manganese chloride; and
more particularly manganese gluconate.
c) Hydrogen peroxide or system that generates hydrogen
peroxide
In the context of the present invention, the third constituent is
hydrogen peroxide or a system that generates hydrogen peroxide, such
as:
a) urea peroxide;
b) polymeric complexes that can release hydrogen peroxide, such
as polyvinylpyrrolidone/H 20 in particular in the form of
powders, and the other polymeric complexes described in US 5
008 093; US 3 376 110; 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 one preferred embodiment of the invention, the
composition contains one or more systems that generate hydrogen
peroxide, chosen from a) urea peroxide, b) polymeric complexes that
can release hydrogen peroxide, chosen from
polyvinylpyrrolidone/H 202; c) oxidases; e) perborates and f)
percarbonates.
Particularly, 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 dye compositions and as defined
hereinbelow.
According to one particular mode of the invention, the
hydrogen peroxide used or the system(s) used that generate hydrogen
peroxide preferably represent from 0.00 1% to 12% by weight of
hydrogen peroxide relative to the total weight of the composition(s)
containing them, and even more preferentially from 0.2% to 2.7% by
weight.
d) (Bi)carbonate(s) or system that generates (bi)carbonate(s)
In accordance with the present invention, the dyeing process
uses one or more (bi)carbonates or one or more systems that generate
(bi)carbonates.
For the purposes of the present invention, the term "system
that generates (bi)carbonate" means a system that generates
(bi)carbonate in situ, for instance carbon dioxide in water or by
buffering carbonate with a mineral or organic acid.
The (bi)carbonates or the system(s) that generate
(bi)carbonates may be employed in one or more cosmetic compositions
in the course of the dyeing process.
The (bi)carbonate(s) are chosen from:
a) carbonates of alkali metals (Met2
+, C0 3 ) , of alkaline-earth
metals (Met' +, C0 3 ) of ammonium ((R" 4N+)2,C0 3 ) or of
phosphonium ((R" 4P+)2,C0 3 with Met' representing an alkalineearth
metal and Met representing an alkali metal, and R" , which may
be identical or different, represent a hydrogen atom, an optionally
substituted group (Ci-C )alkyl such as hydroxyethyl),
b) bicarbonates, also known as hydrogen carbonates, 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 may be identical or different,
represent a hydrogen atom, an optionally substituted group
(Ci-C )alkyl such as hydroxyethyl and, when R' represents a
hydrogen atom, the hydrogen carbonate is then known as a
dihydrogen carbonate (C0 2, H20); and
Met' + (HC0 3 )2 with Met' representing an alkaline-earth
metal.
More particularly, the (bi)carbonate(s) 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
hydrogen carbonates and mixtures thereof, and in particular sodium
hydrogen carbonate. These hydrogen carbonates 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 FR 2 814
943). Particularly, mention may be made of sodium carbonate [497- 19-
8] = Na2C0 3, sodium hydrogen carbonate or sodium bicarbonate [144-
55-8] = NaHCC"3 , and sodium dihydrogen carbonate = Na(HCC"3 ) 2 .
According to the invention, the (bi)carbonate(s) used
preferably represent from 0.00 1% to 10% by weight relative to the
total weight of composition(s) containing the (bi)carbonate(s), and
even more preferentially from 0.005% to 5% by weight.
Preferably, the (bi)carbonate used in the composition during
the dyeing process is ammonium (bi)carbonate or sodium bicarbonate.
e) Basifying agents other than the (bi)carbonate(s)
The basifying agent used in the dyeing process according to the
invention as fifth ingredient is other than the (bi)carbonate(s) iv) as
defined previously. This is an agent for increasing the pH of the
composition(s) in which it is present. The basifying agent is a
Bronsted, Lowry or Lewis base. It may be mineral or organic.
Particularly, the 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) mineral or organic hydroxides,
v) alkali metal silicates such as sodium metasilicate, vi), amino acids,
preferably basic amino acids such as arginine, lysine, ornithine,
citrulline and histidine, and vii) the compounds of formula (II) below:
c R d ( )
in which:
W is a divalent ( C i - C )alkylene group, preferably propylene
optionally substituted especially with a hydroxyl group or a
C 1- C 4 alkyl radical;
Ra, Rb, Rc and Rd, which may be identical for different,
represent a hydrogen atom or a C 1- C 4 alkyl or C 1- C 4
hydroxyalkyl radical.
The mineral 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, iv) hydroxides of lanthanides or actinides,
quaternary ammonium hydroxides and guanidinium hydroxide.
Preferentially, whether it is for the composition according to
the invention or the process used in the invention, the basifying agent
is not sodium hydroxide NaOH. More generally and preferentially,
whether it is for the composition according to the invention or the
process used in the invention, the basifying 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 basifying agent(s) d) as defined previously preferably
represent from 0.00 1% to 10% by weight relative to the weight of the
composition(s) containing them, and more particularly from 0.005% to
8 %) by weight of the composition.
Preferably, the alkaline agent(s) are chosen from
alkanolamines, in particular monoethanolamine.
G) Salts
According to one preferred embodiment, the ingredient f) used
in accordance with the present invention is a titanium salt.
- Titanium salts:
For the purposes of the present invention, the term "titanium
salt" means the oxides of this metal and salts per se derived especially
from the action of an acid on a metal.
According to one particular embodiment of the invention, the
titanium derivative(s) are chosen from:
i) titanium salts of oxidation state 4 such as potassium titanium
oxalate dihydrate K2TiO(C204)2 -2H20 , Ti(S0 4)2,
ii) titanium oxides chosen especially from titanium oxides and
salts thereof, hydrates thereof and supported forms thereof,
iii) titanium complexes such as the phthalocyanins described,
for example, in document US 3 93 1 249.
Among the titanium oxides, examples that may be mentioned
include the titanium oxides and hydroxides described in Ullhamnn
encyclopedia "Titanium, Titanium Alloys and Titanium Compounds",
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim,
10 .1002/14356007. a27 095, pp. 1-33 . More particularly, the metal
derivative(s) are titanium (Ti) and are chosen from titanium (III)
hydroxide and oxide Ti(OH)3 and Ti0 3, dititanium trioxide Ti20 3,
alkaline-earth metal titanium trioxides, alkaline-earth metal titanium
pentoxides, the titanates of general formula MIITi0 4 in which Mil
represents a metal Mg, Zn, Mn or Co, peroxytitanic acid and the
peroxytitanates H4T1O5, titanium (II) dioxide Ti0 2, titanium disulfide
TiS2.
The titanium oxides may also originate from minerals such as
anatase and rutile that contain Ti0 2; perovskite containing calcium
trioxide CaTi0 3, sphene or titanite containing CaTi(Si0 4)0.
Preferentially, the titanium salts are chosen from salts of
titanium of oxidation state 4 such as potassium titanium oxalate
dihydrate K2TiO(C20 4) 2-2H20 .
According to another preferred embodiment, the ingredient f)
in accordance with the present invention is a scandium salt.
- Scandium salts:
For the purposes of the present invention, the term "scandium
salt" means the oxides of this metal and salts per se derived especially
from the action of an acid on a metal.
Preferably, the scandium salts are not oxides.
Among the scandium salts, mention may be made of hydroxide,
halides such as the chloride, sulfate, nitrate, carboxylic acid salts such
as acetate and gluconate, and sulfonic acid salts, in particular
(poly)halo(Ci- C 6)alkylsulfonates such as trifluoromethanesulfonate.
By way of example, mention may be made of scandium
hydroxide, scandium chloride, scandium sulfate, scandium nitrate,
anhydrous or hydrated scandium acetate, and scandium
trifluoromethanesulfonate.
Preferably, the scandium salt used in the dyeing process is
anhydrous or hydrated scandium acetate.
In one preferred embodiment of the invention, the amount in
moles of titanium or scandium salts used in the process or in the
composition is equivalent in moles to that of the dyes.
The titanium or scandium salt(s) 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) containing them.
Preferentially, the titanium or scandium salts according to the
invention are soluble in water to a proportion of at least 0.000 1 g/L.
The titanium or scandium salts may be introduced in solid form
into the compositions or may be derived from a natural, mineral or
spring 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 FR 2 814 943).
- Water:
According to one 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 comes from at least one 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 dye 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
C 1- C 4 lower alcohols, such as ethanol and isopropanol; polyols and
polyol ethers such as 2-butoxyethanol, propylene glycol, propylene
glycol monomethyl ether, diethylene glycol monoethyl ether and
monomethyl ether, 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 dye composition.
- Adjuvants :
The composition(s) of the dyeing process in accordance with
the invention may also contain various adjuvants conventionally used
in hair dye compositions, such as anionic, cationic, nonionic,
amphoteric or zwitterionic surfactants or mixtures thereof, anionic,
cationic, nonionic, amphoteric or zwitterionic polymers or mixtures
thereof, mineral or organic thickeners, and in particular anionic,
cationic, nonionic and amphoteric polymeric associative thickeners,
antioxidants, penetrants, sequestrants, fragrances, buffers, dispersants,
conditioning agents, for instance volatile or non-volatile, modified or
unmodified silicones, film-forming agents, ceramides, preserving
agents and opacifiers.
The said adjuvants are preferably chosen from surfactants such
as anionic or nonionic surfactants or mixtures thereof and mineral 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, a person skilled in the art will take care to
select this or these additional compound(s) such that the advantageous
properties intrinsically associated with the composition(s) that are
useful in the dyeing process in accordance with the invention are not,
or are not substantially, adversely affected by the envisaged
addition(s).
- Additional dyes :
The dyeing process using ingredients a) to f) as defined
previously 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, phthalocyanin 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 henna-based poultices or extracts, may also be used.
According to the invention, the direct dye(s) used in the
composition according to the invention which comprises ingredients a)
to f) as defined previously, or the composition(s) of the dyeing
process according to the invention, preferably represent from 0.00 1%
to 10% by weight approximately and even more preferentially from
0.05% to 5% by weight approximately relative to the total weight of
the composition(s).
The composition according to the invention or the
composition(s) of the process using ingredients a) to f) as defined
previously may also comprise one or more oxidation bases and/or one
or more couplers conventionally used for the dyeing of 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-based couplers and heterocyclic couplers, and the
addition salts thereof.
The said base(s) present in the said composition(s) used in the
process are each generally present in an amount of between 0.00 1%
and 10% by weight relative to the total weight of the composition(s)
containing them.
The cosmetic composition(s) of the invention may be in
various galenical 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 bottle 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,
preferably between 8 and 12 and more preferably between 8 and 10 .
In other words, at least one of the cosmetic compositions used
in 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 systems that generate (bi)carbonate(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 system(s) that
generate(s) (bi)carbonate(s) are used in a single cosmetic composition
and the pH of the said composition is alkaline, i.e. greater than 7,
preferably between 8 and 12 and more particularly between 8 and 10 .
According to one particular embodiment, the pH of the
cosmetic composition(s) comprising d) one or more (bi)carbonate(s) or
one or more systems that generate (bi)carbonate(s) and e) one or more
basifying agents 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
system(s) that generate(s) (bi)carbonate(s) d) and the basifying
agent(s) other than the (bi)carbonate(s) e) are used in a single
cosmetic composition and the pH of the said composition is alkaline,
i.e. greater than 7, preferably between 8 and 12, more particularly
between 8 and 10 and especially between 9 and 10 .
Even more preferentially, the (bi)carbonate(s) chosen from
ammonium bicarbonates and the basifying agents chosen from
alkanolamines are used in a single cosmetic composition and the pH of
the said composition is alkaline, i.e. greater than 7, preferably
between 8 and 12, more particularly between 8 and 10 and especially
between 9 and 10 .
According to one embodiment, if one or more cosmetic
compositions used in the dyeing process do not contain (bi)carbonates,
the pH of the composition(s) containing hydrogen peroxide or a
system that generates hydrogen peroxide is preferably less than 7 and
more particularly between 1 and 5.
Preferably, the composition(s) containing the ortho-diphenol(s)
and not containing any (bi)carbonates have a pH of less than 7 and
preferably between 3 and 6.5 .
According to one particular embodiment of the invention, the
cosmetic composition(s) containing the manganese or zinc salt(s) b)
and not containing any (bi)carbonates have a pH of less than 7 and
preferably between 3 and 6.5 .
According to one particular embodiment of the invention, the
cosmetic composition(s) containing the titanium salt(s) or the
scandium salts f) and not containing any (bi)carbonates have a pH of
less than 7 and preferably between 3 and 6.5 .
The pH of these compositions may be adjusted to the desired
value by means of basifying agents as defined previously in d) or by
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 mineral or organic
acids, for instance hydrochloric acid, orthophosphoric acid or sulfuric
acid, carboxylic acids, for instance acetic acid, tartaric acid, citric
acid and lactic acid, and sulfonic acids.
Among the basifying agents, they are agents as defined
previously under the heading "d) basifying agent(s) ".
- Dyeing process in one or more 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 dye composition comprising:
a) one or more ortho-diphenol derivatives,
b) one or more manganese salts or one or more zinc salts,
c) hydrogen peroxide or one or more systems that generate
hydrogen peroxide,
d) one or more (bi)carbonates or one or more systems that
generate (bi)carbonate(s),
e) one or more basifying agents other than the
(bi)carbonate(s), and
f) one or more salts chosen from titanium salts and scandium
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 dye composition comprising
the ingredients a), b), c), d), e) and f) has an alkaline pH, i.e. 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 or three steps.
According to one particular embodiment of the invention, the
process for dyeing keratin fibres is performed in two steps by applying
to the keratin fibres a dye composition comprising the ingredients a),
b), c), d) and e) as defined previously, and then, in a second step, a
composition comprising the ingredients f) as defined previously is
applied to the said keratin fibres, it being understood that at least one
of the two compositions is aqueous. Preferably, the composition
comprising the ortho-diphenol derivative(s) is aqueous. Even more
preferentially, the two compositions used in this embodiment are
aqueous.
For this process, 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 comprising
ingredient f) in 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.
According to another embodiment, the process for dyeing
keratin fibres is performed in three steps.
In a first variant of the three-step process, the first step
consists in applying to the said keratin fibres a composition
comprising ingredients a), b) and c) as defined previously, and then,
in a second step, a composition comprising ingredients d) and e) as
defined previously is applied to the said fibres, and then, in a third
step, a composition comprising ingredient f) is applied to the said
fibres, it being understood that at least one of the three compositions
is aqueous. Preferably, the composition comprising the ortho-diphenol
derivative(s) is aqueous. Even more preferentially, the three
compositions used in this embodiment are aqueous.
In a second variant of the three-step process, the first step
consists in applying to the said keratin fibres a composition
comprising ingredients a) and b) as defined previously, and then, in a
second step, a composition comprising ingredients c), d) and e) as
defined previously is applied to the said fibres, and then, in a third
step, a composition comprising ingredient f) is applied to the said
fibres, it being understood that at least one of the three compositions
is aqueous.
For these last 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 in 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. The application time of the
composition used in the third step is generally set at between 3 and
120 minutes, preferentially between 3 and 60 minutes and more
preferentially between 5 and 30 minutes.
According to one embodiment, the process for dyeing keratin
fibres is performed in one or more steps by applying to the keratin
fibres one or more cosmetic compositions comprising:
a) one or more ortho-diphenol derivatives, especially those
chosen from catechin, quercetin, haematoxylin and gallic acid,
b) one or more manganese salts chosen from carboxylic acid
salts of manganese, in particular manganese gluconate,
c) hydrogen peroxide,
d) one or more (bi)carbonates, especially ammonium
bicarbonates,
e) one or more basifying agents chosen from alkanolamines,
f) one or more titanium salts, in particular salts of titanium of
oxidation state 4 such as potassium titanium oxalate dihydrate
K2TiO(C20 4) 2-2H20 , or one or more scandium salts, in particular
carboxylic acid salts of scandium, especially anhydrous or hydrated
scandium acetate;
it being understood that the composition comprising ingredient
d) has an alkaline pH, i.e. greater than 7, in particular between 8 and
10, and that the composition comprising the salts chosen from
titanium salts and scandium salts is applied to the keratin fibres in the
last step of the dyeing process.
Preferably, the process for dyeing keratin fibres is performed
in three steps.
In particular, the dyeing process is performed in three steps by
applying to the keratin fibres:
i) a cosmetic composition comprising a) one or more orthodiphenol
derivatives, b) one or more manganese solvents chosen from
carboxylic acid salts of manganese, and c) hydrogen peroxide,
ii) a cosmetic composition comprising d) one or more
(bi)carbonates chosen from ammonium bicarbonates and e) one or
more basifying agents chosen from alkanolamines,
iii) a cosmetic composition comprising f) one or more titanium
salts, in particular salts of titanium of oxidation state 4 such as
potassium titanium oxalate dihydrate K2TiO (C204)2-2H20 , or one or
more scandium salts, in particular carboxylic acid salts of scandium,
especially anhydrous or hydrated scandium acetate,
it being understood that the composition comprising
ingredients d) and e) has an alkaline pH, i.e. greater than 7, in
particular between 8 and 10, and that the composition comprising the
salts chosen from titanium salts and scandium salts is applied to the
keratin fibres in the last step of the dyeing process.
More particularly, the ortho-diphenol(s) used in composition i)
may be chosen from catechin, quercetin, haematin, haematoxylin,
brasilin, gallic acid, and natural extracts containing them chosen from
grape marc, pine bark, green tea, onion, cocoa bean, logwood,
redwood and gall nut. Even more particularly, the ortho-diphenol(s)
are chosen from catechin, quercetin, haematoxylin and gallic acid.
Irrespective of the application method, the application
temperature is generally between room 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 mode of application, mechanical wiping
and/or drying of the keratin fibres may optionally be performed
between each step, especially before performing the step comprising
the application of a composition comprising ingredient d) and/or e),
especially before performing the final step comprising the application
of a composition containing the titanium salt(s) or the scandium salts
f).
The steps of intermediate mechanical wiping and drying are
also known as "controlled non-rinsing" to distinguish from "standard
abundant rinsing with water" and "non-rinsing" . The term "mechanical
wiping of the fibres" means rubbing an absorbent article on the fibres
and 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 a towel, particularly a terry
towel, a cloth or absorbent paper such as household roll towel.
According to one 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-straightening iron, an
infrared ray dispenser or other standard heating appliances.
One particular mode of the invention concerns a dyeing process
that is performed at room temperature (25°C).
In all the particular embodiments and variants of the processes
described previously, the compositions mentioned are ready-to-use
compositions that may result from the extemporaneous mixing of two
or more than two compositions and especially of compositions present
in dyeing kits.
- Dyeing device or "kit"
Another subject 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 ortho-diphenol derivatives,
b) one or more manganese salts or one or more zinc salts, c) hydrogen
peroxide or one or more systems that generate hydrogen peroxide, d)
one or more (bi)carbonates or one or more systems that generate
(bi)carbonate(s), e) one or more basifying agents other than the
(bi)carbonate(s) and f) one or more salts chosen from titanium salts
and scandium salts, the said compositions possibly being aqueous or
pulverulent, with, particularly, at least one of the 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 sixth compartment containing an aqueous composition such as
water. In this case, the compound(s) c) are hydrogen peroxide
precursors.
Another variant concerns a six-compartment kit, at least one of
which contains an aqueous composition, and in which the other
compartments 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
ortho-diphenol derivatives, a second compartment comprising b) one
or more manganese salts or one or more zinc salts, a third
compartment comprising c) hydrogen peroxide or one or more systems
that generate hydrogen peroxide, a fourth compartment containing d)
one or more (bi)carbonates or one or more systems that generate
(bi)carbonate(s), a fifth compartment containing e) one or more
basifying agents other than the (bi)carbonate(s), and a sixth
compartment containing f) one or more salts chosen from titanium
salts and scandium salts. Preferably, at least one of these compositions
is aqueous.
Another preferred embodiment concerns a device comprising
four compartments:
(i) a first compartment contains a composition containing:
a) one or more ortho-diphenol derivatives; and
(ii) a second compartment contains a composition containing:
b) one or more manganese salts or one or more zinc salts,
c) hydrogen peroxide or one or more systems that
generate hydrogen peroxide,
iv) a third compartment contains a composition containing:
d) one or more (bi)carbonates or one or more systems that
generate (bi)carbonate(s), and
e) one or more basifying agents other than the
(bi)carbonate(s),
(iii) a fourth compartment contains a composition containing:
f) one or more salts chosen from titanium salts and
scandium salts.
In this other embodiment, at least one of the four compositions
is aqueous and the ortho-diphenol 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 ortho-diphenol
derivatives and b) one or more manganese salts or one or more zinc
salts, the second ii) containing a composition comprising c) hydrogen
peroxide or a system that generates hydrogen peroxide, and the third
iii) containing a composition comprising d) the (bi)carbonate and e)
the basifying agent other than the (bi)carbonate, and the fourth iv)
containing a composition comprising f) one or more salts chosen from
titanium salts and scandium salts. In this other kit, at least one of the
compositions is preferentially aqueous. More particularly, this
composition contains hydrogen peroxide.
According to one particular embodiment of the invention, the
kit comprises three compartments: a first compartment comprising a
composition containing a) one or more ortho-diphenol derivatives, b)
one or more manganese salts or one or more zinc salts, c) hydrogen
peroxide or one or more systems that generate hydrogen peroxide, a
second compartment containing d) one or more (bi)carbonates and e)
one or more basifying agents other than the (bi)carbonate(s), and a
third compartment containing f) one or more salts chosen from
titanium salts and scandium salts.
Among the three-compartment kits, it is also possible to have
kits that contain, in a first compartment, a composition comprising
compounds 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.
As indicated previously, a subject of the present invention is
also a cosmetic composition for dyeing keratin fibres, comprising
ingredients a), b), c), d), e) and f), it being understood that the pH of
the composition is alkaline, i.e. greater than 7 and preferably between
8 and 12. It is particularly between 8 and 10.5 .
A subject of the invention is also the use of the said cosmetic
dye composition for dyeing keratin fibres.
The present invention also relates to the use of one or more
salts chosen from titanium salts and scandium salts as defined
previously, for improving the chromaticity of the colour of keratin
fibres, in particular human keratin fibres such as the hair, dyed with
one or more ortho-diphenol derivatives as defined previously.
Indeed, the present invention deals with the use of one or more
titanium salts as defined previously, for improving the chromaticity of
the colour of keratin fibres, in particular human keratin fibres such as
the hair, dyed with one or more ortho-diphenol derivatives as defined
previously.
The present invention also deals with the use of one or more
scandium salts as defined previously, for improving the chromaticity
of the colour of keratin fibres, in particular human keratin fibres such
as the hair, dyed with one or more ortho-diphenol derivatives as
defined previously.
In particular, the invention relates to the use of one or more
salts chosen from titanium salts and scandium salts in a dye
composition comprising one or more ortho-diphenol derivatives, for
improving the chromaticity of the colour of keratin fibres.
For the purposes of the present invention, the term "build-up"
of the colour of keratin fibres means the variation in coloration
between locks of undyed grey hair and locks of dyed hair.
The examples that follow serve to illustrate the invention
without, however, being limiting in nature.
Dyeing example I
In the example that follows, the colour build-up DE * and the
chromaticity C* were compared between a dyeing process according to
the invention and a dyeing process (comparative) that is identical but
that does not involve the use of a composition comprising titanium
salts.
1. Test compositions
(*) 0 . 144 g of 167-volume aqueous hydrogen peroxide solution
Composition B (revealer) Amount
Sodium bicarbonate 2.6 g
Monoethanolamine 2 g
Demineralized water qs 100 g
em nera ze water qs g
2 . Procedure:
Each composition Al , A2, A3 and A4 is applied to locks of
permanent-waved grey hair containing 90% white hairs, at a rate of 12
g of composition per 1 g 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.
Composition B is then applied to each of the locks at a rate of
4 g of composition per 1 g of lock. The pH of composition B is 9.5 .
The leave-on time is 10 minutes at room temperature. The hair is then
rinsed with water, washed with a standard shampoo and dried under a
hood.
Composition C is then applied to each of locks at a rate of 4 g
of composition per 1 g of lock; the leave-on time is 10 minutes at
room temperature. The hair is then rinsed with water, washed with a
standard shampoo and dried under a hood.
3. Colorimetric results:
The colour build-up DE * and the chromaticity C* are compared
between a dyeing process according to the invention and a process that
is identical but that uses water instead of composition C based on
titanium salts.
The colour of the locks was evaluated in the CIE L* a * b *
system, using a Minolta CM2600D spectrocolorimeter. In this L* a *
b * system, the three parameters denote, respectively, the intensity
(L*), a * indicates the green/red colour axis and b * the blue/yellow
colour axis.
The variation in coloration between the locks of permanentwaved
grey hair containing 90% white hairs (90 PWG) that are
untreated (control) and after treatment is defined by (DE *) according
to the following equation:
D E*= j L *- L0*) 2 + (a* - a *) 2 + (b* - b *) 2
In this equation, L*, a * and b * represent the values measured
on locks of hair after dyeing and L0*, a0* and bo* represent the values
measured on locks of untreated undyed hair. The greater the value of
DE *, the better the colour build-up.
The chromaticity was also measured by the values a * and b *
and is obtained from the following formula:
C* = [a* 2 + b * ]1 2
The greater the value of C*, the more chromatic the colour
obtained.
The colour build-up DE * and chromaticity C* values are given
in the tables below:
Table 1: Chromaticity C results for catechin
Chromaticity C*
Without titanium salts (comparative) 19.8
With titanium salts 21.6
Table 2 : Chromaticity C results for haematoxylin
Table 3: Chromaticity C and colour build-up results for quercetin and
gallic acid
It is found that the dyeing process according to the invention
gives more chromatic colorations irrespective of the ortho-diphenol
derivative used, only when the post-treatment with titanium salts is
not performed.
Moreover, the dyeing process according to the invention leads
to satisfactory colour build-up for quercetin and gallic acid.
Dyeing example II
In the example that follows, the colour build-up DE * and the
chromaticity C* were compared between a dyeing process according to
the invention and a dyeing process that is identical but that does not
involve the use of a composition comprising scandium salts.
1. Test compositions
(*) 0 . 144 g of 167-volume aqueous hydrogen peroxide solution
2 . Procedure:
Each composition A' l , A'2, and A'3 is applied to locks of
permanent-waved grey hair containing 90% white hairs, at a rate of 12
g of composition per 1 g 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.
Composition B is then applied to each of the locks at a rate of
4 g of composition per 1 g of lock. The pH of composition B is 9.5 .
The leave-on time is 10 minutes at room temperature. The hair is then
rinsed with water, washed with a standard shampoo and dried under a
hood.
Composition C is then applied to each of locks at a rate of 4 g
of composition per 1 g of lock; the leave-on time is 10 minutes at
room temperature. The hair is then rinsed with water, washed with a
standard shampoo and dried under a hood.
3. Colorimetric results:
The colour build-up DE * and the chromaticity C* are compared
between a dyeing process according to the invention and a process that
is identical but that uses water instead of composition C based on
scandium salts.
The colour of the locks was evaluated in the CIE L* a * b *
system, using a Minolta CM2600D spectrocolorimeter. In this L* a *
b * system, the three parameters denote, respectively, the intensity
(L*), a * indicates the green/red colour axis and b * the blue/yellow
colour axis.
The variation in coloration between the locks of permanentwaved
grey hair containing 90% white hairs (90 PWG) that are
untreated (control) and after treatment is defined by (DE *) according
to the following equation:
D E*= j L *- L0*) 2 + (a* - a *) 2 + (b* - b *) 2
In this equation, L*, a * and b * represent the values measured
on locks of hair after dyeing and L0*, a0* and bo* represent the values
measured on locks of untreated undyed hair. The greater the value of
DE *, the better the colour build-up.
The chromaticity was also measured by the values a * and b *
and is obtained from the following formula:
The greater the value of C*, the more chromatic the colour
obtained.
The colour build-up DE * and chromaticity C* values are given
in the tables below:
It is found that the dyeing process according to the invention
gives more chromatic colorations irrespective of the ortho-diphenol
derivative used.
Moreover, the dyeing process according to the invention leads
to satisfactory colour build-up.
It is also seen visually that the process of the invention gives
better colour build-up and better chromaticity of the coloration than
those obtained with the comparative process. This is confirmed by the
colorimetric measurements, which demonstrate that the dyeing process
according to the invention gives more chromatic colorations C* and
more satisfactory colour build-up irrespective of the ortho-diphenol
derivative used, when compared with a process not using a posttreatment
with a scandium salt.

CLAIMS
1. Process for dyeing keratin fibres, in particular human keratin
fibres such as the hair, in which the said fibres are treated with one or
more cosmetic compositions containing, taken together or separately in
the said composition(s), the following ingredients:
a) one or more ortho-diphenol derivatives,
b) one or more manganese salts or one or more zinc salts,
c) hydrogen peroxide or one or more systems that generate
hydrogen peroxide,
d) one or more (bi)carbonates or one or more systems that
generate (bi)carbonate(s), and
e) one or more basifying agents other than the (bi)carbonate(s),
and
f) one or more salts chosen from titanium salts and scandium
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 that the composition comprising f) the
salt(s) chosen from titanium salts and scandium salts is applied to the
keratin fibres as the last step of the dyeing process.
2 . Dyeing process according to Claim 1, characterized in that
the ortho-diphenol derivative(s) are chosen from natural orthodiphenol
derivatives.
3. Dyeing process according to Claim 1, characterized in that
ingredient a) is an ortho-diphenol bearing an aromatic ring chosen
from benzene, naphthalene, tetrahydronaphthalene, indane, indene,
anthracene, phenanthrene, isoindole, indoline, isoindoline, benzofuran,
dihydrobenzofuran, chroman, isochroman, chromene, isochromene,
quinoline, tetrahydroquinoline and isoquinoline, the said aromatic ring
comprising at least two hydroxyl groups borne by two adjacent
contiguous carbon atoms of the aromatic ring.
4 . Dyeing process according to any one of the preceding
claims, characterized in that ingredient a) is an ortho-diphenol of
formula (I) below or an oligomer thereof, in salified or non-salified
form:
which formula (I) the substituents:
Ri to R4, which may be identical or different, represent:
a hydrogen atom;
a halogen atom,
a hydroxyl radical,
a carboxyl radical,
an alkyl carboxylate or alkoxycarbonyl radical,
an optionally substituted amino radical,
an optionally substituted linear or branched alkyl radical,
an optionally substituted linear or branched alkenyl radical,
an optionally substituted cycloalkyl radical,
an alkoxy radical,
an alkoxyalkyl radical,
an alkoxyaryl radical, the aryl group possibly being optionally
substituted,
an aryl radical,
a substituted aryl radical,
a saturated or unsaturated heterocyclic radical, optionally
bearing a cationic or anionic charge, optionally substituted
and/or optionally fused with an aromatic ring, the said aromatic
ring being optionally substituted,
a radical containing one or more silicon atoms,
• in which two of the substituents borne by two adjacent
carbon atoms Ri - R2, R2 - R3 or R3 - R4 form, together with the carbon
atoms that bear them, a saturated or unsaturated, aromatic or nonaromatic
ring, optionally containing one or more heteroatoms and
optionally fused with one or more saturated or unsaturated rings
optionally containing one or more heteroatoms.
5. Composition according to any one of the preceding claims,
characterized in that the ortho-diphenol derivative(s) are chosen from:
- flavonols,
- anthocyanidins,
- anthocyanins or anthocyans,
- ortho-hydroxybenzoates,
- flavones,
- hydroxystilbenes,
- 3,4-dihydroxyphenylalanine and derivatives thereof,
- 2,3-dihydroxyphenylalanine and derivatives thereof,
- 4,5-dihydroxyphenylalanine and derivatives thereof,
- dihydroxycinnamates,
- ortho-polyhydroxycoumarins,
- ortho-polyhydroxyisocoumarins,
- ortho-polyhydroxycoumarones,
- ortho-polyhydroxyisocoumarones,
- ortho-polyhydroxychalcones,
- ortho-polyhydroxychromones,
- ortho-polyhydroxyquinones,
- ortho-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,
- proathocyanins,
- tannic acid,
- ellagic acid,
- and mixtures of the preceding compounds,
6 . Dyeing process according to any one of Claims 2 to 5,
characterized in that the natural ortho-diphenol derivative(s) are
chosen from animal, bacterial, fungal, algal, plant and fruit extracts.
7 . 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 chosen from carboxylic
acid salts of manganese.
8. Dyeing process according to any one of the preceding
claims, characterized in that ingredient c) is hydrogen peroxide or
urea peroxide.
9 . Dyeing process according to any one of the preceding
claims, characterized in that the (bi)carbonate(s) are alkali metal,
alkaline-earth metal or ammonium (bi)carbonates.
10 . Dyeing process according to any one of the preceding
claims, characterized in that the alkaline agent(s) other than the
(bi)carbonate(s) are chosen from:
- aqueous ammonia,
- alkanolamines,
- oxyethylenated ethylenediamines,
- oxypropylenated ethylenediamines,
- mineral or organic hydroxides,
- alkali metal silicates,
- amino acids, and
- the compounds of formula (II) below:
( )
in which formula (II):
-W is a divalent (Ci-Cs)alkylene group, preferably propylene
optionally substituted especially with a hydroxyl group or a C 1-C4
alkyl radical;
-Ra , Rb, Rc and Rd, which may be identical for different,
represent a hydrogen atom or a C 1-C4 alkyl or C 1-C4 hydroxyalkyl
radical.
preferably, the alkaline agent(s) e) are chosen from
alkanolamines, in particular monoethanolamine.
11. Dyeing process according to any one of the preceding
claims, characterized in that the titanium derivative(s) are chosen
from:
i) titanium IV salts such as potassium titanium oxalate
dihydrate K2TiO(C204)2- H20 , Ti(S0 4)2,
ii) titanium oxides and salts thereof, hydrates thereof and
supported forms thereof.
12. Dyeing process according to any one of Claims 1 to 10,
characterized in that scandium salts are chosen from scandium
hydroxide, scandium halides such as scandium chloride, scandium
sulfate, scandium nitrate, carboxylic acid salts of scandium such as
anhydrous or hydrated scandium acetate, and (poly)halo(Ci-
C 6)alkylsulfonates such as scandium trifluoromethanesulfonate.
13. Process according to any one of the preceding claims,
characterized in that it is performed in one step, which consists in
applying to keratin fibres an aqueous composition comprising a), b),
c), d), e) and f) as defined according to any one of the preceding
claims.
14. Process according to any one of Claims 1 to 12,
characterized in that the first step consists in applying to the said
fibres a composition comprising ingredients a), b) and c) as defined
according to any one of Claims 1 to 8, and then, in a second step, a
composition comprising ingredients d) and e) as defined according to
Claims 9 and 10, and then, in a third step, a composition comprising
ingredient f) as defined according to Claim 11 or 12 is applied to the
said fibres, it being understood that at least one of the three
compositions is aqueous.
15. Process according to any one of the preceding claims, in
which mechanical wiping and/or drying and/or rinsing of the keratin
fibres is performed before performing the step comprising the
application of a composition comprising ingredient d) and/or e) as
defined according to any one of Claims 1, 9 and 10 .
16 . Cosmetic composition for dyeing keratin fibres, containing
compounds a), b), c), d), e) and f) as defined according to any one of
Claims 1 to 12.
17 . Multi-compartment device comprising from 2 to 6
compartments containing from 2 to 6 compositions, in which are
distributed ingredients a), b), c), d), e) and f) as defined in any one of
Claims 1 to 12, the said compositions being aqueous or pulverulent,
with at least one of these compositions being aqueous.
18. Use of one or more salts chosen from titanium salts and
scandium salts as defined in Claims 1, 11 and 12, for improving the
chromaticity and/or the colour build-up of keratin fibres, in particular
human keratin fibres such as the hair, dyed with one or more orthodiphenol
derivatives as defined in any one of Claims 1 to 6 .