Hair dyeing process using at least one direct and/or natural dye, a
titanium salt, a cellulose-based polysaccharide and optionally a particular
organic solvent
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 synthetic direct dyes and/or dyes of
natural origin, b) one or more titanium salts and b1) optionally one or more particular
carboxylic acids, c) one or more cellulose-based polysaccharides, d) optionally one or
more organic compounds that are liquid at 25°C, with a Hansen solubility parameter
value H <16 (MPa)½at 25°C, e) optionally one or more chemical oxidizing agents such
as hydrogen peroxide or one or more hydrogen peroxide-generating systems.
It is known practice to dye keratin fibres and in particular human hair with dye
compositions containing direct dyes. The standard dyes that are used are, in particular,
dyes of the nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine or
triarylmethane type, or natural dyes.
These dyes may be nonionic, anionic, cationic or amphoteric. These dyes are
coloured or colouring molecules that have affinity for keratin fibres. These compositions
containing one or more direct dyes are applied to keratin fibres for a time necessary to
obtain the desired colouring, and are then rinsed out. The colourings that result therefrom
are particularly chromatic colourings but are, however, only temporary or semi-permanent
since the nature of the interactions that bind the direct dyes to the keratin fibre and their
desorption from the surface and/or the core of the fibre are responsible for their weak
dyeing power and their poor persistence with respect to light, washing or perspiration.
Progress therefore remains to be made in this field in order to afford powerful,
resistant dyeing results that respect the nature of the hair using compositions containing
dyes that are especially natural.
In the field of dyeing using natural extracts such as ortho- diphenols (ODPs), it is also
known practice to dye keratin materials such as the hair or the skin using ODPs 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 colourings of
keratin materials with atmospheric oxygen or any oxygen-generating system.
However, the colourings obtained using ODPs are not strong enough or intense
enough, and/or are not very persistent, especially in the case of hair fibres.
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 persistent
shades (Ullmann's Encyclopaedia "Metal and Dyes", 2005 § 5.1 , p. 8). However, this
process generally has the drawback of not always respecting the cosmetic nature of the
keratin fibre.
Other documents describe the use of ODPs in combination with Mn and Zn salts and
other metal salts, including titanium salts, and a chemical oxidizing agent (FR 297 673,
WO201 1/086284, WO201 1/086282 and FR 2 951 374).
Nevertheless, improvements should be further made, especially in terms of
persistence of the colour with regard to shampooing and to sweat.
There is thus a real need to develop dyeing processes that make it possible to obtain
more powerful and/or more persistent colourings using synthetic direct dyes and/or dyes
of natural origin, in particular ODPs, preferably using natural extracts that are rich in
ODPs, less aggressive to keratin fibres, or that require smaller amounts of dyes. More
particularly, there is a need to obtain colourings that satisfactorily withstand external
agents (light, bad weather, shampooing or sweat), which are persistent and
homogeneous, i.e. showing little dyeing selectivity between the root and the end, while at
the same time remaining strong and/or chromatic. In addition, it is necessary, in order to
obtain satisfactory dyeing performance, for the product to be stable and to have suitable
working qualities, i.e. a sufficient rheology so as not to run during the leave-on time. For
this, it is preferable for the dye support not to interact in the dyeing process.
This (these) aim(s) are 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 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 dyes chosen from synthetic direct dyes and dyes of natural origin,
preferably chosen from ODPs;
b) one or more titanium salts; in particular, the Ti atom of the salt is of oxidation state 2, 3
or 4, denoted Ti(ll), Ti(lll) or Ti(IV), preferably Ti(IV);
b1) optionally one or more carboxylic acids of formula (I) below:
formula (I) or a salt thereof, in which:
- A represents a saturated or unsaturated, cyclic or non-cyclic and aromatic or nonaromatic
hydrocarbon-based group, which is monovalent when n has the value 0
or polyvalent when n is greater than or equal to 1, comprising from 1 to 50 carbon
atoms, which is optionally interrupted with one or more heteroatoms and/or
optionally substituted, especially with one or more hydroxyl groups; preferably, A
represents a monovalent ( -C6)alkyl group or a polyvalent (CrC 6)alkylene group
optionally substituted with one or more hydroxyl groups;
- n represents an integer between 0 and 10 inclusive; preferably, n is between 0
and 5, such as between 0 and 2;
c) one or more cellulose-based polysaccharides;
d) optionally one or more organic compounds that are liquid at 25°C with a Hansen
solubility parameter value of less than 16 (MPa)½at 25°C; and
e) optionally one or more chemical oxidizing agents chosen in particular from hydrogen
peroxide or one or more hydrogen peroxide-generating systems.
Preferably, the composition(s) used in the process of the invention are aqueous.
Another subject of the invention is a cosmetic composition comprising ingredients a),
b), c), optionally d) and optionally e), as defined previously.
Another subject of the present invention relates to a multi-compartment device
comprising ingredients a), b), c), optionally d) and optionally e), distributed in several
compartments.
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 persistent dyeing results. In particular, the dyeing process according to the
invention can produce colourings that are resistant to washing, perspiration, sebum and
light without impairing the fibres. The resistance to perspiration is particularly good.
Furthermore, the dyeing process used can induce a satisfactory "build-up" and/or
strength of the colouring.
Other subjects, characteristics, aspects and advantages of the present invention will
emerge even more clearly on reading the description and the examples that follow.
a) dve(s)
In accordance with the present invention, the dyeing process uses a) one or more
synthetic direct dyes and/or dyes of natural origin.
The dye(s) of the invention may be present in one or more cosmetic compositions
used during the dyeing process.
According to a particular embodiment of the invention, the dye(s) are chosen from
synthetic direct dyes.
The synthetic direct dye(s) that may be used in the context of the invention may be
chosen from fluorescent or non-fluorescent, anionic, cationic or neutral direct dyes.
These synthetic direct dyes are chosen in particular from those conventionally used in
direct dyeing, any commonly used aromatic and/or non-aromatic dyes such as neutral,
acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes,
natural direct dyes, neutral, acidic or cationic quinone and in particular anthraquinone
direct dyes, azine, polyarylmethane such as triarylmethane, indoamine, polymethine such
as styryl, porphyrin, metalloporphyrin, phthalocyanine, methine cyanine direct dyes.
According to a particular embodiment of the invention, the dye(s) are chosen from
anionic direct dyes. These dyes are commonly referred to as "acidic" direct dyes or "acid
dyes" on account of their affinity for alkaline substances. The term "anionic direct dyes"
means any direct dye comprising in its structure at least one C0 2 or S0 3R substituent
with R denoting a hydrogen atom or a cation originating from a metal or an amine, or an
ammonium ion. The anionic dyes may be chosen from acidic nitro direct dyes, acidic azo
dyes, acidic azine dyes, acidic triarylmethane dyes, acidic indoamine dyes, acidic
anthraquinone dyes, indigoid dyes and acidic natural dyes.
According to another particular embodiment of the invention, the dye(s) are chosen
from cationic direct dyes or dyes commonly referred to as "basic" direct dyes or "basic
dyes" on account of their affinity for acidic substances. The cationic dyes are
preferentially chosen from hydrazono, (poly)azo, polymethine such as styryl and
(poly)arylmethane dyes. More preferentially, the cationic dye(s) of the invention are
chosen from the hydrazono dyes of formulae (Va) and (V'a), the azo dyes (Via) and (Vl'a)
and the diazo dyes (Vila) below:
Het+-C(Ra)=N-N(R )-Ar, Q Het+-N(Ra)-N=C(R )-Ar, Q Het+-N=N-Ar, Q
(Va) (Va) (Via)
Ar+-N=N-Ar", Q and Het+-N=N-Ar'-N=N-Ar, Q
(Vl'a) (Vila)
formulae (Va), (Va), (Via), (Vl'a) and (Vila) with:
• Het+ representing a cationic heteroaryl radical, preferentially bearing an
endocyclic cationic charge, such as imidazolium, indolium or pyridinium, optionally
substituted, preferentially with one or more (Ci-C8) alkyl groups such as methyl;
• Ar+ representing an aryl radical, such as phenyl or naphthyl, bearing an exocyclic
cationic charge, preferentially ammonium, particularly tri (Ci-C8)alkylammonium
such as trimethylammonium;
• Ar represents an aryl group, especially phenyl, which is optionally substituted,
preferentially with one or more electron-donating groups such as i) optionally
substituted (CrC 8)alkyl, ii) optionally substituted (CrC 8)alkoxy, iii) (di)(Ci-
C8)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group,
iv) aryl (Ci-C8)alkylamino, v) optionally substituted N-(Ci-C8)alkyl-N-aryl (Ci-
C8)alkylamino or alternatively Ar represents a julolidine group;
• Ar' is an optionally substituted divalent (hetero)arylene group such as phenylene,
particularly para-phenylene, or naphthalene, which are optionally substituted,
preferentially with one or more (CrC 8)alkyl, hydroxyl or ( -C8)alkoxy groups;
• Ar" is an optionally substituted (hetero)aryl group such as phenyl or pyrazolyl,
which are optionally substituted, preferentially with one or more groups (C
C8)alkyl, hydroxyl, (di)(Ci-C 8)(alkyl)amino, (Ci-C8)alkoxy or phenyl;
• Ra and Rb, which may be identical or different, represent a hydrogen atom or a
(Ci-C8)alkyl group, which is optionally substituted, preferentially with a hydroxyl
group;
or alternatively the substituent Ra with a substituent of Het+ and/or R with a
substituent of Ar and/or Ra with R form, together with the atoms that bear them, a
(hetero)cycloalkyl;
particularly, Ra and R represent a hydrogen atom or a (Ci-C4)alkyl group, which
is optionally substituted with a hydroxyl group;
• Q represents an anionic counterion as defined previously.
According to a preferred variant of the invention, the cationic dyes are chosen from
the polymethine dyes of formulae (Villa) and (Vlll'a) below:
W+-[C(R )=C(R )]m-Ar', Q Ar-[C(R )=C(R )]m W'+, Q
(Vllla) (Vlll'a)
formulae (Villa) or (Vlll'a) with:
• W+ representing a cationic heterocyclic or heteroaryl group, particularly comprising a
quaternary ammonium optionally substituted with one or more (CrC 8)alkyl groups
optionally substituted especially with one or more hydroxyl groups;
• W'+ representing a heterocyclic or heteroaryl radical as defined for W+;
• Ar representing a (hetero)aryl group such as phenyl or naphthyl, optionally substituted
preferentially with i) one or more halogen atoms such as chlorine or fluorine; ii) one or
more (Ci-C8)alkyl groups, preferably of C C4 such as methyl; iii) one or more hydroxyl
groups; iv) one or more (Ci-C8)alkoxy groups such as methoxy; v) one or more
hydroxy(CrC 8)alkyl groups such as hydroxyethyl, vi) one or more amino groups or
(di)(Ci-C 8)alkylamino, preferably with the C C4 alkyl part optionally substituted with
one or more hydroxyl groups, such as (di)hydroxyethylamino, vii) with one or more
acylamino groups; viii) one or more heterocycloalkyl groups such as piperazinyl,
piperidyl or 5- or 6-membered heteroaryl such as pyrrolidinyl, pyridyl and imidazolinyl;
• Ar' is a (hetero)aryl radical as defined for Ar;
• m' represents an integer between 1 and 4 inclusive, and in particular m has the value
1 or 2; more preferentially 1;
• R , Rd, which may be identical or different, represent a hydrogen atom or an optionally
substituted (Ci-C8)alkyl group, preferentially of Ci-C4, or alternatively R contiguous
with W+ or W'+ and/or R contiguous with Ar or Ar' and/or contiguous R and R form,
with the atoms that bear them, a (hetero)cycloalkyl, particularly R is contiguous with
W+ orW'+ and forms a (hetero)cycloalkyl such as cyclohexyl;
• Q as defined previously preferably represents a halide or a mesylate.
Mention may be made more particularly of the azo and hydrazono dyes bearing an
endocyclic cationic charge of formulae (Va), (Va), (Via) and (Vl'a) as defined previously.
More particularly those of formulae (Va), (Va) and (Via) derived from the dyes described
in patent applications WO 95/15144, WO 95/01772 and EP-714954. Preferentially, the
cationic dyes comprise an endocyclic cationic charge and have the following formula:
(Va-1) (Vla-1)
formulae (Va-1) and (Vla-1) with:
- R representing a (CrC4)alkyl group such as methyl;
- R2 and R3, which may be identical or different, represent a hydrogen atom or a (C
C4)alkyl group, such as methyl; and
- R4 represents a hydrogen atom or an electron-donating group such as optionally
substituted (CrC8)alkyl, optionally substituted (CrC8)alkoxy, or (di)(Ci-C 8)(alkyl)amino
optionally substituted on the alkyl group(s) with a hydroxyl group; particularly, R4 is a
hydrogen atom;
- Z represents a CH group or a nitrogen atom, preferentially CH;
- Q as defined previously preferably represents a halide or a mesylate.
Particularly, the dyes of the invention are chosen from those of formula (llla-1 ) and (IVa-
1) is chosen from Basic Red 5 1, Basic Yellow 87 and Basic Orange 3 1 or derivatives
thereof:
Q- QBasic
Red 5 1 Basic Orange 3 1 Basic Yellow 87
with Q as defined previously preferably representing a halide or a mesylate.
According to a particularly advantageous embodiment of the invention, the dye(s) are
chosen from dyes of natural origin or "natural" dyes.
Among the natural dyes, mention may be made of lawsone, juglone, indigo, isatin,
curcumin, chlorophyllin, laccaic acid, kermesic acid, carminic acid, sorghum, spinulosin,
apigenidin, orceins, polyphenols or ortho-diphenols (ODPs) and any extract rich in ODPs.
Use may also be made of extracts or decoctions comprising these natural dyes and
especially henna-based and/or indigo-based extracts or poultices.
According to a particularly preferred embodiment of the invention, the dye(s) are
chosen from ortho-diphenol(s) or ODP(s).
The invention relates to one or more ODPs or mixtures of compounds comprising one
or more aromatic rings, at least one of which is a benzene ring substituted with at least
two hydroxyl (OH) groups borne by two adjacent carbon atoms of said benzene group
being present in the structure of the ortho-diphenol(s).
The aromatic ring is more particularly a fused aryl or fused heteroaromatic ring, i.e.
optionally comprising one or more heteroatoms, such as benzene, naphthalene,
tetrahydronaphthalene, indane, indene, anthracene, phenanthrene, indole, isoindole,
indoline, isoindoline, benzofuran, dihydrobenzofuran, chroman, isochroman, chromene,
isochromene, quinoline, tetrahydroquinoline and isoquinoline, 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 ODPs according to the invention is a
benzene ring.
The term "fused ring" means that at least two saturated or unsaturated and
heterocyclic or non-heterocyclic rings have a shared bond, i.e. at least one ring is placed
side-by-side with another ring.
The ODP(s) according to the invention may or may not be salified. They may also be
in aglycone form (without bonded sugar) or in the form of glycosylated compounds.
More particularly, the ODP(s) a) represent a compound of formula (II), or an oligomer,
tautomer, optical isomer or geometrical isomer thereof, and also salts or solvates thereof,
such as hydrates:
which formula (II):
R to R4, which may be identical or different, represent: i) a hydrogen atom, ii) a
halogen atom, or a group chosen from iii) hydroxyl, iv) carboxyl, v) (CrC 2o)alkyl
carboxylate or (CrC 2o)alkoxycarbonyl, vi) optionally substituted amino, vii) optionally
substituted linear or branched (Ci-C 2o)alkyl , viii) optionally substituted linear or
branched (C2-C2o)alkenyl, ix) optionally substituted cycloalkyl, x) (CrC 2o)alkoxy, xi)
(Ci-C 2o)alkoxy(Ci-C 2o)alkyl , xii) (Ci-C 2o)alkoxyaryl, xiii) aryl which can optionally be
substituted, xiv) aryl, xv) substituted aryl, xvi) heterocyclic which is saturated or
unsaturated, optionally bearing a cationic or anionic charge and which is optionally
substituted and/or optionally fused with an aromatic ring, preferably a benzene ring,
said aromatic ring optionally being substituted, in particular with one or more hydroxyl
or glycosyloxy groups, xvii) a radical containing one or more silicon atoms;
or two of the substituents borne by two adjacent carbon atoms R - R2, R2 - R3 or R3 -
R4 form, together with the carbon atoms bearing them, a saturated or unsaturated and
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. In particular, the compound of formula (II) comprises from
one to four rings.
A particular embodiment of the invention relates to one or more ODPs of formula (II),
two adjacent substituents R - R2, R2 - R3 or R3 - R4 of which cannot form, with the carbon
atoms that bear them, a pyrrolyl radical. According to a variant, R2 and R3 form a pyrrolyl
or pyrrolidinyl radical fused to the benzene ring bearing the two hydroxyls.
For the purposes of the present invention and unless otherwise indicated:
- the saturated or unsaturated and optionally fused rings may also be optionally
substituted;
- the "alky radicals are saturated, linear or branched, generally Ci-C 2o, particularly -
Cio, hydrocarbon-based radicals, preferably Ci-C 6 alkyl radicals, such as methyl, ethyl,
propyl, butyl, pentyl and hexyl;
- the "alkenyP' radicals are unsaturated and linear or branched C2-C20 hydrocarbon-based
radicals; preferably comprising at least one double bond, such as ethylene, propylene,
butylene, pentylene, 2-methylpropylene and decylene;
- the "aryP' radicals are monocyclic or fused or non-fused polycyclic carbon-based
radicals preferentially comprising from 6 to 30 carbon atoms, at least one ring of which
is aromatic; preferentially, the aryl radical is chosen from phenyl, biphenyl, naphthyl,
indenyl, anthracenyl and tetrahydronaphthyl;
- the "alkoxy" radicals are alkyl-oxy radicals with alkyl as defined previously, preferably
C -C 0 alkyl, such as methoxy, ethoxy, propoxy and butoxy;
- the "alkoxyalkyr radicals are (Ci-C 20)alkoxy (Ci-C 20)alkyl radicals, such as
methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, etc.;
- the "cycloalkyr radicals are C4-C8 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 "alkyi' or "alkenyP' radicals, when they are "optionally substituted", may be
substituted with at least one atom or group borne by at least one carbon atom chosen
from: i) halogen; ii) hydroxyl; iii) (CrC 2)alkoxy; iv) (Ci-Ci0)alkoxycarbonyl; v)
(poly)hydroxy(C 2-C4)alkoxy; vi) amino; vii) 5- or 6-membered heterocycloalkyl; viii)
optionally cationic 5- or 6-membered heteroaryl, preferably imidazolium, optionally
substituted with a (CrC4)alkyl radical, preferably methyl; ix) amino substituted with one
or two identical or different Ci-C6 alkyl radicals optionally bearing at least: a) one
hydroxyl group, b) one amino group optionally substituted with one or two optionally
substituted (CrC 3)alkyl radicals, it being possible for said alkyl radicals to form, 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 nitrogen or non-nitrogen heteroatom, c) 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 C C4 alkyl group; and M represents the counterion of the
corresponding organic acid, mineral acid or halide, d) or one optionally cationic 5- or 6-
membered heteroaryl radical, preferentially imidazolium, optionally substituted with a
(CrC4)alkyl radical, preferably methyl; x) acylamino (-N(R)-C(0)-R') in which the R
radical is a hydrogen atom or a (CrC4)alkyl radical optionally bearing at least one
hydroxyl group and the R' radical is a Ci-C2 alkyl radical; a carbamoyl ((R)2N-C(0)-)
radical in which the R radicals, which may be identical or different, represent a
hydrogen atom or a (CrC 4)alkyl radical optionally bearing at least one hydroxyl group;
xi) alkylsulfonylamino (R'-S(0) 2-N(R)-) in which the R radical represents a hydrogen
atom or a (CrC 4)alkyl radical optionally bearing at least one hydroxyl group and the R'
radical represents a (CrC4)alkyl radical, a phenyl radical; xii) aminosulfonyl ((R)2NS(
0) 2-) in which the R radicals, which may be identical or different, represent a
hydrogen atom or a (CrC4)alkyl radical optionally bearing at least one group chosen
from a) hydroxyl, b) carboxyl -C(0)-OH in the acid or salified form (preferably salified
with an alkali metal or a substituted or unsubstituted ammonium); xiii) cyano; xiv) nitro;
xv) carboxyl or glycosylcarbonyl; xvi) phenylcarbonyloxy optionally substituted with
one or more hydroxyl groups; xvii) glycosyloxy; and phenyl group optionally substituted
with one or more hydroxyl groups;
- the "ary or "heterocyclic" radicals or the aryl or heterocyclic part of the radicals, when
they are "optionally substituted", may be substituted with at least one atom or group
borne by at least one carbon atom chosen from:
i) (CrCio)alkyl, preferably Ci-C8 alkyl, optionally substituted with one or more radicals
chosen from the following radicals: hydroxyl, (CrC 2)alkoxy, (poly)hydroxy(C 2-
C4)alkoxy, acylamino, amino substituted with two identical or different -C4 alkyl
radicals optionally bearing at least one hydroxyl group or it being possible for the two
radicals to form, 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 nitrogen or non-nitrogen
heteroatom; ii) halogen; iii) hydroxyl; iv) Ci-C 2 alkoxy; v) C1-C10 alkoxycarbonyl; vi)
(poly)hydroxy(C 2-C4)alkoxy; vii) amino; viii) 5- or 6-membered heterocycloalkyl; ix)
optionally cationic 5- or 6-membered heteroaryl, preferably imidazolium, optionally
substituted with a (CrC 4)alkyl radical, preferably methyl; x) amino substituted with one
or two identical or different Ci-C 6 alkyl radicals optionally bearing at least: a) one
hydroxyl group, b) one amino group optionally substituted with one or two optionally
substituted C1-C3 alkyl radicals, it being possible for said alkyl radicals to form, 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
nitrogen or non-nitrogen heteroatom, c) 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 C4 alkyl group; and M represents the counterion of the corresponding
organic acid, mineral acid or halide, d) one optionally cationic 5- or 6-membered
heteroaryl radical, preferably imidazolium, optionally substituted with a (CrC 4)alkyl
radical, preferably methyl; xi) acylamino (-N(R)-C(0)-R') in which the R radical is a
hydrogen atom or a C C4 alkyl radical optionally bearing at least one hydroxyl group
and the R' radical is a C1-C2 alkyl radical; xii) carbamoyl ((R)2N-C(0)-) in which the R
radicals, which may be identical or different, represent a hydrogen atom or a C C4
alkyl radical optionally bearing at least one hydroxyl group; xiii) alkylsulfonylamino
(R'S(0) 2-N(R)-) in which the R radical represents a hydrogen atom or a C C4 alkyl
radical optionally bearing at least one hydroxyl group and the R' radical represents a
Ci-C 4 alkyl radical, a phenyl radical; xiv) aminosulfonyl ((R)2N-S(0) 2-) in which the R
radicals, which may be identical or different, represent a hydrogen atom or a C C4
alkyl radical optionally bearing at least one hydroxyl group; xv) carboxyl in the acid or
salified form (preferably salified with an alkali metal or a substituted or unsubstituted
ammonium); xvi) cyano; xvii) nitro; xviii) polyhaloalkyl, preferably trifluoromethyl; xix) a
glycosylcarbonyl; xx) a phenylcarbonyloxy group optionally substituted with one or
more hydroxyl groups; xxi) a glycosyloxy group; and xxii) a phenyl group optionally
substituted with one or more hydroxyl groups;
- for the purposes of the present invention, the term "glycosyr radical means a radical
derived from a mono- or polysaccharide;
- the radicals "containing one or more silicon atoms" are preferably polydimethylsiloxane,
polydiphenylsiloxane, polydimethylphenylsiloxane or stearoxy dimethicone radicals;
- the "heterocyclic" radicals are radicals comprising, in at least one ring, one or more
heteroatoms chosen in particular from O, N and S, preferably O or N, optionally
substituted in particular with one or more alkyl, alkoxy, carboxyl, hydroxyl, amine or
ketone groups. These rings may comprise one or more oxo groups on the carbon
atoms of the heterocycle; mention may in particular be made, among the heterocyclic
radicals that may be used, of furyl, pyranyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl or
thienyl groups; even 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, it
being possible for these groups to be substituted, in particular with one or more OH
groups.
The ODP(s) that are useful in the process of the invention may be natural or synthetic.
Among the natural ODPs are compounds that may be present in nature and that are
reproduced by chemical (semi)synthesis.
The salts of the ODPs of the invention may be salts of acids or of bases. The acids
may be mineral or organic. Preferably, the acid is hydrochloric acid, which results in
chlorides.
The term "basifying agents" means that the bases as defined for e) may be mineral 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 ODPs 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 ODPs.
More particularly, the ODP(s) that may be used in the process of the invention
according to a) are in particular:
- flavanols, for instance catechin and epicatechin gallate,
- flavonols, for instance quercetin,
- anthocyanidins, for instance cyanidin, delphinidin and petunidin,
- anthocyanins or anthocyans, for instance myrtillin,
- ortho-hydroxybenzoates, for example gallic acid salts,
- flavones, for instance luteolin,
- 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 A 1, A2, B 1, B2, B3 and C 1,
- chroman and chromene compounds,
- proathocyanins,
- tannic acid,
- ellagic acid,
- and mixtures of the preceding compounds.
According to the invention, the term "chromene or chroman" ODP compounds means
ODPs which comprise, in their structure, at least one bicycle of formula (A) below:
(A)
the endocyclic bond representing a carbon-carbon single bond or else a carboncarbon
double bond, as illustrated by formula (A1) below, denoting the chromene family,
and formula (A2) b
(A1) (A2)
More particularly, the ODPs of the invention are of formula (A) and are preferably
chosen from the dyes of the following formulae:
> formula (III), comprising, in its structure, the bicycle of formula (A2):
and also the tautomeric and/or mesomeric forms thereof, the stereoisomers thereof,
the addition salts thereof with a cosmetically acceptable acid or base, and the hydrates
thereof;
in which formula (III):
• represents a carbon-carbon single bond or a carbon-carbon double bond,
the sequence of these bonds denoting two carbon-carbon single bonds and
two carbon-carbon double bonds, said bonds being conjugated,
• X represents a group:
// /
HO— C o r 0=C
\ • R , R2, R3, R4, R5 and R6, which may be identical or different, represent a hydrogen
atom, a hydroxyl group, an optionally substituted alkyl group, an optionally
substituted alkoxy group or an optionally substituted acyloxy group; and
> formula (IV), comprising, in its structure, the bicycle of formula (A1):
the addition salts thereof with a cosmetically acceptable acid or base, and the hydrates
thereof;
in which formula (IV):
• Ri i , Ri2, Ri3, Ri6, Ri9 and R2o, which may be identical or different, represent a
hydrogen atom or a CrC 4 alkyl radical, and
• R 4, R-I5, R-I7 and R 8, which may be identical or different, represent a hydrogen
atom, a hydroxyl radical or a C C4 alkoxy radical.
As regards the ortho-diphenols of formula (III) as defined above, they may be found in
two tautomeric forms denoted (Ilia) and (lllb):
The alkyl radicals mentioned in the preceding definitions of the substituents are
saturated and linear or branched hydrocarbon-based radicals, generally C1-C20,
particularly C1-C10, preferably Ci-C 6, hydrocarbon-based radicals, such as methyl, ethyl,
propyl, butyl, pentyl and hexyl.
The alkoxy radicals are alkyl-oxy radicals with the alkyl radicals as defined above and
preferably the alkoxy radicals are C1-C10 alkoxy radicals, such as methoxy, ethoxy,
propoxy and butoxy.
The alkyl or alkoxy radicals, when they are substituted, may be substituted with at
least one substituent borne by at least one carbon atom chosen from: i) a halogen atom
or ii) a hydroxyl group; iii) a Ci-C 2 alkoxy group; iv) a C1-C10 alkoxycarbonyl group; v) a
(poly)hydroxy(C 2-C4)alkoxy group; vi) an amino group; vii) a 5- or 6-membered
heterocycloalkyi group; viii) an optionally cationic 5- or 6-membered heteroaryl group,
preferably imidazolium, optionally substituted with a (CrC 4)alkyl radical, preferably
methyl; ix) an amino radical substituted with one or two identical or different Ci-C 6 alkyl
radicals optionally bearing at least: a) one hydroxyl group,
b) one amino group optionally substituted with one or two optionally substituted C1-C3
alkyl radicals, it being possible for said alkyl radicals to form, 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 nitrogen or nonnitrogen
heteroatom, c) 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 Ci-C 4
alkyl group and M represents the counterion of the corresponding organic acid, mineral
acid or halide, d) or one optionally cationic 5- or 6-membered heteroaryl radical,
preferably imidazolium, optionally substituted with a (Ci-C 4)alkyl radical, preferably
methyl; x) an acylamino (-NR-COR') radical in which the R radical is a hydrogen atom
or a Ci-C 4 alkyl radical optionally bearing at least one hydroxyl group and the R' radical
is a C1-C2 alkyl radical; xi) a carbamoyl ((R)2N-CO-) radical in which the R radicals,
which may be identical or different, represent a hydrogen atom or a Ci-C 4 alkyl radical
optionally bearing at least one hydroxyl group; xii) an alkylsulfonylamino (R'S0 2-NR-)
radical in which the R radical represents a hydrogen atom or a C C4 alkyl radical
optionally bearing at least one hydroxyl group and the R' radical represents a Ci-C4
alkyl radical, a phenyl radical; xiii) an aminosulfonyl ((R)2N-S0 2-) radical in which the R
radicals, which may be identical or different, represent a hydrogen atom or a C C4
alkyl radical optionally bearing at least one hydroxyl group; xiv) a carboxyl radical in the
acid or salified form (preferably salified with an alkali metal or a substituted or
unsubstituted ammonium); xv) a cyano group; xvi) a nitro group; xvii) a carboxyl or
glycosylcarbonyl group; xviii) a phenylcarbonyloxy group optionally substituted with one
or more hydroxyl groups; xix) a glycosyloxy group; and xx) a phenyl group optionally
substituted with one or more hydroxyl groups.
The term "glycosyl radical" means a radical derived from a monosaccharide or
polysaccharide.
Preferably, the alkyl or alkoxy radicals of formula (III) are unsubstituted.
According to a particular embodiment of the invention, the dyes of formula (III)
comprise a radical R6 representing a hydroxyl group.
Another particular embodiment of the invention relates to the ODPs of formula (III) for
which the radical R represents a hydrogen atom or a hydroxyl group.
More particularly, the composition according to the invention may comprise one or
more ODPs of formula (III) chosen from haematoxylin, haematein, brazilin and brazilein.
Haematoxylin (Natural Brazilin (Natural Red 24 -
CAS 517-28-2) CAS 474-07-7)
Brazilein is a conjugated form of a chroman compound of formula (A2). The
tautomeric structures (Ilia) and (lllb) illustrated above are found in the scheme below.
Brazilein
Among the ODPs of haematoxylin/haematein and brazilin/brazilein type, examples
that may be mentioned include haematoxylin (Natural Black 1 according to the INCI
name) and brazilin (Natural Red 24 according to the INCI name), dyes of the
indochroman family, which are commercially available. The latter dyes may exist in an
oxidized form and may be obtained synthetically or by extraction of plants or vegetables
known to be rich in these dyes.
The ODPs of formula (III) may be used in the form of extracts. Use may be made of
the following plant extracts (genus and species): Haematoxylon campechianum,
Haematoxylon brasiletto, Caesalpinia echinata, Caesalpinia sappan, Caesalpinia
spinosa and Caesalpinia brasiliensis.
The extracts are obtained by extracting the various plant parts, for instance the root,
the wood, the bark or the leaves.
According to one particular embodiment of the invention, the natural ODPs are of
formula (I) and are obtained from logwood, pernambuco wood, sappan wood and Brazil
wood.
According to a particular embodiment of the invention, the ODPs are of formula (IV),
preferably those for which R and R 3 represent an alkyl radical, preferably methyl.
Preferably, R 2, Ri6, R19 and R20 denote, independently of each other, a hydrogen
atom or an alkyl radical, preferably methyl.
Preferably, R 4 and R 7 denote, independently of each other, a hydrogen atom or an
alkoxy radical, preferably methoxy.
Preferably, R 8 and R 5 denote, independently of each other, a hydrogen atom, a
hydroxyl radical or an alkoxy radical, preferably methoxy.
A first particularly preferred family of ODPs that are suitable for use in the present
invention is that of the dyes corresponding to formula (II) above for which R 2 , R15, R16,
R 7 , R 9 and R2o each represent a hydrogen atom. R and R 3 each represent a methyl
radical and R 4 represents a methoxy radical.
The preferred ODPs of this first family include those for which R 8 represents a
methoxy radical (santalin B) or a hydroxyl radical (santalin A).
A second particularly preferred family of ODPs that are suitable for use in the present
invention is that of the dyes corresponding to the formula (IV) above for which:
- R and R 3 each represent a methyl radical,
- R-I7 represents a methoxy radical.
A preferred dye of this second family is that for which, in addition, R 9 represents a
methyl radical, R2o, R12, Ri4, Ris and R 6 each represent a hydrogen atom and R 5
represents a hydroxyl radical (santarubin A).
A second preferred dye of this second family is that for which R 8 , R20, R12, Ri4 and
R 6 represent a hydrogen atom, R15 represents a methoxy radical and R 9 represent a
methyl radical (santarubin B).
A third preferred family of ODPs of this second family is that for which R2o, R12, R ,
Ris, Ri 6 and R 9 represent hydrogen and R 8 represents a hydroxyl radical (santarubin
C).
The preferred ODP(s) of this second family is that for which R 5 represents a methoxy
radical, R 8 and R 4 represent a hydrogen atom and R2o, R12, Ri6 and R 9 represent a
methyl radical (tetra-O-methylsantarubin).
The ODP(s) of formula (IV) may be used in the form of extracts. Use may be made of
plant extracts of red woods, bringing together generally the species of red woods from
Asia and West Africa of the genus Pterocarpus and of the genus Baphia. These woods
are, for example, Pterocarpus santalinus, Pterocarpus osun, Pterocarpus soyauxii,
Pterocarpus erinaceus, Pterocarpus indicus or Baphia nitida. These woods may also be
called padauk, sandalwood, narra wood, camwood or bar wood.
Thus, extracts that may be used, comprising ODPs of formula (II), in the present
invention may be obtained, for example, from red sandalwood (Pterocarpus santalinus)
by aqueous basic extraction, such as the product sold under the trade name Santal
Concentre SL 709C by the company COPIAA, or also by means of solvent extraction of
sandalwood powder, such as the product sold under the trade name Santal Poudre SL
PP by the same company COPIAA. Mention may also be made of the aqueous/alcoholic
extract of powdered red sandalwood from the company Alban Muller.
Extracts also suitable for the present invention can be obtained from woods such as
camwood (Baphia nitida) or also bar wood (Pterocarpus soyauxii, Pterocarpus
erinaceus): the latter is thus split up and then ground: a conventional alcoholic extraction
or one by percolation is subsequently carried out on this ground material in order to
collect a pulverulent extract particularly suitable for the implementation of the present
invention.
The ODP salts of formulae (III) and (IV) of the invention may be salts of acids or
bases that are cosmetically acceptable.
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.
Preferably, the ODP(s) of formulae (III) and (IV) included in the composition
according to the invention result from plant extracts. Use may also be made of mixtures
of plant extracts.
The natural extracts of ODPs according to the invention may be in the form of
powders or liquids. Preferably, the extracts are in powder form.
In particular, the ODPs of the invention are included among catechin, quercetin,
brazilin, haematein, haematoxylin, chlorogenic acid, caffeic acid, gallic acid, catechol, LDOPA,
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 C 1, procyanidins DP 4-8, tannic acid,
purpurogallin, 5,6-dihydroxy-2-methyl-1 ,4-naphthoquinone, alizarin, wedelolactone,
variegatic acid, gomphidic acid, xerocomic acid and carnosol, and natural extracts
containing them.
Preferably, the ODPs of the invention are chromenes or chromans and are chosen
from haematein, haematoxylin, brazilein, brazilin and santalin A.
The term "carboxylate" means carboxylic acid salt.
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.
According to one embodiment, the natural ODPs are derived from extracts of animals,
bacteria, fungi, algae, plants and fruits, used in their entirety or partially. In particular
regarding plants, the extracts are derived from fruit, including citrus fruit, from vegetables,
from trees and from shrubs. Use may also be made of mixtures of these extracts, which
are rich in ODPs as defined above.
Preferably, the natural ODP(s) of the invention are derived from extracts of plants or
plant parts.
For the purposes of the invention, these extracts will be placed in the same category
as compounds 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 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 and
extracts of logwood.
Use may also be made of mixtures of plant extracts.
According to a particular embodiment of the invention, the ortho-diphenol derivative(s)
are natural extracts, rich in ODPs.
According to a preferred embodiment, the dye(s) of the invention are solely natural
extracts.
Preferentially, the dye(s) according to the invention are chosen from catechin,
quercetin, haematein, haematoxylin, brazilin, brazilein, gallic acid and tannic acid, and
natural extracts containing them chosen from grape marc, pine bark, green tea, onion,
cocoa bean, logwood, red wood and gall nut.
More preferentially, the ODP(s) of the invention are chosen from:
- haematein, brazilein, gallic acid or tannic acid, when the dyeing process does not use a
chemical oxidizing agent;
or else
- haematoxylin, brazilin, gallic acid or tannic acid, when the dyeing process uses a
chemical oxidizing agent.
The natural extracts according to the invention may be in the form of powders or
liquids. Preferably, the extracts of the invention are provided in the form of powders.
According to the invention, the synthetic or natural dye(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 0.001 % to 20% by weight of the total
weight of the composition(s) containing them.
As regards the pure dyes, especially the pure ODPs, the content in the composition(s)
containing them is preferably between 0.001% and 5% by weight of each of these
compositions containing them.
As regards the extracts, the content in the composition(s) containing the extracts per
se is preferably between 0.1% and 20% by weight of each of these compositions, and
better still between 0.5% and 10% by weight of the compositions containing them.
b) titanium salt(s):
The titanium salt(s) of the invention may be one or more organic or mineral titanium
salts.
For the purposes of the present invention, the term "organic titanium salt" means the
salts per se resulting from the action of at least one organic acid on Ti.
The term "organic acid" means an acid, i.e. a compound that is capable of releasing a
cation or proton H+ or H30 +, in aqueous medium, which comprises at least one optionally
unsaturated, linear or branched Ci-C2o hydrocarbon-based chain, or a (hetero)cycloalkyl
or (hetero)aryl group and at least one acid chemical function chosen in particular from
carboxyl COOH, sulfuric S0 3H, S0 2H, and phosphoric P0 3H2, P0 4H2. In particular, the
organic acid(s) for forming the organic titanium salt(s) of the invention are chosen from
the carboxylic acid(s) of formula (I) as defined previously and are preferably a-hydroxy
acids such as lactic acid, glycolic acid, tartaric acid or citric acid.
Preferentially, the organic titanium salt derived from the action of one or more organic
acids as defined previously, preferably carboxylic acids of formula (I) as defined
previously, is an optionally charged (in particular negatively charged) complex, which is
complexed with one or more carboxylate groups of carboxylic acids.
Preferentially, the organic titanium salt(s) of the invention are chosen from those of
formula (l-A) below:
(l-A)
in which formula (l-A):
• A is identical to that of formula (I);
• n, n' and n", which may be identical or different, are equal to 1, 2, 3 or 4 and n' + n" =
6;
• M and M2, which may be identical or different, represent a cationic counterion chosen
in particular from cations of an alkali metal such as Na or K or of an alkaline-earth
metal such as Ca or an organic cation such as ammonium, preferably ammonium or a
hydrogen atom;
• TiYn- denoting Ti(OH) , or Ti(0) n"/2, or Ti(OH)m1(0) m2 with m +m2 = n".
Preferentially, the radical A of compound (l-A) as defined previously represents a
monovalent (CrC 6)alkyl or polyvalent (CrC 6)alkylene group optionally substituted with
one or more hydroxyl groups, and n representing an integer between 0 and 5, such as
between 0 and 2, inclusive; in particular, the carboxylic acid(s) used to form the organic
titanium salt(s) of the invention are chosen from a-hydroxy acids; preferably, the acid is
chosen from citric acid, lactic acid, tartaric acid and glycolic acid, better still from lactic
acid and glycolic acid.
Preferentially, the organic titanium salt(s) of the invention are chosen from those of
formula (l-B) below:
(l-B)
in which formula (l-B):
• L' and L", which may be identical or different, represent a divalent (hetero)arylene,
(CrC6)alkylene or (C2-C6)alkenylene group, said alkylene and arylene groups being
optionally substituted with one or more atoms or groups chosen from halo, (C
C4)alkyl, hydroxyl, thiol and (di )(Ci -C4)(alkyl)amino, carboxyl, and/or optionally
interrupted with one or more heteroatoms such as oxygen;
preferably, L' and L" are identical and represent a methylene or ethylene group
optionally substituted with a (Ci -C4)alkyl group;
• X' and X", which may be identical or different, represent a heteroatom such as
oxygen, sulfur or amino R -N with R representing a hydrogen atom or a (CrC4)alkyl
group; preferably, X' and X" are identical and represent an oxygen atom;
• Y and Y', which may be identical or different, are as defined for X' and X"; preferably,
Y and Y' are identical and represent an oxygen atom;
• Ra and Rb, which may be identical or different, represent a hydrogen atom or a (C
C6)alkyl, (C2-C6)alkenyl or (hetero)aryl group; particularly, Ra and R , which are
identical, represent a hydrogen atom or a (Ci -C4)alkyl group, preferably hydrogen;
• M+, which may be identical or different, represents a cationic counterion such as a
cation of an alkali metal (Na or K) or of an alkaline-earth metal (Ca) or an organic
cation such as ammonium, preferably ammonium.
Preferably, the organic titanium salt(s) of the dyeing process are
dihydroxybis(lactato)titanium(IV) salts such as those having the following formula:
The dyeing process may use one or more organic acids b 1) of formula (I) as defined
previously.
According to an advantageous variant, the dyeing process also uses b 1) one or more
carboxylic acids of formula (I) as defined previously. More preferentially, the carboxylic
acid(s) b 1) are other than the carboxylic acids complexed to the Ti salts.
For example, if the carboxylic acid complexed to the titanium salt b) is lactic acid or the
carboxylate salt thereof (lactate), the second acid b1) is other than lactic acid or lactate,
and may be, for example, glycolic acid.
For the purposes of the present invention, the term "mineral titanium salt" means the
salts per se derived from the action of a mineral acid on Ti.
The term "mineral acid" means an acid which does not comprise carbon atoms, apart
from carbonic acid.
The mineral titanium salts are preferably chosen from titanium halides, titanium sulfates
and titanium phosphates. Preferably, the titanium salts are mineral Ti(ll), Ti(lll) or Ti(IV)
salts, more particularly Ti(lll) or Ti(IV).
Preferably, the titanium salt(s) are organic titanium salts, and better still organic Ti(IV)
salts. According to an advantageous embodiment of the invention, the organic Ti salt
consists of a Ti(IV) atom and of 2 to 3 molar equivalents of at least one carboxylic acid of
formula (I).
The titanium salt(s) (b) are present in the cosmetic composition(s) used in the process
according to the invention in a content ranging from 0.001% to 20% by weight, relative to
the total weight of the composition(s) containing them.
Particularly, the organic titanium salt(s) and the mineral titanium salt(s) according to
the invention are soluble in water in a proportion of at least 0.0001 g/l and better still at
least 1 g/l.
c) cellulose-based polysaccharide(s)
In accordance with the present invention, the dyeing process uses c) one or more
cellulose-based polysaccharides, i.e. one or more cellulose-based polysaccharide
polymers, which are preferably thickeners.
The cellulose-based polymers may be associative or non-associative anionic,
cationic, amphoteric or nonionic polymers.
According to the invention, the term "cellulose-based polysaccharide" means any
polymer bearing in its structure sequences of glucose residues linked via - 1,4 bonds;
besides unsubstituted celluloses, the cellulose derivatives may be anionic, cationic,
amphoteric or nonionic. Thus, the cellulose-based polysaccharides of the invention may
be chosen from unsubstituted celluloses, including those in a microcrystalline form, and
cellulose ethers. Among these cellulose-based polysaccharides, cellulose ethers,
cellulose esters and cellulose ester ethers are distinguished. Among the cellulose esters
are mineral esters of cellulose (cellulose nitrates, sulfates, phosphates, etc.), organic
cellulose esters (cellulose monoacetates, triacetates, amidopropionates,
acetatebutyrates, acetatepropionates and acetatetrimellitates, etc.), and mixed
organic/mineral esters of cellulose, such as cellulose acetatebutyrate sulfates and
cellulose acetatepropionate sulfates. Among the cellulose ester ethers, mention may be
made of hydroxypropylmethylcellulose phthalates and ethylcellulose sulfates.
The term "associative polymers" means polymers that are capable, in an aqueous
medium, of reversibly combining with each other or with other molecules. Their chemical
structure more particularly comprises at least one hydrophilic region and at least one
hydrophobic region, preferably one or more hydrophobic hydrocarbon-based side chains.
The term "hydrophobic group" means a radical or polymer with a saturated or
unsaturated, linear or branched hydrocarbon-based chain, comprising at least 10 carbon
atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms
and more preferentially from 18 to 30 carbon atoms. Preferentially, the hydrocarbonbased
group is derived from a monofunctional compound. By way of example, the
hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl
alcohol or decyl alcohol. It may also denote a hydrocarbon-based polymer, for instance
polybutadiene. According to a particular embodiment of the invention, the cellulose-based
polysaccharide(s) are non-associative.
The "non-associative" cellulose-based polysaccharides of the invention are cellulosebased
polysaccharides not comprising any fatty chains, i.e. preferably not comprising any
C10-C30 chains in their structure.
According to a first variant, the non-associative cellulose-based polysaccharide(s) are
nonionic. Mention may be made of nonionic cellulose ethers without a C 0-C30 fatty chain,
i.e. which are "non-associative", mention may be made of (Ci-C 4)alkylcelluloses, such as
methylcelluloses and ethylcelluloses (for example, Ethocel standard 100 Premium from
Dow Chemical); (poly)hydroxy(Ci-C 4)alkylcelluloses, such as hydroxymethylcelluloses,
hydroxyethylcelluloses (for example, Natrosol 250 HHR provided by Aqualon) and
hydroxypropylcelluloses (for example, Klucel EF from Aqualon); mixed (poly)hydroxy(d-
C4)alkyl(Ci-C 4)alkylcelluloses, such as hydroxypropylmethylcelluloses (for example,
Methocel E4M from Dow Chemical), hydroxyethylmethylcelluloses,
hydroxyethylethylcelluloses (for example, Bermocoll E 481 FQ from Akzo Nobel) and
hydroxybutylmethylcelluloses.
According to a second variant, the non-associative cellulose-based polysaccharide(s)
are anionic. Among the anionic cellulose ethers without a fatty chain, mention may be
made of (poly)carboxy(Ci-C 4)alkylcelluloses and salts thereof. Examples that may be
mentioned include carboxymethylcelluloses, carboxymethylmethylcelluloses (for example
Blanose 7M from the company Aqualon) and carboxymethylhydroxyethylcelluloses, and
the sodium salts thereof.
According to a third variant, the non-associative cellulose-based polysaccharide(s)
are cationic. Among the cationic cellulose ethers without a fatty chain, mention may be
made of cationic cellulose derivatives such as cellulose copolymers or cellulose
derivatives grafted with a water-soluble quaternary ammonium monomer, and described
in particular in patent US 4 131 576, such as (poly)hydroxy(CrC 4)alkyl celluloses, for
instance hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses grafted especially with
a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or
dimethyldiallylammonium salt. The commercial products corresponding to this definition
are more particularly the products sold under the names Celquat® L 200 and Celquat® H
100 by the company National Starch.
According to another particular embodiment of the invention, the cellulose-based
polysaccharide(s) are associative.
Mention may be made especially of quaternized (poly)hydroxyethylcelluloses modified
with groups comprising at least one fatty chain, such as alkyl, arylalkyi or alkylaryl groups
comprising at least 8 carbon atoms, or mixtures thereof. The alkyl radicals borne by the
above quaternized celluloses or hydroxyethylcelluloses preferably comprise from 8 to 30
carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl
groups. Examples of quaternized alkylhydroxyethylcelluloses containing C8-C30 fatty
chains that may be indicated include the products Quatrisoft LM 200®, Quatrisoft LM-X
529-1 8-A®, Quatrisoft LM-X 529-1 8B® (C 2 alkyl) and Quatrisoft LM-X 529-8® (Ci 8 alkyl)
sold by the company Aqualon, and the products Crodacel QM®, Crodacel QL® (C12
alkyl) and Crodacel QS® (Ci 8 alkyl) sold by the company Croda and the product Softcat
SL 100® sold by the company Aqualon.
Mention may also be made of celluloses or derivatives thereof, modified with groups
comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups or mixtures
thereof in which the alkyl groups are of C8, and in particular:
• nonionic alkylhydroxyethylcelluloses such as the products Natrosol Plus Grade
330 CS and Polysurf 67 (Ci 6 alkyl) sold by the company Aqualon;
• nonionic nonoxynylhydroxyethylcelluloses such as the product Amercell HM-1500
sold by the company Amerchol;
• nonionic alkylcelluloses such as the product Bermocoll EHM 100 sold by the
company Berol Nobel.
Among the cellulose-based polysaccharides according to the invention, mention may
be made of fatty-phase thickeners, especially polymers bearing in the backbone at least
one crystallizable block. As cellulose-based polysaccharides, which are in particular fattyphase
thickeners, use may thus be made of semicrystalline cellulose-based
polysaccharides. The semicrystalline cellulose-based polysaccharides that may be used
in the context of the invention may be non-crosslinked or partially crosslinked, provided
that the degree of crosslinking does not impede their dissolution or dispersion in the liquid
oily phase by heating above their melting point. It may then be a case of chemical
crosslinking, by reaction with a multifunctional monomer during the polymerization. It may
also be a case of physical crosslinking, which may then be due either to the
establishment of bonds of hydrogen or dipolar type between groups borne by the
polysaccharide, for instance dipolar interactions between carboxylate ionomers, these
interactions being in small amount and borne by the polymer backbone; or due to a
phase separation between the crystallizable blocks and the amorphous blocks borne by
the polysaccharide.
Preferably, the semicrystalline cellulose-based polysaccharides that are suitable for
use in the invention are non-crosslinked.
According to a particular embodiment of the invention, the cellulose-based
polysaccharide(s) are especially monoalkyl or polyalkyl esters of cellulose and of fatty
acids, especially corresponding to formula (C1) below:
in which formula (C1):
• n is an integer ranging from 3 to 200, especially ranging from 20 to 150 and in
particular ranging from 25 to 50,
• , R2 and R3, which may be identical or different, are chosen from hydrogen and
an acyl group (R-C(O)-) in which the radical R is a linear or branched, saturated or
unsaturated hydrocarbon-based group containing from 7 to 29, in particular from 7
to 2 1, especially from 11 to 19, more particularly from 13 to 17, or even 15, carbon
atoms, with the proviso that at least one of said radicals , R2 or R3 is other than
hydrogen.
In particular, R R2 and R3 may represent hydrogen or an acyl group (R-C(O)-) in
which R is a hydrocarbon-based radical as defined above, with the proviso that at least
two of said radicals R , R2 and R3 are identical and other than hydrogen.
The radicals R , R2 and R3 may all contain an acyl group (R-C(O)), which is identical
or different and especially identical.
In particular, n mentioned previously advantageously ranges from 25 to 50 and is
especially equal to 38 in the general formula of the saccharide ester that may be used in
the present invention.
In particular, when the radicals R , R2 and/or R3, which may be identical or different,
contain an acyl group (R-C(O)), these radicals may be chosen especially from caprylic,
capric, lauric, myristic, palmitic, stearic, arachic, behenic, isobutyric, isovaleric, 2-
ethylbutyric, ethylmethylacetic, isoheptanoic, 2-ethylhexanoic, isononanoic, isodecanoic,
isotridecanoic, isomyristic, isopalmitic, isostearic, isoarachic, isohexanoic, decenoic,
dodecenoic, tetradecenoic, myristoleic, hexadecenoic, palmitoleic, oleic, elaidic,
asclepinic, gondoleic, eicosenoic, sorbic, linoleic, linolenic, punicic, stearidonic,
arachidonic and stearolic radicals, and mixtures thereof.
The cellulose-based polysaccharides, which are in particular thickeners, may be used
alone or as mixtures in all proportions. Preferably, the thickeners are aqueous-phase
thickeners.
Preferably, the cellulose-based polysaccharides in accordance with the present
invention advantageously have in solution or in dispersion, at 1% active material in water,
a viscosity, measured using a rheometer at 25°C, of greater than 0.1 ps and even more
advantageously greater than 0.2 cp, at a shear rate of 200 s
Preferably, the cellulose-based polysaccharide(s) c) of the invention are chosen from
cellulose ethers, in particular hydroxyalkylcelluloses, in particular hydroxy(Cr
C4)alkylcelluloses, and especially chosen from hydroxymethylcelluloses,
hydroxyethylcelluloses and hydroxypropylcelluloses.
The hydroxyalkylcelluloses may be nonionic, cationic and anionic. They are preferably
nonionic. The hydroxyalkylcelluloses of the invention are preferably
hydroxyethylcelluloses and more preferentially nonionic hydroxyethylcelluloses.
Use will be made even more preferentially of nonionic hydroxyethylcelluloses free of
fatty chains or of cetylhydroxyethylcelluloses, for instance the compounds sold under the
names Polysurf 67CS®, Natrosol 250MR ®, Natrosol 250HHR® and Natrosol Plus 330® by
the company Ashland, and mixtures thereof.
The cellulose-based polysaccharide(s) of the invention may be present in the dye
composition(s) of the invention in contents ranging from 0.01% to 30% by weight, in
particular from 0.05% to 20% by weight and better still from 0.1% to 10% by weight,
relative to the total weight of the composition containing them.
d) liquid organic compound(s) with a value <16 (MPa)
According to a particular prefered embodiment of the invention, the dyeing process
also uses d) one or more liquid organic compounds which have a Hansen solubility
parameter value of less than 16 (MPa) 2 at 25°C and preferably less than or equal to
15 (MPa) 2 .
It is understood that the liquid organic compound(s) with a Hansen solubility
parameter value of less than 16 (MPa) 2 at 25°C d) are different from the carboxylic
acid(s) b1) of formula (I) as defined previously. It is also understood that the organic
compound(s) with a solubility parameter value < 16 (MPa) 2 at 25°C d) are soluble in
water with a solubility of greater than 10 g/l of water at 25°C.
For the purposes of the present invention, the term "liquid organic compound" means
an organic compound that is liquid at room temperature at 25°C.
The liquid organic compound(s) with a Hansen solubility parameter value of less
than 16 (MPa) 2 at 25°C are described, for example, in the reference book Hansen
solubility parameters A user's handbook, Charles M. Hansen, CRC Press, 2000, pages
167 to 185 and also in the book Handbook of solubility parameters and other cohesion
parameters CRC Press, pages 95 to 121 and pages 177 to 185, The 3 dimensional
solubility parameter & solvent diffusion coefficient, their importance in surface coating
formulation, Charles M. Hansen, Copenhagen Danish Technical Press, 1967, pages 13-
29.
As a reminder, the organic compounds have a global Hansen solubility parameter ,
which is defined in the article "Solubility parameter values" by Eric A. Grulke in the
"Polymer Handbook', 3rd Edition, Chapter VII, pages 519-559, by the relationship:
= ( d
2 + p2+ h
2 ) 2
in which relationship:
• d characterizes the London dispersion forces derived from the formation of dipoles
induced during molecular impacts, i.e. nonpolar interactions,
• characterizes the Debye interaction forces between permanent dipoles,
• h characterizes the interaction forces of hydrogen bonding type.
Thus, the Hansen solubility parameter takes into account the solubility associated
with the formation of hydrogen bonds in the liquid organic compounds.
According to one embodiment, the liquid organic compound(s) have a Hansen
solubility parameter value ranging from 6 (MPa) 2 to 14 (MPa) 2 at 25°C, and
preferably ranging from 4 (MPa) 2 to 10 (MPa) 2 at 25°C.
Preferably, the liquid organic compound(s) comprise a molecular weight of less than
500 g/mol and even more preferentially less than 250 g/mol.
Among the liquid organic compounds with a Hansen solubility parameter value of
less than 16 and particularly less than or equal to 15 (MPa) 2 at 25°C, mention may be
made of propylene glycol derivatives, phenyl alcohols such as benzyl alcohol, alkylene
carbonates and lactones, in particula formula (D1):
(D1)
in which formula (D1):
• n is 1, 2 or 3;
• R' represents a hydrogen atom; a linear or branched CrC 8 alkyl radical; a linear or
branched Ci-C4 hydroxyalkyl radical.
In accordance with an advantageous embodiment, the liquid organic compound(s)
with a Hansen solubility parameter value of less than 16 (MPa) 2 at 25°C are chosen
from the following compounds:
2-Phenyl-1 -propanol 12.9
Ethylene glycol 2-ethylhexyl ether 5.1
1-Octanol 11.9
1-Decanol 10
Tridecyl alcohol 9
-Butyrolactone 7.4
Propylene carbonate 4.1
Preferably, the liquid organic compound(s) with a Hansen solubility parameter value
of less than 16 (MPa) 2 at 25°C are chosen from alcohols, ethers and acids and/or a
mixture of these compounds.
Preferably, the liquid organic compound(s) with a Hansen solubility parameter value
of less than 16 (MPa) 2 at 25°C are chosen from :
-propylene glycol derivatives such as propylene glycol butyl ether, dipropylene glycol
methyl ether, tripropylene glycol methyl ether or propylene glycol propyl ether,
propylene glycol n-butyl ether, dipropylene glycol monomethyl ether acetate ;
- aromatic alcohols, preferably phenyl alcohols such as benzyl alcohol, 3-phenyl-1-
propanol or 2-phenyl-1-ethanol ;
-alkylene carbonates ;
-lactones, in particular the lactones of formula (D1);
-alcohols such as 1-Decanol or 1-Octanol;
- ethers such as ethylene glycol 2-ethylhexyl ether ;
-and/or a mixture of these compounds.
Preferably, the liquid organic compound(s) with a Hansen solubility parameter value 
of less than 16 (MPa) 2 at 25°C are chosen from alcohols, aromatic alcohols, in particular
from benzyl alcohol, ethers, propylene glycol derivatives, and/or a mixture of these
compounds.
According to one embodiment, the liquid organic compound(s) with a Hansen
solubility parameter value of less than 16 (MPa) 2 at 25°C are chosen from alcohols.
In particular, the alcohol(s) that may be used as liquid organic compounds with a
Hansen solubility parameter as described above may be chosen from aromatic
alcohols, in particular from benzyl alcohol, 3-phenyl-1 -propanol and 2-phenyl-1-ethanol,
and/or a mixture of these compounds.
According to one embodiment, the liquid organic compound(s) with a Hansen
solubility parameter value of less than 16 (MPa) 2 at 25°C are chosen from ethers.
In particular, the ethers that may be used as liquid organic compounds with a Hansen
solubility parameter as described above may be propylene glycol butyl ether,
dipropylene glycol methyl ether, tripropylene glycol methyl ether or propylene glycol
propyl ether.
Preferably, the liquid organic compound(s) with a Hansen solubility parameter value
of less than 16 (MPa) 2 at 25°C are chosen from benzyl alcohol, preferably benzyl
alcohol.
The liquid organic compound(s) with a Hansen solubility parameter of less than 16
(MPa) 2 at 25°C may be present in the composition containing them in a content of
greater than or equal to 0.5% by weight, preferably in a content of greater than or equal
to 1% by weight, more preferentially in a content ranging from 1% to 40% by weight and
better still from 5% to 30% by weight relative to the total weight of the composition
containing them.
e chemical oxidizing agent(s)
According to a particular embodiment of the invention, the dyeing process also uses
one or more chemical oxidizing agents. The term "chemical oxidizing agent" means an
oxidizing agent other than atmospheric oxygen. More particularly, the dyeing process
uses i) hydrogen peroxide; ii) urea peroxide; iii) polymeric complexes that can release
hydrogen peroxide, such as polyvinylpyrrolidone/H 202, provided in particular in the form
of powders, and the other polymeric complexes described in US 5 008 093, US 3 376
110 and US 5 183 901 ; iv) oxidases in the presence of an appropriate substrate (for
example, glucose in the case of glucose oxidase or uric acid with uricase); v) metal
peroxides which generate hydrogen peroxide in water, such as calcium peroxide or
magnesium peroxide; vi) perborates; and/or vii) percarbonates.
According to a preferred embodiment of the invention, the composition comprises one
or more chemical oxidizing agents chosen from i) urea peroxide; ii) polymeric complexes
which can release hydrogen peroxide chosen from polyvinylpyrrolidone/H 202; iii)
oxidases; iv) perborates and v) percarbonates.
In particular, the dyeing process uses hydrogen peroxide.
Moreover, the composition(s) comprising hydrogen peroxide or a hydrogen peroxidegenerating
system may also include various adjuvants conventionally used in
compositions for dyeing keratin fibres as defined below.
According to a particular embodiment of the invention, the chemical oxidizing agent(s)
used preferably represent from 0.001% to 12% by weight of chemical oxidizing agents (of
hydrogen peroxide) relative to the total weight of the composition(s) containing it or them,
and even more preferentially from 0.2% to 2.7% by weight.
f) basifying agent(s)
According to a particular embodiment of the invention, the dyeing process uses one or
more basifying agents f). These are base(s) that can increase the pH of the
composition(s) in which they are present. The basifying agent is a Bransted, Lowry or
Lewis base. It may be mineral or organic.
Particularly, said agent is chosen from i) (bi)carbonates, ii) aqueous ammonia, iii)
alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and
derivatives thereof, iv) oxyethylenated and/or oxypropylenated ethylenediamines, v)
mineral or organic hydroxides, vi) alkali metal silicates such as sodium metasilicate, vii)
amino acids, preferably basic amino acids such as arginine, lysine, ornithine, citrulline
and histidine, and viii) the compounds of formula (XIII) below:
N- W - N
c d (XIII)
in which formula (XIII) W is a divalent (CrC 8)alkylene radical optionally substituted with at
least one hydroxyl group or at least one (CrC 4)alkyl radical and/or optionally interrupted
with at least one heteroatom, such as oxygen or sulfur, or with an -N(R e)- group; Ra, Rb,
Rc, R and Re, which may be identical or different, represent a hydrogen atom or a (C
C4)alkyl or hydroxy(Ci-C 4)alkyl radical; preferably, W represents a propylene radical. The
mineral or organic hydroxides are preferably chosen from a) hydroxides of an alkali
metal, b) hydroxides of an alkaline-earth metal, for instance sodium hydroxide or
potassium hydroxide, c) hydroxides of a transition metal, such as hydroxides of metals
from groups III, IV, V and VI, d) hydroxides of lanthanides or actinides, quaternary
ammonium hydroxides and guanidinium hydroxide.
The hydroxide may be formed in situ, for instance guanidine hydroxide, formed by
reacting calcium hydroxide with guanidine carbonate.
The term "(bi)carbonates" i) is understood to mean:
a) carbonates of alkali metals (Met2
+, C0 3
2 ) , of alkaline-earth metals (Met' 2+, C0 3
2 ) of
ammonium ((R"4N+)2,C0 3
2 ) or of phosphonium ((R"4P+)2,C0 3
2 with Met'
representing an alkaline-earth metal and Met representing an alkali metal, and R",
which may be identical or different, represent a hydrogen atom or an optionally
substituted (CrC 6)alkyl group such as hydroxyethyl); and
b) bicarbonates, also known as hydrogen carbonates, of the following formulae:
> R'+, HC03 , with R' representing a hydrogen atom, an alkali metal, an ammonium
group R"4N+- or a phosphonium group R"4P+- , where R", which may be identical
or different, represent a hydrogen atom or an optionally substituted (CrC 6)alkyl
group, such as hydroxyethyl, and, when R' represents a hydrogen atom, the
hydrogen carbonate is then known as dihydrogen carbonate (C02, H20); and
> Met'2+ (HC03 )2, with Met' representing an alkaline-earth metal.
More particularly, the basifying agent is chosen from alkali metal or alkaline-earth
metal (bi)carbonates and amino acids such as arginine; preferentially alkali metal
(bi)carbonates and amino acids.
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. patent, for example the document FR
2 814 943). Mention may in particular be made of sodium carbonate [497-19-8] =
Na2C0 3, sodium hydrogen carbonate or sodium bicarbonate [144-55-8] = NaHC0 3, and
sodium dihydrogen carbonate = Na(HC0 3 )2-
According to a particularly advantageous embodiment, the basifying agent(s) f) are
chosen from amino acids, such as arginine, and (bi)carbonates, in particular alkali metal
or alkaline-earth metal (bi)carbonates, alone or as mixtures. They are preferentially
together during the dyeing process.
The basifying agent(s) as defined above preferably represent from 0.001% 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.
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 e) 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.
The compositions:
The compositions according to the invention generally comprise 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.
The compositions according to the invention may optionally comprise an organic
solvent other than the liquid organic compound(s) which have a Hansen solubility
parameter value of less than 16 (MPa) 2 at 25°C d) as defined previously.
The 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 other than the
cellulose-based polysaccharides c) as defined previously, mineral or organic thickeners
other than the cellulose-based polysaccharides c) as defined previously, 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 dyeing process of the invention may also use, in addition to compounds a), b),
optionally c) and optionally d), at least one other particular carboxylic acid of formula (I)
as defined previously. More particularly, the carboxylic acid(s) of formula (I) are such that
A represents a monovalent ( -C6)alkyl or polyvalent (CrC 6)alkylene group optionally
substituted with one or more hydroxyl groups, and n represents an integer between 0 and
5, such as between 0 and 2, inclusive.
More particularly, the carboxylic acid(s) of the invention are chosen from the acids of
formula (I) having a solubility in water of greater than or equal to 1% by weight at 25°C
and at atmospheric pressure.
Preferably, the acids of formula (I) comprise at least one hydroxyl group in their
structure. Even more preferentially, the acid is chosen from a-hydroxy acids. The
preferred acids of the invention are chosen from glycolic acid, lactic acid, tartaric acid and
citric acid.
The salts of the acids of formula (I) may be salts of organic or mineral bases, such as
sodium hydroxide, aqueous ammonia or potassium hydroxide, or salts of organic amines,
such as alkanolamines. The acids of formula (I) or salts thereof are present in the
composition(s) containing them in a content ranging from 0.1% to 20% by weight.
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
0.01% 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
optional 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).
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):
According to a preferred embodiment of the invention, the pH of at least one of the
cosmetic compositions comprising at least one of the ingredients a), b), c), d) and e) is
acidic, i.e. less than 7.0, preferably less than 5.0, in particular at a pH of between 0 and 4
inclusive, more particularly between 0.5 and 3.5.
According to one embodiment, the pH of the cosmetic composition(s) comprising one
or more alkaline agents preferably chosen from (bi)carbonates is alkaline, i.e. greater
than 7, preferably of between 8 and 12 and more particularly of between 8 and 10.5
inclusive.
When the process according to the invention uses one or more ODP dyes, the
composition containing the ODP(s) a) preferably has an acidic pH of less than 7,
preferably less than 5, in particular a pH between 0 and 4 inclusive and better still
between 1 and 3.
According to a particular embodiment of the invention, the composition containing the
titanium salt(s) b) and not containing (bi)carbonates has a pH of less than 7 and
preferably of less than 5, in particular a pH between 0 and 4 inclusive, more particularly
between 0.5 and 3.5.
The pH of these compositions may be adjusted to the desired value by means of
basifying agents as defined previously in f) 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, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid,
citric acid or lactic acid, or sulfonic acids.
The term "carboxylic acid" means a compound comprising at least one carboxylic acid
-C(0)-OH group, preferably of formula (I) as defined previously, preferably comprising
between 1 and 4 carboxylic acid groups, such as 1 or 2; or 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 heterocylic group, such as pyrrolidone, it being
possible for the alkyl or het group to be optionally substituted with one or more groups
chosen especially from OH, and (di )(Ci-C6)(alkyl)amino.
Dyeing process in one or more steps
The process for dyeing keratin fibres consists in treating, in one or more steps, with
one or more cosmetic compositions containing the following ingredients, taken together
or separately in said composition(s):
a) one or more dyes chosen from synthetic direct dyes and dyes of natural origin as
defined previously, preferably chosen from the ODPs as defined previously;
b) one or more titanium salts; optionally b1) one or more carboxylic acids of formula (I)
as defined previously;
c) one or more cellulose-based polysaccharides as defined previously;
d) optionally one or more liquid organic compounds which have a Hansen solubility
parameter value of less than 16 (MPa) 2 at 25°C and preferably less than or
equal to 15 (MPa) 2 ;
e) optionally one or more chemical oxidizing agents chosen especially from hydrogen
peroxide or one or more hydrogen peroxide-generating systems;
preferably, the composition or at least one of the compositions used in the dyeing
process is at acidic pH, i.e. less than 7, preferably less than 5, in particular at a pH of
between 0 and 4 inclusive.
According to a particular embodiment of the invention, the dyeing process is
performed in at least two steps which comprise a first step in which the keratin fibres are
treated with a cosmetic composition comprising a) one or more dyes chosen from
synthetic direct dyes and dyes of natural origin, preferably one or more ODPs as defined
previously, b) one or more titanium salts and optionally b1) one or more carboxylic acids
as defined previously, c) one or more cellulose-based polysaccharides as defined
previously, and d) optionally one or more liquid organic compounds with a Hansen
solubility parameter value <16 (MPa) 2 at 25°C, preferably less than or equal to 15
(MPa) 2 ; followed by a second step in which an alkaline cosmetic composition, i.e. a
composition whose pH is greater than 7, preferably between 8 and 12 and in particular
between 8 and 10.5, which comprises e) one or more basifying agents and optionally f)
one or more chemical oxidizing agents, is applied.
Preferentially, the composition comprising a) + b) +c) + optionally d) and optionally
b1) and optionally e) is at acidic pH, i.e. less than 7, preferably less than 5, in particular at
a pH of between 1 and 3 inclusive.
Preferentially, the cosmetic composition applied to the keratin fibres during the
second step also comprises e) one or more chemical oxidizing agents chosen especially
from hydrogen peroxide and one or more hydrogen peroxide-generating systems,
preferably hydrogen peroxide.
The leave-on time after applying the composition comprising the dye(s), especially the
ODP(s) as defined previously, is generally set at between 3 and 120 minutes,
preferentially between 10 and 60 minutes and more preferentially between 15 and 45
minutes.
According to a 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 ingredients a), b), b 1) , c) and optionally d) as defined previously and then, in a
second step, a composition comprising ingredient e) and optionally ingredient f) 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 dye(s),
especially the ODP(s) a) is aqueous. Even more preferentially, the two compositions
used in this embodiment are aqueous.
According to a particular embodiment of the invention, the dyeing process is
performed in several steps by applying to the keratin fibres, in a first step, a cosmetic
composition comprising:
a) one or more ODPs as defined previously, especially chosen from:
- haematein, brazilein, gallic acid or tannic acid, when the dyeing process does not use
a chemical oxidizing agent e);
or else
- haematoxylin or brazilin, when the dyeing process uses a chemical oxidizing agent e);
b) one or more organic titanium salts as defined previously; advantageously, ingredient b)
is chosen from Ti(IV) salts or complexes; b 1) optionally one or more carboxylic acids
of formula (I) as defined previously; and
c) one or more cellulose-based polysaccharide(s) as defined previously;
d) optionally one or more organic compounds that are liquid at 25°C with a solubility
parameter value of less than 16 (MPa)½ at 25°C as defined previously;
and then, in a second step, applying to said fibres a cosmetic composition comprising:
e) optionally one or more chemical oxidizing agents chosen from hydrogen peroxide or
one or more hydrogen peroxide-generating systems as defined previously; f) one or
more basifying agents chosen from amino acids and (bi)carbonates, in particular alkali
metal or alkaline-earth metal (bi)carbonates, alone or as a mixture;
it being understood that:
- preferentially, the composition comprising a) + b) + c) + optionally d) and optionally b1)
is at acidic pH, i.e. less than 7, preferably less than 5, in particular at a pH of between 1
and 3 inclusive; and
- the composition comprising the basifying agent(s) is at alkaline pH, preferably of
between 8 and 12 and more particularly of between 8 and 10.
For this dyeing 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 the ingredient e) during the second step is generally set at
between 3 and 120 minutes, preferably between 3 and 60 minutes and more preferably
between 5 and 30 minutes.
According to another embodiment, the process for dyeing keratin fibres is performed
in two or three steps.
According to this embodiment, the process for dyeing keratin fibres is performed in
several steps by applying to the keratin fibres, in a first step, a cosmetic composition
comprising:
a) one or more dyes chosen from synthetic direct dyes and dyes of natural origin, in
particular one or more ODPs, especially chosen from:
- haematein, brazilein, gallic acid or tannic acid, when the dyeing process does not use
a chemical oxidizing agent e);
or else
- haematoxylin or brazilin, when the dyeing process uses a chemical oxidizing agent e);
b) one or more titanium salts as defined previously, and
b1) optionally one or more carboxylic acids of formula (I) as defined previously with A
representing a monovalent ( -C6)alkyl or polyvalent (CrC 6)alkylene group optionally
substituted with one or more hydroxyl groups, and n representing an integer between
0 and 5, such as between 0 and 2, inclusive; more particularly, the carboxylic acid or
acids of the invention are chosen from citric acid, lactic acid, glycolic acid and tartaric
acid;
and then, in a second step, applying to said fibres a cosmetic composition comprising:
c) one or more cellulose-based polysaccharides as defined previously, which are
particularly nonionic and non-associative, preferably chosen from hydroxy(Cr
C4)alkylcelluloses such as hydroxyethylcelluloses (HEC);
d) optionally one or more liquid organic compounds with a Hansen solubility parameter
value of < 16 (MPa) 2 at 25°C, preferably chosen from aromatic alcohols such as
benzyl alcohol;
e) optionally one or more chemical oxidizing agents chosen from hydrogen peroxide or
one or more hydrogen peroxide-generating systems;
f) one or more basifying agent(s) chosen from amino acids, such as arginine, and
(bi)carbonates, in particular alkali metal or alkaline-earth metal (bi)carbonates, alone
or as mixtures;
it being understood that:
- preferentially, the composition comprising a) + b) and optionally b1) is at acidic pH, i.e.
less than 7, preferably less than 5, in particular at a pH of between 1 and 3 inclusive; and
- the composition comprising the basifying agent(s) is at alkaline pH, preferably of
between 8 and 12 and more particularly of between 8 and 10.
In particular, the dyeing process of the invention is performed in at least two steps: in the
first step, ingredients a), b) and c) and optionally d) are applied together to the keratin
fibres, in particular the hair, and then, in the second step, ingredients e) and f) are applied
together to said fibres.
Irrespective of the application method, the application temperature is generally
between room temperature (15 to 25°C) and 220°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 for smoothing the head of 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, it is possible to perform rinsing or mechanical
wiping and/or drying of the keratin fibres between each step, in particular before
performing the final step comprising the application of a composition containing the
ingredient e).
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 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
present in one or more compositions used in the process of the invention, comprising or
not comprising one or more ingredients a) to e) 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.
A particular embodiment of the invention relates to a dyeing process which is
performed at room temperature (25°C).
In all the particular forms and variants of the processes previously described, the
compositions mentioned are ready-to-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 of the invention is a multi-compartment dyeing device or "kit".
Advantageously, this kit comprises from 2 to 5 compartments comprising from 2 to 5
compositions in which are distributed the ingredients a) to e) as defined above, which can
be aqueous or pulverulent, with in particular at least one of said compositions being
aqueous.
According to a first variant, the kit comprises five compartments, the first four
compartments respectively comprising ingredients a), b), c) and f) as defined previously
and the fifth compartment containing an aqueous oxidizing composition, such as water
comprising e) as defined previously. Optionally, d) and/or b1) are preferably contained
with a).
In this other embodiment, at least one of the four compositions is aqueous and the
dye(s), in particular the ODP(s), may be in powder form.
In another kit variant, this kit comprises two compartments, in which the first
composition contained in the first compartment comprises a), b) and c) and the second
compartment comprises e) in powder form or in aqueous medium; preferably, the second
composition is aqueous.
In another kit variant, this kit comprises four compartments, in which the first
composition contained in the first compartment comprises a), the second compartment
comprises b), the third compartment comprises e) and the fourth compartment comprises
f)-
Compound c) may be in any compartment, but preferably with a). Compound d) is
preferably with a), and compound b 1) is preferably with b).
In another kit variant, this kit comprises three compartments, in which the first
composition contained in the first compartment comprises a), the second compartment
comprises e) in powder form or in aqueous medium; preferably, the second composition
is aqueous and the third compartment comprises f).
Compound b) may be in any compartment, but preferably with a). Compound b) is
with a) or e) and preferably with a). Compound d) is preferably with a).
According to a particular embodiment of the invention, the kit comprises five separate
compartments in which the first compartment contains a) one or more dyes chosen from
synthetic direct dyes and dyes of natural origin, preferably chosen from the ODPs as
defined previously, the second compartment contains b) the Ti salt(s) as defined
previously, and optionally b 1) one or more carboxylic acids as defined previously, the
third compartment contains c) one or more cellulose-based polysaccharides as defined
previously, the fourth compartment contains e) one or more chemical oxidizing agents as
defined previously, especially hydrogen peroxide, and a fifth compartment comprises f )
one or more alkaline agents, it being understood that the solvent d) as defined previously
may optionally be in at least one of the five compartments.
According to a particular embodiment of the invention, the kit comprises four separate
compartments in which the first compartment contains a) one or more dyes chosen from
synthetic direct dyes and dyes of natural origin, preferably chosen from the ODPs as
defined previously, the second compartment contains b) the Ti salt(s) as defined
previously, and optionally b 1) one or more carboxylic acids as defined previously, the
third compartment contains e) one or more chemical oxidizing agents as defined
previously, especially hydrogen peroxide, and a fourth compartment comprises f) one or
more alkaline agents, it being understood that:
- c) one or more cellulose-based polysaccharides as defined previously are in at least
one of the four compartments, and
- the solvent d) as defined previously may optionally be in at least one of the four
compartments.
According to a particular embodiment of the invention, the kit comprises three
separate compartments in which the first compartment contains a) one or more dyes
chosen from synthetic direct dyes and dyes of natural origin, preferably chosen from the
ODPs as defined previously, the second compartment contains e) one or more chemical
oxidizing agents as defined previously, especially hydrogen peroxide, and a third
compartment comprises f) one or more alkaline agents, it being understood that:
- b) the Ti salt(s) as defined previously, and optionally b 1) one or more carboxylic acids
as defined previously, are with the dye(s) or with the chemical oxidizing agent(s), in
particular H20 2; preferably, the Ti salt(s) are with the dye(s),
- c) one or more cellulose-based polysaccharides as defined previously are in at least
one of the three compartments, preferably with the dye(s), and
- the solvent d) as defined previously may optionally be in at least one of the three
compartments.
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.
A subject of the invention is also the use of said cosmetic dye composition for dyeing
keratin fibres.
A subject of the invention is also a cosmetic composition for dyeing keratin fibres,
containing compounds a), b), b 1) , c), d) and e) as defined previously.
For the purposes of the present invention, the term "build-up" of the colour of keratin
fibres means the variation in colouring between locks of undyed grey hair and locks of
dyed hair.
The example that follows serves to illustrate the invention without, however, being
limiting in nature.
Examples of dyeing
Example 1:
The following compositions are prepared from the following ingredients in the following
proportions, indicated in grams per 100 grams of composition:
Dyeing composition:
Developing composition:
The dye compositions 1 to 3 and then composition B are applied with a brush to
permanent-waved Caucasian hair containing 90% white hairs.
Compositions 1 to 3 are then left on for a time of 45 minutes at 40°C and composition B is
left on for a time of 15 minutes at 40°C. Rinsing is performed before applying composition
B.
After these leave-on times, the locks are washed with Elvive Multivitamin shampoo,
rinsed and then dried under a hood.
Dyeing results
It is found that very strongly coloured black locks are obtained, which is corroborated by
the colorimetric measurements below. In addition, it is seen that the colouring is visually
homogeneous and persistent with respect to successive shampooing.
The colour of the locks was evaluated in the CIE L* a* b* system using a Minolta
Spectrophotometer CM3600D 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* ) .
Colour build-up:
The variation in colouring between the locks of permanent-waved Caucasian hair
containing 90% white hairs, before and after treatment or dyeing, is defined by (* )
according to the following equation:
AE* = ( * - *)2 + (a* - a0 *) 2 + (b*-b 0 *) 2
In this equation, L* , a* and b* represent the values measured on locks of hair after dyeing
and L0
* , a0
* and b0
* represent the values measured on locks of undyed virgin hair. The
higher the * value, the better the colour build-up.
The results L, a, b of colour build-up are collated in the table below:
After the keratin fibres have been treated with compositions 1 to 3, the locks obtained are
a very strong and intense black.
Example 2:
The following dye compositions are prepared according to the same protocol as in
Example 1:
D ein com osition:
Very strongly coloured red locks (composition 4) and violet locks (composition 5) are
obtained.
CLAIMS
1. 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 dyes chosen from synthetic direct dyes and/or dyes of natural origin,
preferably chosen from ortho-diphenols (ODPs);
b) one or more titanium salts;
optionally b 1) one or more carboxylic acids of formula (I) below:
formula (I) and a salt thereof, in which:
- A represents a monovalent group when n has the value 0 or a polyvalent group
when n is greater than or equal to 1, saturated or unsaturated, cyclic or non-cyclic
and aromatic or non-aromatic hydrocarbon-based group comprising from 1 to 50
carbon atoms which is optionally interrupted with one or more heteroatoms and/or
optionally substituted, in particular with one or more hydroxyl groups; preferably, A
represents a monovalent ( -C6)alkyl group or a polyvalent (CrC 6)alkylene group
optionally substituted with one or more hydroxyl groups;
- n represents an integer between 0 and 10 inclusive; preferably, n is between 0
and 5, such as 0, 1 or 2;
c) one or more cellulose-based polysaccharides;
d) optionally one or more organic compounds that are liquid at 25°C with a Hansen
solubility parameter value of less than 16 (MPa)½at 25°C; and
e) optionally one or more chemical oxidizing agents chosen especially from hydrogen
peroxide or one or more hydrogen peroxide-generating systems.
2. Dyeing process according to Claim 1, characterized in that at least one of the
compositions used in the dyeing process is at acidic pH, i.e. less than 7.0, preferably less
than 5, in particular at a pH of between 0 and 4 inclusive.
3. Dyeing process according to either of the preceding claims, characterized in that
ingredient a) is an ODP comprising an aromatic ring, this aromatic ring being chosen from
benzene, naphthalene, tetrahydronaphthalene, indane, indene, anthracene,
phenanthrene, isoindole, indoline, isoindoline, benzofuran, dihydrobenzofuran, chroman,
isochroman, chromene, isochromene, quinoline, tetrahydroquinoline and isoquinoline,
said aromatic ring comprising at least two hydroxyl groups borne by two contiguous
adjacent atoms of the aromatic ring.
4. Dyeing process according to any one of the preceding claims, characterized in
that ingredient a) is an ODP of formula (II) below, or an oligomer, tautomer, optical isomer
or geometrical isomer thereof, and also salts or solvates thereof, such as hydrates:
in which formula (II):
• R to R4, which may be identical or different, represent: i) a hydrogen atom, ii) a
halogen atom, or a group chosen from iii) hydroxyl, iv) carboxyl, v) (CrC 2o)alkyl
carboxylate or (CrC 2o)alkoxycarbonyl, vi) optionally substituted amino, vii) optionally
substituted linear or branched (CrC 2o)alkyl , viii) optionally substituted linear or
branched (C2-C2o)alkenyl, ix) optionally substituted cycloalkyl, x) (CrC 20)alkoxy, xi)
(Ci-C20)alkoxy (Ci-C20)alkyl, xii) (CrC 20)alkoxyaryl, xiii) aryl which may optionally be
substituted, xiv) aryl, xv) substituted aryl, xvi) heterocyclic which is saturated or
unsaturated, optionally bearing a cationic or anionic charge and which is optionally
substituted and/or optionally fused with an aromatic ring, preferably a benzene ring,
said aromatic ring optionally being substituted, in particular with one or more hydroxyl
or glycosyloxy groups, xvii) a radical containing one or more silicon atoms;
or two of the substituents borne by two adjacent carbon atoms R - R2, R2 - R3 or R3 -
R4 form, together with the carbon atoms bearing them, a saturated or unsaturated and
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; in particular, R to R4 together form from one to four rings; more
particularly, R2 and R3 form a pyrrolyl or pyrrolidinyl radical fused to the benzene ring
bearing the two hydroxyls;
in particular, the ODP(s) a) are chosen from:
- flavanols, for instance catechin and epicatechin gallate,
- flavonols, for instance quercetin,
- anthocyanidins, for instance cyanidin, delphinidin and petunidin,
- anthocyanins or anthocyans, for instance myrtillin,
- ortho-hydroxybenzoates, for example gallic acid salts,
- flavones, for instance luteolin,
- 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 A 1, A2, B 1, B2, B3 and C 1,
- chromans and chromenes,
- proanthocyanins,
- tannic acid,
- ellagic acid,
- and mixtures of the preceding compounds;
preferably, the ortho-diphenol(s) are chosen from haematein, brazilein, gallic acid, tannic
acid, haematoxylin, brazilin and mixtures thereof.
5. Dyeing process according to either of Claims 3 and 4, characterized in that the
natural ODP(s) a) are chosen from extracts of animals, of bacteria, of fungi, of algae, of
plants and of fruit.
6. Dyeing process according to any one of the preceding claims, characterized in
that the acid(s) b1) are present and are of formula (I) with A representing a monovalent
(CrC 6)alkyl or polyvalent (CrC 6)alkylene group optionally substituted with one or more
hydroxyl groups, and n representing an integer between 0 and 5, such as 0, 1 or 2; in
particular, the carboxylic acid or acids of the invention are chosen from ohydroxy acids;
preferentially, the acid(s) b 1) are chosen from citric acid , lactic acid, tartaric acid and
glycolic acid .
7. Dyeing process according to any one of the preceding claims, in which the acid(s)
b 1) of formula ( I) or the salts thereof are present in the composition(s) containing them in
a content ranging from 0.1% to 20% by weight.
8. Dyeing process according to any one of the preceding claims, characterized in
that the titanium salt(s) are chosen from organic or mineral titanium salts, preferably from
organic titanium salts, and in particular in which the titanium is of oxidation state 2, 3 or 4,
preferably of oxidation state 4.
9. Dyeing process according to the preceding claim, characterized in that the organic
titanium salt(s) b) are derived from the reaction of organic acid(s) with titanium, in which
the organic acid(s) are chosen from organic acids comprising:
a) at least one optionally unsaturated, linear or branched Ci-C 2o hydrocarbon-based
chain , or a (hetero)cycloalkyl or (hetero)aryl group, and
b) at least one acid chemical function chosen in particular from carboxyl COOH,
sulfuric S0 3H, S0 2H, and phosphoric P0 3H2, P0 4H2;
preferably, the organic acid(s) are chosen from the carboxylic acids of formula (I) as
defined in Claim 1 or 7, better still from citric acid, lactic acid, tartaric acid and glycolic
acid and more particularly lactic acid and glycolic acid.
10. Dyeing process according to any one of the preceding claims, characterized in
that the acid(s) b 1) are of formula (I) as defined in Claim 1 or 6 and these acids are
different from the organic acid(s) of the titanium salt as defined in Claim 8 or 9.
11. Dyeing process according to any one of the preceding claims, characterized in
that the organic titanium s rmula (l-A) below:
n
in which formula (l-A):
• A is as defined in Claim 1 or 6;
• n, n' and n", which may be identical or different, are equal to 1, 2, 3 or 4 with n' + n" =
6;
• M and M2, which may be identical or different, represent a cationic counterion such as
a cation of an alkali metal such as Na or K or of an alkaline-earth metal such as Ca or
an organic cation such as ammonium, preferably ammonium or a hydrogen atom;
• TiY represents Ti(OH) , Ti(0) n"/2 or Ti(OH)m1(0) m2 with mi+m2 = n";
preferably, the organic titanium salt(s) of the dyeing process are
dihydroxybis(lactato)titanium(IV) salts such as those having the following formula:
12. Dyeing process according to any one of the preceding claims, characterized in
that said process uses c) one or more associative or non-associative nonionic cellulosebased
polysaccharides; in particular, the cellulose-based polysaccharide(s) c) are nonassociative
and nonionic, preferably chosen from nonionic cellulose ethers: (C
C4)alkylcelluloses such as methylcelluloses and ethylcelluloses; (poly)hydroxy(d-
C4)alkylcelluloses such as hydroxymethylcelluloses, hydroxyethylcelluloses and
hydroxypropylcelluloses; (poly)hydroxy(Ci-C 4)alkyl(Ci-C 4)alkylcellulose mixed celluloses
such as hydroxypropyl-methylcelluloses, hydroxyethyl-methylcelluloses, hydroxyethylethylcelluloses
and hydroxybutyl-methylcelluloses; more preferentially, the cellulosebased
polysaccharide(s) c) are chosen from hydroxyalkylcelluloses, in particular
hydroxy(CrC 4)alkylcelluloses, and especially chosen from hydroxymethylcelluloses,
hydroxyethylcelluloses and hydroxypropylcelluloses, in particular nonionic
hydroxyethylcelluloses.
13. Dyeing process according to any one of the preceding claims, characterized in
that said process uses d) one or more organic compounds that are liquid at 25°C with a
solubility parameter value of less than 16 (MPa)½ at 25°C, preferably chosen from
organic solvents, especially chosen from :
-propylene glycol derivatives such as propylene glycol butyl ether, dipropylene glycol
methyl ether, tripropylene glycol methyl ether or propylene glycol propyl ether,
propylene glycol n-butyl ether, dipropylene glycol monomethyl ether acetate ;
- aromatic alcohols, preferably phenyl alcohols such as benzyl alcohol, 3-phenyl-1-
propanol or 2-phenyl-1-ethanol ;
-alkylene carbonates ;
-lactones, in particular the lactones of formula (D1)
(D1)
in which formula (D1):
• n is 1, 2 or 3;
• R' represents a hydrogen atom; a linear or branched CrC 8 alkyl radical; a linear or
branched Ci-C4 hydroxyalkyl radical;
-alcohols such as 1-Decanol or 1-Octanol;
- ethers such as ethylene glycol 2-ethylhexyl ether ;
-and/or a mixture of these compounds.
14. Dyeing process according to any one of the preceding claims, characterized in
that said process uses d) one or more organic compounds that are liquid at 25°C with a
solubility parameter value of less than 16 (MPa)½ at 25°C, are chosen from alcohols,
aromatic alcohols, in particular from benzyl alcohol, ethers, propylene glycol derivatives,
and/or a mixture of these compounds, preferably chosen from aromatic alcohols such as
benzyl alcohol.
15. Dyeing process according to any one of the preceding claims, characterized in
that said process uses e) one or more chemical oxidizing agents chosen from hydrogen
peroxide or one or more hydrogen peroxide-generating systems, in particular chosen
from hydrogen peroxide or urea peroxide, preferably hydrogen peroxide.
16. Dyeing process according to any one of the preceding claims, characterized in
that the dyeing process uses f) one or more basifying agents chosen in particular from: i)
(bi)carbonates, ii) aqueous ammonia, iii) alkanolamines, such as monoethanolamine,
diethanolamine, triethanolamine and derivatives thereof, iv) oxyethylenated and/or
oxypropylenated ethylenediamines, v) mineral or organic hydroxides, vi) alkali metal
silicates, such as sodium metasilicates, vii) amino acids, preferably basic amino acids
such as arginine, lysine, ornithine, citrulline and histidine, and viii) the compounds of
formula (XIII) below:
N - W - N
(XIII)
in which formula (XIII) W is a divalent (CrC 8)alkylene radical optionally substituted with
at least one hydroxyl group or at least one (CrC 4)alkyl radical and/or optionally
interrupted with at least one heteroatom, such as oxygen or sulfur, or with a group -
N(Re)-; Ra, Rb, Rc, R and Re, which may be identical or different, represent a hydrogen
atom or a (Ci-C4)alkyl or hydroxy(Ci-C 4)alkyl radical; preferentially, W represents a
propylene radical; preferably, the basifying agent(s) are chosen from (bi)carbonates
and amino acids, alone or as mixtures.
17. Dyeing process according to any one of the preceding claims, characterized in
that said process is performed in at least two steps which comprise a first step in which
the keratin fibres are treated with a cosmetic composition comprising a) one or more dyes
chosen from synthetic direct dyes and/or dyes of natural origin, especially ODPs as
defined in any one of Claims 1 to 5, b) one or more titanium salts chosen especially from
the organic titanium salts as defined in any one of Claims 1, 8, 9 and 11; b 1) one or more
carboxylic acids of formula (I) as defined in any one of Claims 1, 6 and 10; c) one or more
cellulose-based polysaccharides as defined in Claim 1 or 12 and optionally d) one or
more organic compounds that are liquid at 25°C with a solubility parameter value of
less than 16 (MPa)½ at 25°C as defined in Claim 1, 13 or 14; followed by a second step in
which an alkaline cosmetic composition, i.e. a composition whose pH is greater than 7,
preferably between 8 and 12 inclusive and in particular between 8 and 10.5, which
comprises f) one or more basifying agents as defined in Claim 16, is applied;
preferentially, the cosmetic composition applied to the keratin fibres during the second
step also comprises e) one or more chemical oxidizing agents as defined in Claim 15,
chosen in particular from hydrogen peroxide or one or more hydrogen peroxidegenerating
systems, preferably hydrogen peroxide.
18. Dyeing process according to the preceding claim, performed in several steps by
applying to the keratin fibres, in a first step, a cosmetic composition comprising:
a) one or more ODPs as defined in any one of Claims 1 to 5, chosen especially from:
- haematein, brazilein, gallic acid or tannic acid, when the dyeing process does not use
a chemical oxidizing agent e);
or else
- haematoxylin or brazilin, when the dyeing process uses a chemical oxidizing agent e);
b) one or more organic titanium salts as defined in any one of Claims 1, 8, 9 and 11;
advantageously, ingredient b) is chosen from Ti(IV) salts or complexes; b 1) optionally
one or more carboxylic acids of formula (I) as defined in any one of Claims 1, 6 and
10; and
c) one or more cellulose-based polysaccharides as defined in either of Claims 1 and 12;
d) optionally one or more organic compounds that are liquid at 25°C with a solubility
parameter value of less than 16 (MPa)½ at 25°C as defined in Claim 1,13 or 14;
and then, in a second step, applying to said fibres a cosmetic composition comprising:
e) optionally one or more chemical oxidizing agents chosen from hydrogen peroxide or
one or more hydrogen peroxide-generating systems as defined in Claim 15; f ) one or
more basifying agents chosen from amino acids and (bi)carbonates, in particular alkali
metal or alkaline-earth metal (bi)carbonates, alone or as a mixture;
it being understood that:
- preferentially, the composition comprising a) + b) +c) + optionally d) and optionally b 1) is
at acidic pH, i.e. less than 7, preferably less than 5, in particular at a pH of between 1 and
3 inclusive; and
- the composition comprising the basifying agent(s) is at alkaline pH, preferably of
between 8 and 12 and more particularly of between 8 and 10.
19. Cosmetic composition for dyeing keratin fibres, containing compounds a), b), b 1) ,
c), d) and e) as defined according to any one of Claims 1 to 18.
20. Multi-compartment device comprising from 2 to 5 compartments containing from 2
to 5 compositions, in which are distributed the ingredients a), b), b1), c), d) and e) as
defined according to any one of Claims 1 to 18, said compositions being aqueous or
pulverulent, with at least one of these compositions being aqueous.