COSMETIC ARTICLE FOR DRY-DYEING THE HAIR, USE THEREOF AND
PROCESS FOR USING THE SAID ARTICLE
The present invention relates to a cosmetic article for dyeing
keratin materials, especially human keratin materials, via dry heat
transfer. The invention furthermore relates to a process for dyeing
keratin materials using this dry heat-transfer cosmetic article. The
invention also relates to the use of this article for dyeing keratin
materials, especially human keratin materials, via dry heat transfer.
The invention more particularly relates to the field of dyeing
human keratin fibres, and especially the hair.
It has been known for a long time how to modify the colour of
the hair, and in particular how to mask white hairs.
Essentially, two types of techniques used for dyeing human
keratin fibres are known.
The first method, known as direct or semi-permanent dyeing,
consists in changing or providing colour by applying a coloured
molecule that penetrates diffusively into the fibre and/or remains
adsorbed on its surface.
The second method, known as oxidative dyeing or permanent
dyeing, consists in changing or providing colour by performing, inside
the fibre itself, an oxidative condensation of dye precursors, which are
uncoloured or sparingly coloured compounds. After this reaction, the
dyes formed are insoluble and are trapped inside the fibre.
The two methods summarized above allowed access to a wide
range of colours.
The dye composition is generally in various forms, such as a
lotion, a mousse, a cream or a gel. However, most of these forms have
the drawback of running onto the face or onto areas that it is not desired
to dye. Furthermore, the use of these products is generally soiling, to
clothing, hairstyling accessories (combs, towels, etc.), tanks, etc.
Moreover, the duration of the dyeing process is long. The
reason for this is that, after the leave-on time of the dye composition, it
-2-

is necessary to rinse the hair thoroughly, or even to perform a shampoo
wash, and to dry it.
Finally, the use certain dyes that afford advantageous dyeing
performance on the fibres is occasionally limited on account of their
poor solubility in the aqueous formulation supports.
As may be observed, the search continues for methods for
dyeing human keratin materials, which, while allowing effective
colorations to be obtained, do not have the drawbacks mentioned above.
Recently, in its patent applications FR 0502034, FR 0502030
and FR 0502031, the Applicant has discovered that it is possible to dye
the hair using dyeing powders via heat transfer.
It has been demonstrated that certain direct dyes can colour the
hair simply by transferring dye from a dry composition onto the hair
under the action of the temperature, without using a liquid vehicle
support. Moreover, still by virtue of the fact that the dye is initially used
in solid form, there is no need either for rinsing or for shampooing
and/or drying of the keratin fibres. Moreover, since the heat transfer is
rapid (a few minutes), the leave-on times are short.
This novel dyeing technique via dry heat transfer uses a dye
composition that is in the form of a dry polymer film containing a
dispersion of one or more dyes, deposited on a non-porous solid
substrate (aluminium, plastic, etc.). This route for manufacturing dry
films by dissolving the film-forming polymer in aqueous-alcoholic
medium and then dispersing the dyes, spreading this preparation as a
thin layer onto the solid substrate and finally drying, is long and has
problems in terms of solubility, formulation and drying time.
Furthermore, the compositions provided in this form are not easy to use,
since the solid substrate is too rigid and sparingly conformable. It is thus
necessary to have available an article that is easier to prepare and to use
and that allows better contact with the fibre.
The Applicant has discovered a simpler method, which is very
easy to perform, for dyeing the hair via heat transfer.
-3-

Thus, one subject of the present invention is a substantially
dry cosmetic article for dyeing keratin materials, preferably human
keratin fibres such as the hair, comprising
- a porous flexible substrate, and
- one or more direct dyes or direct dye precursors in powder
form, which are capable of dyeing the keratin material via heat transfer,
the substrate and the direct dye or direct dye precursor being non-
covalently bonded to and/or in the substrate,
the porous flexible substrate being chosen from nonwoven fibrous
substrate or cellulose substrates of foam type.
The invention also relates to a process for dyeing keratin
materials using this article via dry heat transfer of these dyes or dye
precursors.
Finally, a subject of the invention is also the use of this article
for dyeing keratin materials such as keratin fibres, especially the hair.
The cosmetic article according to the invention is a dry article,
i.e. during its use, it is never brought into contact with a liquid and it
comprises no adhesive for bonding the colouring agent to the support.
The articles of the invention are prepared by impregnating the
porous flexible substrate with powders of direct dyes or direct dye
precursors, directly and without solvent. This has the advantage of not
requiring the use of a liquid formulation support for the dye, which
makes the dyeing operation very sparingly soiling. Furthermore, the fact
that the dyes are used directly in their solid form makes it possible to
use dyes that are sparingly soluble or sparingly stable in standard dyeing
media. This may contribute towards further broadening the range of
possible colours and towards obtaining faster colours.
The term "substantially dry" means that it contains less than
5% by weight of water relative to the weight of the article.
The expression "non-permanently bonded" means non-
covalently bonded.
The term "human keratin materials" more particularly denotes
keratin fibres, such as the hair and the eyelashes.
-4-

Finally, it is recalled that, unless otherwise indicated, the
limits delimiting a range of values form part of this range.
The porous flexible substrate is more generally known as a
wipe.
Wipes, especially cosmetic wipes, are generally constituted of
a substrate made of a material of natural or synthetic origin, which is
preferably a nonwoven, but which may also be a foam or fabric, the said
substrate being impregnated with a composition suited to the intended
purpose. These wipes are commonly used and are appreciated for their
practical aspect since they are disposable and are impregnated with the
necessary and sufficient amount of cleansing or treating product.
According to the invention, the porous flexible substrate are,
for example, woven or nonwoven fibrous substrates or cellulose
substrates of foam type. The term "flexible" used herein refers to thin
supports, between 0.5 mm and 20 mm and preferably between 1 mm and
3 mm thick, which can easily follow the contours of the surface to be
treated. They may, for example, be easily rolled up around a lock of hair.
The materials constituting these substrates are chosen such that
the article withstands the temperature required for the heat transfer of
the dyes onto the hair without degradation of the substrate. Nonwoven
substrates constituted of non-hot-melt natural fibres, linked together by
means of techniques not involving chemical binding agents that risk
melting during the heat transfer of the dyes, are thus preferably chosen.
Techniques that may be mentioned include hydrobonding or needle-
bonding, the web of fibres having been made before hand by carding or
via an aerodynamic route ("airlaid"). ). By non-hot-melt natural fibres, it
is understood fibres, which keep their bodily integrity under heat,
especially during the heat transfert, which they will incur according to
the present invention. Examples of natural fibres that may be mentioned
include silk fibres and cellulose fibres. Examples of cellulose fibres that
may be mentioned include wood pulp fibres, cotton fibres, jute fibres
and flax fibres, and a combination thereof. Synthetic fibres may also be
used, for instance cellulose ester (cellulose acetate) fibres, viscose,
polylactic acid fibres or polyamides fibres.
-5-

In the context of the present invention, the direct dyes or
direct dye precursors in powder form may be used alone or as a mixture
with other types of powder. The particle size of these powders is
generally between 0.1 and 100 µm and more preferentially between 0.5
and 60 µm.
These direct dyes or direct dye precursors may be used in
unmodified form or in the form of microcapsules containing direct dyes
or direct dye precursors.
Preferentially, the direct dyes or the direct dye precursors used
in the context of the present invention are chosen from compounds with
a heat of vaporization of less than or equal to 200 KJ/mol.
These dyes may be nonionic, cationic or nonionic.
Examples of suitable dyes that may be mentioned include
acridine, acridone, anthranthrone, anthrapyrimidine, anthraquinone,
azine, azo, azomethine, methine, benzanthrone, benzimidazole,
benzimidazolone, benzindole, benzoxazole, benzopyran, benzothiazole,
benzoquinone, bis-azine, bis-isoindoline, carboxanilide, coumarin,
cyanin (for instance azacarbocyanin, diazacarbocyanin, diazahemicyanin,
hemicyanin or tetraazacarbocyanin), diazine, diketopyrrolopyrrole,
dioxazine, diphenylamine, diphenylmethane and dithiazine dyes,
flavonoids such as flavanthrones and flavones, fluorindine and formazan
dyes, hydrazones, in particular aryl-hydrazone dyes, hydroxy ketone,
indamine, indanthrone, indigoid and pseudo-iondigoid, indophenol,
indoaniline, isoindoline, isoindoline, isoindolinone, isoviolanthrone,
lactone, methine, naphthalimide, naphthanilide, naphtholactam,
naphthoquinone, nitro-(hetero)aromatic, oxadiazole, oxazine, perilone,
perinone, perylene, phenazine, phenothiazine, phthalocyanin,
polyene/carotenoid, porphyrin, pyranthrone, pyrazolanthrone,
pyrazolone, pyrimidinoanthrone, pyronine, quinacridone, quinoline,
quinophthalone, squarane, stilbene, tetrazolium, thiazine, thioindigo,
thiopyronine, triarylmethane and xanthene dyes, alone or as mixtures.
According to one particularly advantageous embodiment of the
invention, the direct dye is chosen from:
- an azomethine dye corresponding to formula (I) below:
-6-


in which:
R1 represents:
a hydrogen atom;
a hydroxyl group;
an amino group;
an amino group mono- or disubstituted with one or two
radicals, which may be identical or different, chosen from:
C1-C6 alkyl radicals optionally substituted with a (C1-C4)
alkylSO2NH group or an NH2CO- group;
a (Cl-C6)alkylO2SNH-(Cl-C6)alkylNH- group,
a (C6)aryl(Cl-C6)alkyl group;
a C6 aryl group;
a (Cl-C4)alkylpiperidine group;
the radicals borne by the amino group may form, with the
nitrogen atom to which they are attached, a 5- or 6-membered
heterocycle optionally comprising a heteroatom chosen from oxygen and
nitrogen,
R2, which may be identical or different, represent:
a hydrogen atom;
a linear or branched C1-C6 alkyl group, optionally substituted
with a hydroxyl or C1-C6 alkoxy group;
a C5-C6 cycloalkyl group optionally substituted with a
hydroxyl or C1-C6 alkoxy group;
a C1-C6 alkoxy group;
a halogen atom, in particular chlorine;
a cyano group;
a (C6)aryl(Cl-C6)alkyl group; the aryl group being optionally
substituted with at least one C1-C6 alkyl, hydroxyl or C1-C6 alkoxy
group;
a C6 aryl group optionally substituted with at least one C1-C6
alkyl, hydroxyl or C1-C6 alkoxy group;
—7 —

a (Cl-C6)alkylcarbonyl group;
a (Cl-C6)alkylcarbonylamino group;
a (Cl-C6)alkylsulfonylamino group;
an aminocarbonylamino group;
a (Cl-C6)alkylcarbonylamino group;
a (Cl-C6)alkylsulfoamino group;
an amino group substituted with one or two radicals, which
may be identical or different, chosen from C1-C6 alkyl, C1-C6
hydroxyalkyl and trifluoromethyl radicals;
R3, which may be identical or different, represent:
- a hydrogen atom,
- a halogen atom, in particular a chlorine atom,
- a C1-C6 alkyl group optionally substituted with a hydroxyl
or C1-C6 alkoxy group,
- a C1-C6 alkoxy group,
- a (C1-C6)alkylcarbonylamino group;
- an amino group,
- an amino(Cl-C6)alkylcarbonylamino group,
- an aminocarbonylamino group,
- a (C1-C6)alkoxycarbonylamino group (C1-C4 aminoester
alkyl),
- an aminocarbonyl group in which the amino group may be
mono- or disubstituted with radicals, which may be identical or
different, chosen from C1-C6 alkyl, C1-C6 haloalkyl, (C6)aryl(Cl-C6)
alkyl, C6 aryl, (Cl-C6)alkylcarbonylamino and (C1-C6)alkylsulfonyl-
amino radicals, RaCONH- in which Ra is a C1-C4 haloalkyl group, a
(C6)aryl(C1-C6)alkyl group, a C6 aryl group, a (C1-C6)alkoxy(C1-C6)
alkyl group, a C1-C6 hydroxyalkyl group, a cyano(C1-C6)alkyl group, a
methanesulfonamide group, a (C1-C6)alkylamino(C1-C6)alkyl group, a
substituted or unsubstituted C3-C6 cycloalkenyl group, a β-thienyl
group, or one of the following groups:
-8-


in which Rb and Rc, independently of each other, represent a
hydrogen atom, a halogen atom or a C1-C6 alkyl chain and in which Z
represents CH2, O, S or NRd, in which Rd represents a hydrogen atom or
a C1-C6 alkyl chain;
- two radicals R3 borne by two adjacent carbon atoms may
form a benzene ring optionally substituted with a halogen atom, a C1-C6
alkyl group, an amino group or an amino group mono- or disubstituted
with a C1-C6 alkyl or C1-C6 hydroxyalkyl radical;
X represents an oxygen atom or an NH group;
- a particular anthraquinone radical of formula (II) below:

in which:
R, independently of each other, represent:
a hydrogen atom;
a hydroxyl group;
an amino group;
an amino group mono- or disubstituted with one or two
radicals, which may be identical or different, chosen from C1-C6 alkyl,
C1-C6 hydroxyalkyl and C6 aryl radicals optionally substituted with one
or more C1-C6 alkyl radicals;
R', independently of each other, represent:
a hydrogen atom;
a halogen atom;
a hydroxyl group;
an amino group;
an amino group mono- or disubstituted with one or two
radicals, which may be identical or different, chosen from C1-C6 alkyl,
-9-

C1-C6 alkylamino, C5-C8 cycloalkyl and (C1-C6)alkoxy(C1-C6)alkyl
radicals;
a C6 aryl radical optionally substituted with one or more
groups, which may be identical or different, chosen from halogen atoms
and C1-C6 alkyl, C1-C6 alkoxy and (C1-C6)alkoxy(C1-C6)alkyl
radicals;
a (C6)aryloxy group;
a (C6)aryloxy group substituted with a (C6)aryl-SO3 group,
the aryl group being optionally substituted with one or more groups,
which may be identical or different, chosen from halogen atoms and
hydroxyl, trifluoromethyl, C1-C6 alkyl, C1-C6 alkoxy, C6 aryl, (C6)aryl
(Cl-C4)alkyl, (C6)aryloxy, nitro, C2-C6 acyl, (C2-C6)acylamino, (Cl-
C6)alkylmercapto, C6 thiophenyl, sulfonyloxy and (C1-C6)
alkylbenzenesulfonyl groups
a (C6)aryloxy group substituted with a group -SO2N(Ra)2 with
Ra, which may be identical or different, representing a hydrogen atom or
a C1-C6 alkyl, C2-C6 alkenyl, (C6)aryl(C1-C6)alkyl or C5-C8 cycloalkyl
radical, the two radicals Ra possibly forming, with the nitrogen atom to
which they are attached, a 5- or 6-membered heterocycle;
a group -SRb with Rb representing a 5- or 6-membered
heterocycle, comprising the sulfur atom and optionally comprising a
nitrogen, sulfur or oxygen atom;
-COORc with Re representing a C1-C4 hydroxyalkyl, (C1-C4)
alkylphenyl, C5-C8 cycloalkyl, carbonyloxy(C6)aryl or carbonyl(C6)aryl
group;
- SO3-(C6)aryl, the aryl radical being optionally substituted
with one or more groups, which may be identical or different, chosen
from halogen atoms and hydroxyl, trifluoromethyl, C1-C6 alkyl, C1-C6
alkoxy, C6 aryl, (C6)aryl(Cl-C4)alkyl, (C6)aryloxy, nitro, C2-C6 acyl,
(C2-C6)acylamino, (C1-C6)alkylmercapto, thiophenyl, sulfonyloxy and
(C1-C6)alkylbenzenesulfonyl groups.
- an azo dye corresponding to formula (III) below:
-10-


R, which may be identical or different, and R', which may be
identical or different, independently of each other, represent
a hydrogen atom;
a linear, branched or cyclic, saturated, unsaturated or aromatic
C1-C30 hydrocarbon-based chain,
optionally substituted with one or more halogen atoms; with
one or more groups, which may be identical or different, chosen from the
following groups: hydroxyl; nitro; cyano; carboxylic acid; allyl;
haloallyl; C1-C10 alkoxy; (C1-C4)alkylcarbonylamino; (C1-C4)-
alkylaminocarbonyl; hydrogeno-carbonylamino; (C1-C4)alkyl-
sulfonylamino; (C1-C4)alkoxycarbonylamino; (C1-C4)alkoxycarbonyl;
(C1-C4)alkylcarbonyl(C1-C4)alkoxycarbonyl; CF3; amino; amino
optionally substituted with one or more identical or different C1-C10
alkyl, C1-C10 hydroxyalkyl, C1-C10 alkoxyalkyl, C1-C10 aminoalkyl,
(di)(C1-C10)alkylamino(C1-C10)alkyl, cyano(C1-C10)alkyl, C6-C30
aryl, (C6-C30)aryl(C1-C4)alkyl, (C4-C30)cyclo(Cl-C12)alkyl, (C1-C4)
alkylcarbonyl, (C1-C4)alkylcarboxy(C1-C4)alkyl, allyl, haloallyl;
optionally interrupted with or attached to the aromatic nucleus
via one or more heteroatoms or a group comprising one or more
heteroatoms chosen from oxygen, sulfur and nitrogen;
a group chosen from: hydroxyl; C1-C4 alkoxy; carboxylic acid;
amino; amino substituted with one or more radicals, which may be
identical or different, chosen from C1-C4 alkyl, C2-C4 alkenyl, cyano
(C1-C4)alkyl, C1-C4 hydroxyalkyl, C6-C30 aryl, (C6-C30)aryl(C1-C4)
alkyl, allyl, (C1-C4)alkoxy(C1-C4)alkyl, (C4-C30)cyclo(Cl-C12)alkyl,
(C1-C4)alkylcarbonyl, (C1-C4)carboxy(C1-C4)alkyl, haloallyl, amino
(C1-C4)alkyl, (di)(C1-C4)alkylamino(C1-C4)alkyl, (C1-C4)
alkylsulfonyl, (C1-C4)alkoxycarbonyl; halogen; allyl;
hydrogenocarbonyl; trifluoromethyl; nitro; cyano; radicals
-11-

it being understood that at least one of the radicals R or R'
represents a group chosen from hydroxyl; nitro; cyano; amino; amino
optionally substituted with one or more radicals; and
optionally, two radicals R borne by two adjacent carbon atoms
or two radicals R' borne by two adjacent carbon atoms may form, with
the aromatic ring bearing the carbon atoms to which each is attached, a
fused nucleus of naphthalene type optionally substituted with an
aminosulfonyl or (C1-C4)alkylaminosulfonyl group.
According to one particular embodiment of the invention, the
radical R1 of formula (I) represents:
a hydroxyl group;
an amino group;
an amino group mono- or disubstituted with one or two
radicals, which may be identical or different, chosen from:
C1-C4 alkyl optionally substituted with a (C1-C4)alkylSO2NH
group or an NH2C0- group,
the radicals borne by the amino group may form, with the
nitrogen atom to which they are attached, a 5- or 6-membered
heterocycle optionally comprising a heteroatom chosen from oxygen and
nitrogen.
Moreover, the radicals R2 of formula (I), which may be
identical or different, more particularly represent:
a hydrogen atom;
a linear or branched C1-C4 alkyl group;
a C1-C4 alkoxy group;
a halogen atom, in particular chlorine.
As regards the radicals R3 of formula (I), these radicals, which
may be identical or different, preferably represent:
- a hydrogen atom,
- a C1-C6 alkyl group optionally substituted with a hydroxyl
or C1-C6 alkoxy group,
-12-

- a C1-C4 alkoxy group,
- an amino group,
- a (C1-C6)alkylcarbonylamino group,
- a (C1-C4)alkoxycarbonylamino group,
- two radicals R3 borne by two adjacent carbon atoms may
form a benzene ring optionally substituted with a halogen atom, a C1-C6
alkyl group, an amino group or an amino group mono- or disubstituted
with a C1-C6 alkyl or C1-C6 hydroxyalkyl radical.
Preferably, the anthraquinone direct dye corresponds to
formula (IIa) below:

R1, represents a hydrogen atom or a hydroxyl or amino
group, or an amino group mono- or disubstituted with one or two
radicals, which may be identical or different, chosen from C1-C4 alkyl,
C1-C6 hydroxyalkyl and phenyl radicals optionally substituted with one
or more C1-C4 alkyl radicals;
R'1 represents a hydrogen atom or a hydroxyl or amino
group;
R2 and R'2, independently of each other, represent
a hydrogen atom;
a halogen atom, preferably chlorine or bromine;
a hydroxyl group;
an amino group;
an amino group mono- or disubstituted with one or two
radicals, which may be identical or different, chosen from C1-C6 alkyl,
C1-C6 alkylamino, C5-C8 cycloalkyl and (C1-C6)alkoxy(C1-C6)alkyl
radicals;
a C6 aryl radical optionally substituted with one or more
groups, which may be identical or different, chosen from halogen atoms
-13-

and C1-C6 alkyl, C1-C6 alkoxy and (C1-C6)alkoxy(C1-C6)alkyl
radicals;
a ,(C6)aryloxy group;
R3 represents a hydrogen atom; a hydroxyl group; an amino
group; an amino group mono- or disubstituted with one or two radicals,
which may be identical or different, chosen from C1-C6 alkyl, C1-C6
hydroxyalkyl and C6 aryl radicals optionally substituted with one or
more C1-C6 alkyl radicals;
R'3 represents a hydrogen atom; a hydroxyl group; an amino
group.
In accordance with one advantageous embodiment of the
invention, the anthraquinone direct dye of formula (II) is chosen from
the following direct dyes: Disperse Blue 1 [2475-45-8], Disperse Blue 3
[2475-46-9], Disperse Blue 14 [2475-44-7], Disperse Blue 19 [4395-65-
7], Disperse Blue 26 [3860-63-7], Disperse Blue 56 [31810-89-6],
Disperse Orange 11 [82-28-0], Disperse Red 60 [17418-58-5], Disperse
Violet 1 [128-95-0], Solvent Blue 35 [17354-14-2], Solvent Blue 59
[6994-46-3], Solvent Green 3 [17418-58-5], 6-methyl-l,3,8-
trihydroxyanthraquinone (Emodine) [518-82-1], purpurin [81-54-9],
quinalizarin [81-61-8], and mixtures thereof.
Preferably, the azo direct dye corresponds to formula (IIIa)
below:

R'1 represents a hydrogen atom, an amino group or a hydroxyl
group;
R'2 represents a hydrogen atom, a halogen atom, a carboxylic
acid group, a C1-C4 alkyl group, a C1-C4 alkoxy group, an allyl group
or an aminocarbonyl(C1-C4)alkyl group;
-14-

R'3 represents a hydrogen atom, a hydroxyl group or a group
of the type NR'1R'2 in which R'l and R'2 represent, independently of
each other, a hydrogen atom, a C1-C4 alkyl group, a C2-C4 alkenyl
group, a cyano(C1-C4)alkyl group, a C1-C4 hydroxyalkyl group, a C6-
C30 aryl group, a (C6-C30)aryl(C1-C4)alkyl group, an allyl group, a
(Cl~C4)alkoxy(C1-C4)alkyl group, a (C4-C30)cyclo(C1-C12)alkyl
group, a (C1-C4)alkylcarbonyl group, a (C1-C4)alkylcarboxy(C1-C4)
alkyl group or a haloallyl group, a C1-C4 aminoalkyl group or a (di)(Cl-
C4)alkylamino(C1-C4)alkyl group;
R'2 and R'3 may form, with the benzene nucleus, a fused
nucleus of naphthalene type optionally substituted with a group -SO2-
NHR in which R represents a hydrogen atom or an optionally substituted
C1-C4 alkyl chain;
R'4 represents a hydrogen atom, a halogen atom, a hydroxyl
group, a C1-C4 alkyl group, a C1-C4 alkoxy group or a (C1-C4)alkoxy
(C1-C4)alkyl group;
R'5 represents a hydrogen atom, a halogen atom, a hydroxyl
group, an amino group, a C1-C4 alkyl group, a C1-C4 alkoxy group, a
(C1-C4)alkylcarbonylamino group, a hydrogenocarbonylamino group,
(C1-C4)alkylsulfonylamino, a (C1-C4)alkoxycarbonylamino group or a
CF3 group;
R'4 and R'5 may form, with the benzene nucleus, a fused
nucleus of naphthalene type;
R1 represents a hydrogen atom, a halogen atom, a hydroxyl
group, a nitro group or a cyano group;
R2 represents a hydrogen atom, a nitro group or a C1-C4 alkyl
group;
R3 represents a hydrogen atom, a C1-C4 alkyl group, a C1-C4
alkoxy group, a (C4-C30)cyclo(Cl-C12)alkyl group, a C2-C4 alkenyl
group, a (C1-C4)alkoxycarbonyl group, a (C1-C4)alkylcarbonyl group, a
(C1-C4)alkoxycarbonyl(C1-C4)alkoxycarbonyl group, (C1-C4)
alkylcarbonyl(C1-C4)alkoxycarbonyl, an aryl group, an amino group, a
nitro group, a cyano group or a CF3 group;
R4 represents a hydrogen atom or a nitro group;
-15-

R5 represents a hydrogen atom, a halogen atom, a carboxylic
acid group, a hydroxyl group, an amino group, a cyano group or a C1-C4
alkyl group;
it being understood that at least one of the radicals R'1 to R'5
and Rl to R5 represents a group chosen from hydroxyl; nitro; cyano;
amino; amino optionally substituted with one or more radicals.
According to one advantageous embodiment, the radicals R'l,
R'2, R1, R2 and R4 of formula (IIIa), represent a hydrogen atom.
More particularly, the radical R'3 of formula (IIIa) represents
a hydrogen atom or a group of the type NR"1R"2 in which R" 1 and
R"2 represent, independently of each other, a hydrogen atom, a C1-C4
alkyl group, a cyano(C1-C4)alkyl group, a C1-C4 hydroxyalkyl group or
a C1-C4 aminoalkyl group.
As regards the radical R'4 of formula (IIIa), it more
particularly represents a hydrogen atom.
Preferably, the radical R'5 of formula (IIIa) represents a
hydrogen atom or a C1-C4 alkyl group.
According to another embodiment, the radicals R'4 and R'5 of
formula (IIIa) form, with the benzene nucleus, a fused nucleus of
naphthalene type.
The radical R3 of formula (IIIa) more particularly represents
an amino group or a nitro group.
The radical R5 of formula (IIIa) more particularly represents a
hydrogen atom; a halogen atom, preferably chlorine or fluorine; an
amino group.
In accordance with one advantageous embodiment of the
invention, the azo direct dye of formula (IIIa) is chosen from the
following direct dyes: Solvent Brown 1 [6416-57-5], Solvent Orange 1
[2051-85-6], Solvent Orange 7 [3118-97-6], Solvent Yellow 2 [60-11-7],
Solvent Yellow 3 [97-56-3], Solvent Yellow 7 [1689-82-3], Solvent
Yellow 14 [842-07-9], Disperse Orange 1 [2581-69-3], Disperse Orange
3 [730-40-5], Disperse Orange 25 [31482-56-1], Disperse Red 1 [2872-
52-8], Disperse Red 13 [3180-81-2], Disperse Red 19 [2734-52-3],
-16-

Disperse Red 50 [ 12223-35-7] + [40880-51-1 ], Disperse Yellow 3,
Mordant Brown 4 [6247-28-5], Mordant Brown 6 [6247-28-5], Mordant
Brown 24 [6370-46-3], Mordant Brown 48 [6232-53-7], Mordant Orange
1 [2243-76-7], Pigment Red 3 [2425-85-6], 4-dimethylamino-2-
methylazobenzene [54-88-6], 2-(4-diethylaminophenylazo)benzoic acid
[7605 8-33-8], N-ethyl-N-(2-aminoethyl)-4-(4-nitrophenylazo)aniline,
N,N~hydroxyethyl-4-(4-nitrophenylazo)-2-methylaniline, N,N-
hydroxyethyl-4-(4-aminophenylazo)-2-aniline, and mixtures thereof.
Precursors of these direct dyes may also be used. Precursors
that may be mentioned include the leuco forms.
Direct dyes or precursors of direct dyes capable of reacting
with the amine functions present in keratin fibres such as the hair may
also be used.
According to the invention, the direct dye(s) or direct dye
precursor(s) used according to the invention generally represent from
0.5% to 50% by weight approximately and more preferentially from 5%
to 50% by weight approximately relative to the total weight of the
cosmetic article.
The powder compositions of the invention may moreover
contain one or more cosmetic additives in powder form chosen from
other cosmetic agents such as polymers (which may be hot-melt
polymers), fragrances, preserving agents, pH agents, surfactants,
screening agents, antioxidants, fatty substances, silicones, amino acids
or any other adjuvant usually used in the dyeing of keratin materials.
Usually, the content of additives in the powder represents for
each of them from 0.01% to 20%; the total content of additives, when
they are present, does not exceed 80% by weight of the powder.
According to the process for preparing the cosmetic article
used, it is possible either to obtain a cosmetic article impregnated with
the said sparingly coloured or uncoloured direct dye(s) or direct dye
precursor(s), or to obtain a substantially coloured article.
The term "sparingly coloured or uncoloured" means an article
whose difference in coloration before and after impregnation with the
-17-

dye(s) or the precursor(s) is less than or equal to 10, this preferably
being evaluated by the colour difference

colorimetric coordinates in the La*b* system of the fibre after and
-before impregnation, and whose difference in chromaticity

The term "substantially coloured" means an article for which
the value DE defined above is greater than 5 and/or whose difference in
chromaticity is greater than 5.
In the context of substantially coloured particles, the preferred
dyes are the direct dyes of formulae (I), (II) and (III) described above
and the dye precursors mentioned above.
The process for preparing the article according to the invention
may be any known dry impregnation process. It may in particular be an
impregnation process using an alternating electric field, cold plasma (0.1
to 20 kV/mm) after having sprinkled the direct dye or the direct dye
precursor onto the porous flexible substrate. It is not necessary in the
context of the invention to perform a step of fixing the dyes or dye
precursors.
This process is performed so as to obtain uniform distribution
of the said direct dye(s) or direct dye precursor(s) on and/or in the
substrate.
In the context of the sparingly coloured or uncoloured articles,
this impregnation is not followed by thermal fixing.
In the context of the substantially coloured articles, the
impregnation is followed by thermal fixing in a temperature range of
between 70 and 240°C. In both cases, the optionally heat-fixed
impregnated substrates may be covered with a protective film generally
of polymeric nature.
The invention also relates to a hair dyeing process using the
said article. The process comprises the following steps.

A strip of the powder-impregnated cosmetic article or
nonwoven wipe may be cut to the desired size, this step being dependent
on the shape and size of the available wipes.
The wipe is then positioned on either side of the keratin
fibres, for example a lock of hair. The wipe may, for example, encircle
or sandwich the lock of hair.
A heat source is then applied to the wipe, resulting in thermal
transfer of the dye(s) onto the surface of and/or into the keratin
materials.
Moreover, for the purposes of the present invention, the term
"thermal transfer" means the application of heat to the dry composition
placed in contact with or close to the keratin materials to be treated.
This heat is obtained by means of a source at a temperature more
particularly of between 100 and 500°C, advantageously between 130 and
250°C and even more advantageously between 140 and 220°C.
The source of heat may be provided in a conventional manner,
for instance a hairdryer, a styling hood, a smoothing iron, a crimping
iron, a pulsed or non-pulsed laser system (UV, visible or high-energy
infrared light radiation), a system of heating tips, etc.
Preferably, this source of heat is placed in contact with the
assembly of the wipe and the keratin materials to be treated
The source of heat is applied to the wipe, for instance a
smoothing iron, for a time generally of between 1 second and 5 minutes
and preferably between 30 seconds and 3 minutes. The higher the
temperature, the shorter will be the treatment.
Without wishing to be bound by any theory, one of the possible
mechanisms for the dyeing of the keratin materials proceeds via a step of
vaporization or sublimation of the direct dye present in the dry
composition according to the invention.
Concrete but non-limiting examples of the invention will now
be presented.
EXAMPLES
-19-

Composition:
The wipes of the invention are prepared from two 100%
viscose nonwoven substrates (non-hot-melt fibres) below:
- fine, relatively thin nonwoven of low basis weight: V 68 L
Aquadim: Tharreau
- thick, thicker nonwoven of higher basis weight: VI 41 17C:
Tharreau,
and impregnated with the dyes Disperse Blue 3 or Disperse
Red 60 via the cold plasma technique to a degree of impregnation of the
dye powders (relative to the weight of the nonwoven) of, respectively,
10% for the thick nonwoven and 15% for the thin nonwoven.

Dyeing process:
A strip of dye-impregnated nonwoven is cut to sizes of 5 x
9 cm and then positioned on either side of a lock of natural hair
containing 90% white hairs, which has been spread out beforehand.
The smoothing iron is then applied for 5 minutes at 180°C.
Results:
The samples of nonwovens allow colour transfer onto the hair:
fuchsia red for Disperse Red 60 and cyan blue for Disperse Blue 3.
-20-

WE CLAIM:
1. Substantially dry cosmetic article for dyeing keratin
materials, comprising
- a porous flexible substrate, and
- one or more direct dyes or direct dye precursors in powder
form, which are capable of dyeing the keratin material via heat transfer,
the substrate and the direct dye(s) or direct dye precursor(s) being non-
covalently bonded to and/or in the substrate,
the porous flexible substrate being chosen from nonwoven fibrous
substrates and cellular substrates of foam type.
2. Cosmetic article according to Claim 1, characterized in
that it is obtained by dry impregnation process.
3. Cosmetic article according to Claim 2, characterized in
that it is obtained by dry impregnation process using an alternating
electric field.
4. Cosmetic article according to any one of the preceding
Claims, characterized in that the thickness of the porous flexible
substrate is between 0.5 mm and 20 mm and preferably between 1 mm
and 3 mm.

5. Cosmetic article according to any one of the preceding
claims, characterized in that the porous flexible substrate is chosen from
nonwoven substrates constituted of non-hot-melt natural fibres.
6. Cosmetic article according to any one of the preceding
claims, characterized in that the porous flexible substrate is chosen from
silk fibres, cellulose fibres, wood pulp fibres, cotton fibres, jute fibres
and flax fibres, and a combination thereof, cellulose ester fibres,
viscose, polylactic acid fibres and polyamides fibres.
-21-

7. Cosmetic article according to any one of the preceding
claims, characterized in that the particle size of the powder of direct
dyes or of direct dye precursors is between 0.1 and 100 µm and even
more preferentially between 0.5 and 60 µm.
8. Cosmetic article according to any one of the preceding
claims, characterized in that the direct dye or the direct dye precursor is
chosen from compounds with a heat of vaporization of less than or equal
to 200 KJ/mol.
9. Cosmetic article according to any one of the preceding
claims, characterized in that it comprises one or more nonionic, cationic
or anionic direct dyes or direct dye precursors.
10. Cosmetic article according to Claim 9, characterized in
that the direct dye is chosen from acridine, acridone, anthranthrone,
anthrapyrimidine, anthraquinone, azine, azo, azomethine, methine,
benzanthrone, benzimidazole, benzimidazolone, benzindole,
benzoxazole, benzopyran, benzothiazole, benzoquinone, bis-azine, bis-
isoindoline, carboxanilide, coumarin, cyanin, diazine,
diketopyrrolopyrrole, dioxazine, diphenylamine, diphenylmethane and
dithiazine dyes, flavonoid, fluorindine, formazan, hydrazone, hydroxy
ketone, indamine, indanthrone, indigoid and pseudo-iondigoid,
indophenol, indoaniline, isoindoline, isoindoline, isoindolinone,
isoviolanthrone, lactone, methine, naphthalimide, naphthanilide,
naphtholactam, naphthoquinone, nitro(hetero)aromatic, oxadiazole,
oxazine, perilone, perinone, perylene, phenazine, phenothiazine,
phthalocyanin, polyene/carotenoid, porphyrin, pyranthrone,
pyrazolanthrone, pyrazolone, pyrimidinoanthrone, pyronine,
quinacridone, quinoline, quinophthalone, squarane, stilbene, tetrazolium,
thiazine, thioindigo, thiopyronine, triarylmethane and xanthene dyes,
alone or as mixtures.
-22-

11. Cosmetic article according to Claim 9 or 10, characterized
in that the direct dye is chosen from:
- an azomethine dye corresponding to formula (I) below:

Rl represents:
a hydrogen atom;
a hydroxyl group;
an amino group;
an amino group mono- or disubstituted with one or two
radicals, which may be identical or different, chosen from:
C1-C6 alkyl radicals optionally substituted with a (C1-C4)
alkylSO2NH group or an NH2CO- group;
a (C1-C6)alkylO2SNH-(C1-C6)alkylNH- group,
a (C6)aryl(C1-C6)alkyl group;
a C6 aryl group;
a (C1-C4)alkylpiperidine group;
the radicals borne by the amino group may form, with the
nitrogen atom to which they are attached, a 5- or 6-membered
heterocycle optionally comprising a heteroatom chosen from oxygen and
nitrogen,
R2, which may be identical or different, represent:
a hydrogen atom;
a linear or branched C1-C6 alkyl group, optionally substituted
with a hydroxyl or C1-C6 alkoxy group;
a C5-C6 cycloalkyl group optionally substituted with a
hydroxyl or C1-C6 alkoxy group;
a C1-C6 alkoxy group;
a halogen atom, in particular chlorine;
a cyano group;
-23-

a (C6)aryl(C1-C6)alkyl group; the aryl group being optionally
substituted with at least one C1-C6 alkyl, hydroxyl or C1-C6 alkoxy
group;
a C6 aryl group optionally substituted with at least one C1-C6
alkyl, hydroxyl or C1-C6 alkoxy group;
a (C1-C6)alkylcarbonyl group;
a (C1-C6)alkylcarbonylamino group;
a (C1-C6)alkylsulfonylamino group;
an aminocarbonylamino group;
a (C 1-C6)alkylcarbonylamino group;
a (C1-C6)alkylsulfoamino group;
an amino group substituted with one or two radicals, which
may be identical or different, chosen from C1-C6 alkyl, C1-C6
hydroxyalkyl and trifluoromethyl radicals;
R3, which may be identical or different, represent:
- a hydrogen atom,
- a halogen atom, in particular a chlorine atom,
- a C1-C6 alkyl group optionally substituted with a hydroxyl
or C1-C6 alkoxy group,
- a C1-C6 alkoxy group,
- a (C1-C6)alkylcarbonylamino group;
- an amino group,
- an amino(C1-C6)alkylcarbonylamino group,
- an aminocarbonylamino group,
- a (C1-C6)alkoxycarbonylamino group (C1-C4 aminoester
alkyl),
- an aminocarbonyl group in which the amino group may be
mono- or disubstituted with radicals, which may be identical or
different, chosen from C1-C6 alkyl, C1-C6 haloalkyl, (C6)aryl(C1-C6)
alkyl, C6 aryl, (C1-C6)alkylcarbonylamino and (C1-C6)
alkylsulfonylamino radicals, RaCONH- in which Ra is a C1-C4 haloalkyl
group, a (C6)aryl(C1-C6)alkyl group, a C6 aryl group, a (C1-C6)alkoxy
(C1-C6)alkyl group, a C1-C6 hydroxyalkyl group, a cyano(C1-C6)alkyl
group, a methanesulfonamide group, a (C1-C6)alkylamino(C1 -C6)alkyl
-24-

group, a substituted or unsubstituted C3-C6 cycloalkenyl group, a fi-
thienyl group, or one of the following groups:

in which Rb and Rc, independently of each other, represent a
hydrogen atom, a halogen atom or a C1-C6 alkyl chain and in which Z
represents CH2, O, S or NRd, in which Rd represents a hydrogen atom or
a C1-C6 alkyl chain;
- two radicals R3 borne by two adjacent carbon atoms may
form a benzene ring optionally substituted with a halogen atom, a C1-C6
alkyl group, an amino group or an amino group mono- or disubstituted
with a C1-C6 alkyl or C1-C6 hydroxyalkyl radical;
X represents an oxygen atom or an NH group;
- a particular anthraquinone radical of formula (II) below:

R, independently of each other, represent:
a hydrogen atom;
a hydroxyl group;
an amino group;
an amino group mono- or disubstituted with one or two
radicals, which may be identical or different, chosen from C1-C6 alkyl,
C1-C6 hydroxyalkyl and C6 aryl radicals optionally substituted with one
or more C1-C6 alkyl radicals;
R', independently of each other, represent:
a hydrogen atom;
a halogen atom;
a hydroxyl group;
an amino group;
-25-

an arnino group mono- or disubstituted with one or two
radicals, which may be identical or different, chosen from C1-C6 alkyl,
C1-C6 alkylamino, C5-C8 cycloalkyl and (C1-C6)alkoxy(C1-C6)alkyl
radicals;
a C6 aryl radical optionally substituted with one or more
groups, which may be identical or different, chosen from halogen atoms
and C1-C6 alkyl, C1-C6 alkoxy and (C1-C6)alkoxy(C1-C6)alkyl
radicals;
a (C6)aryloxy group;
a (C6)aryloxy group substituted with a (C6)aryl-SO3 group,
the aryl group being optionally substituted with one or more groups,
which may be identical or different, chosen from halogen atoms and
hydroxyl, trifluoromethyl, C1-C6 alkyl, C1-C6 alkoxy, C6 aryl, (C6)aryl
(C1-C4)alkyl, (C6)aryloxy, nitro, C2-C6 acyl, (C2-C6)acylamino, (C1-
C6)alkylmercapto, C6 thiophenyl, sulfonyloxy and (C1-C6)
alkylbenzenesulfonyl groups
a (C6)aryloxy group substituted with a group -SO2N(Ra)2 with
Ra, which may be identical or different, representing a hydrogen atom or
a C1-C6 alkyl, C2-C6 alkenyl, (C6)aryl(C1-C6)alkyl or C5-C8 cycloalkyl
radical, the two radicals Ra possibly forming, with the nitrogen atom to
which they are attached, a 5- or 6-membered heterocycle;
a group -SRb with Rb representing a 5- or 6-membered
heterocycle, comprising the sulfur atom and optionally comprising a
nitrogen, sulfur or oxygen atom;
-COORc with Rc representing a C1-C4 hydroxyalkyl, (C1-C4)
alkylphenyl, C5-C8 cycloalkyl, carbonyloxy(C6)aryl or carbonyl(C6)aryl
group;
-SO3-(C6)aryl, the aryl radical being optionally substituted
with one or more groups, which may be identical or different, chosen
from halogen atoms and hydroxyl, trifluoromethyl, C1-C6 alkyl, C1-C6
alkoxy, C6 aryl, (C6)aryl(C1-C4)alkyl, (C6)aryloxy, nitro, C2-C6 acyl,
(C2-C6)acylamino, (C1-C6)alkylmercapto, thiophenyl, sulfonyloxy and
(C1-C6)alkylbenzenesulfonyl groups;
-26-

- an azo dye corresponding to formula (III) below:

R, which may be identical or different, and R', which may be
identical or different, independently of each other, represent
a hydrogen atom;
a linear, branched or cyclic, saturated, unsaturated or aromatic
C1-C30 hydrocarbon-based chain,
optionally substituted with one or more halogen atoms; with
one or more groups, which may be identical or different, chosen from the
following groups: hydroxyl; nitro; cyano; carboxylic acid; allyl;
haloallyl; C1-C10 alkoxy; (C1-C4)alkylcarbonylamino; (C1-C4)
alkylaminocarbonyl; hydrogeno-carbonylamino; (C1-C4)
alkylsulfonylamino; (C1-C4)alkoxycarbonylamino; (C1-C4)
alkoxycarbonyl; (C1-C4)alkylcarbonyl(C1-C4)alkoxycarbonyl; CF3;
amino; amino optionally substituted with one or more identical or
different C1-C10 alkyl, C1-C10 hydroxyalkyl, C1-C10 alkoxyalkyl, Cl-
C10 aminoalkyl, (di)(Cl -C10)alkylamino(C l-C10)alkyl, cyano(Cl-ClO)
alkyl, C6-C30 aryl, (C6-C30)aryl(Cl -C4)alkyl, (C4-C30)cyclo(Cl-C12)
alkyl, (C1-C4)alkylcarbonyl, (C1-C4)alkylcarboxy(C1-C4)alkyl, allyl,
haloallyl;
optionally interrupted with or attached to the aromatic nucleus
via one or more heteroatoms or a group comprising one or more
heteroatoms chosen from oxygen, sulfur and nitrogen;
a group chosen from: hydroxyl; C1-C4 alkoxy; carboxylic acid;
amino; amino substituted with one or more radicals, which may be
identical or different, chosen from C1-C4 alkyl, C2-C4 alkenyl, cyano
(C1-C4)alkyl, C1-C4 hydroxyalkyl, C6-C30 aryl, (C6-C30)aryl(Cl -C4)
alkyl, allyl, (C1-C4)alkoxy(C1-C4)alkyl, (C4-C30)cyclo(Cl-C12)alkyl,
(C1-C4)alkylcarbonyl, (C1-C4)carboxy(Cl-C4)alkyl, haloallyl, amino
(C1-C4)alkyl, (di)(C1-C4)alkylamino(C1-C4)alkyl, (C1-C4)
alkylsulfonyl, (C1-C4)alkoxycarbonyl; halogen; allyl; hydrogeno-
carbonyl; trifluoromethyl; nitro; cyano; radicals
-27-

it being understood that at least one of the radicals R or R'
represents a group chosen from hydroxyl; nitro; cyano; amino; amino
optionally substituted with one or more radicals; and
optionally, two radicals R borne by two adjacent carbon atoms
or two radicals R' borne by two adjacent carbon atoms may form, with
the aromatic ring bearing the carbon atoms to which each is attached, a
fused nucleus of naphthalene type optionally substituted with an
aminosulfonyl or (C1-C4)alkylaminosulfonyl group.
12. Cosmetic article according to Claim 11, characterized in
that the radical R1 of formula (I) represents:
a hydroxyl group;
an amino group;
an amino group mono- or disubstituted with one or two
radicals, which may be identical or different, chosen from:
C1-C4 alkyl optionally substituted with a (C1-C4)alkylSO2NH
group or an NH2C0- group,
the radicals borne by the amino group may form, with the
nitrogen atom to which they are attached, a 5- or 6-membered
heterocycle optionally comprising a heteroatom chosen from oxygen and
nitrogen.
13. Cosmetic article according to Claim 11 or 12,
characterized in that the radicals R2 of formula (I), which may be
identical or different, more particularly represent:
a hydrogen atom;
a linear or branched C1-C4 alkyl group;
a C1-C4 alkoxy group;
a halogen atom, in particular chlorine.
14. Cosmetic article according to any one of Claims 11 to 13,
characterized in that the radicals R3 of formula (I), which radicals may
be identical or different, preferably represent:
a hydrogen atom,
-28-

- a C1-C6 alkyl group optionally substituted with a hydroxyl
or C1-C6 alkoxy group,
- a C1-C4 alkoxy group,
- an amino group,
- a (C1-C6)alkylcarbonylamino group,
- a (C1-C4)alkoxycarbonylamino group,
- two radicals R3 borne by two adjacent carbon atoms may
form a benzene ring optionally substituted with a halogen atom, a C1-C6
alkyl group, an amino group or an amino group mono- or disubstituted
with a C1-C6 alkyl or C1-C6 hydroxyalkyl radical.
15. Cosmetic article according to Claim 11, characterized in
that the anthraquinone direct dye corresponds to formula (Ha) below:

R1, represents a hydrogen atom or a hydroxyl or amino group,
or an amino group mono- or disubstituted with one or two radicals,
which may be identical or different, chosen from C1-C4 alkyl, C1-C6
hydroxyalkyl and phenyl radicals optionally substituted with one or more
C1-C4 alkyl radicals;
R' 1 represents a hydrogen atom or a hydroxyl or amino group;
R2 and R'2, independently of each other, represent
a hydrogen atom;
a halogen atom, preferably chlorine or bromine;
a hydroxyl group;
an amino group;
an amino group mono- or disubstituted with one or two
radicals, which may be identical or different, chosen from C1-C6 alkyl,
C1-C6 alkylamino, C5-C8 cycloalkyl and (C1-C6)alkoxy(C1-C6)alkyl
radicals;
-29-

a C6 aryl radical optionally substituted with one or more
groups, which may be identical or different, chosen from halogen atoms
and C1-C6 alkyl, C1-C6 alkoxy and (C1-C6)alkoxy(C1-C6)alkyl
radicals;
a (C6)aryloxy group;
R3 represents a hydrogen atom; a hydroxyl group; an amino
group; an amino group mono- or disubstituted with one or two radicals,
which may be identical or different, chosen from C1-C6 alkyl, C1-C6
hydroxyalkyl and C6 aryl radicals optionally substituted with one or
more C1-C6 alkyl radicals;
R'3 represents a hydrogen atom; a hydroxyl group; an amino
group.
16. Cosmetic article according to Claim 15, characterized in
that the anthraquinone direct dye of formula (IIa) is chosen from the
following direct dyes: Disperse Blue 1 [2475-45-8], Disperse Blue 3
[2475-46-9], Disperse Blue 14 [2475-44-7], Disperse Blue 19 [4395-65-
7], Disperse Blue 26 [3860-63-7], Disperse Blue 56 [31810-89-6],
Disperse Orange 11 [82-28-0], Disperse Red 60 [17418-58-5], Disperse
Violet 1 [128-95-0], Solvent Blue 35 [17354-14-2], Solvent Blue 59
[6994-46-3], Solvent Green 3 [17418-58-5], 6-methyl-l,3,8-
trihydroxyanthraquinone (Emodine) [518-82-1], purpurin [81-54-9],
quinalizarin [81-61-8], and mixtures thereof.
17. Cosmetic article according to Claim 11, characterized in
that the azo direct dye corresponds to formula (IIIa) below:

R'1 represents a hydrogen atom, an amino group or a hydroxyl
group;
-30-

R'2 represents a hydrogen atom, a halogen atom, a carboxylic
acid group, a C1-C4 alkyl group, a C1-C4 alkoxy group, an allyl group
or an aminocarbonyl(C1-C4)alkyl group;
R'3 represents a hydrogen atom, a hydroxyl group or a group
of the type NR'1R'2 in which R'1 and R'2 represent, independently of
each other, a hydrogen atom, a C1-C4 alkyl group, a C2-C4 alkenyl
group, a cyano(C1-C4)alkyl group, a C1-C4 hydroxyalkyl group, a C6-
C30 aryl group, a (C6-C30)aryl(C1-C4)alkyl group, an allyl group, a
(C1-C4)alkoxy(C1-C4)alkyl group, a (C4-C30)cyclo(Cl-C12)alkyl
group, a (C1-C4)alkylcarbonyl group, a (C1-C4)alkylcarboxy(C1-C4)
alkyl group or a haloallyl group, a C1-C4 aminoalkyl group or a (di)(Cl-
C4)alkylamino(C1-C4)alkyl group;
R'2 and R'3 may form, with the benzene nucleus, a fused
nucleus of naphthalene type optionally substituted with a group -SO2-
NHR in which R represents a hydrogen atom or an optionally substituted
C1-C4 alkyl chain;
R'4 represents a hydrogen atom, a halogen atom, a hydroxyl
group, a C1-C4 alkyl group, a C1-C4 alkoxy group or a (C1-C4)alkoxy
(C1-C4)alkyl group;
R'5 represents a hydrogen atom, a halogen atom, a hydroxyl
group, an amino group, a C1-C4 alkyl group, a C1-C4 alkoxy group, a
(C1-C4)alkylcarbonylamino group, a hydrogenocarbonylamino group,
(C1-C4)alkylsulfonylamino, a (C1-C4)alkoxycarbonylamino group or a
CF3 group;
R'4 and R'5 may form, with the benzene nucleus, a fused
nucleus of naphthalene type;
R1 represents a hydrogen atom, a halogen atom, a hydroxyl
group, a nitro group or a cyano group;
R2 represents a hydrogen atom, a nitro group or a C1-C4 alkyl
group;
R3 represents a hydrogen atom, a C1-C4 alkyl group, a C1-C4
alkoxy group, a (C4-C30)cyclo(C1-C12)alkyl group, a C2-C4 alkenyl
group, a (C1-C4)alkoxycarbonyl group, a (C1-C4)alkylcarbonyl group, a
(C1-C4)alkoxycarbonyl(C1-C4)alkoxycarbonyl group, (C1-C4)alkyl-
-31-

carbonyl(C 1-C4)alkoxycarbonyl, an aryl group, an amino group, a nitro
group, a cyano group or a CF3 group;
R4 represents a hydrogen atom or a nitro group;
R5 represents a hydrogen atom, a halogen atom, a carboxylic
acid group, a hydroxyl group, an amino group, a cyano group or a C1-C4
alkyl group;
it being understood that at least one of the radicals R'1 to R'5
and Rl to R5 represents, a group chosen from hydroxyl; nitro; cyano;
amino; amino optionally substituted with one or more radicals.
18. Cosmetic article according to Claim 17, characterized in
that the radicals R'1, R'2, Rl, R2 and R4 of formula (IIIa) represent a
hydrogen atom.
19. Cosmetic article according to Claim 17, characterized in
that the radical R'3 of formula (IIIa) represents a hydrogen atom or a
group of the type NR"1R"2 in which R" 1 and R"2 represent,
independently of each other, a hydrogen atom, a C1-C4 alkyl group, a
cyano(C1-C4)alkyl group, a C1-C4 hydroxyalkyl group or a C1-C4
aminoalkyl group.
20. Cosmetic article according to any one of Claims 17 to 19,
characterized in that the radical R'4 of formula (IIIa) represents a
hydrogen atom.
21. Cosmetic article according to any one of Claims 1 7 to 20,
characterized in that the radical R'5 of formula (IIIa) represents a
hydrogen atom or a C1-C4 alkyl group.
22. Cosmetic article according to any one of Claims 17 to 19,
characterized in that the radicals R'4 and R'5 of formula (IIIa) form,
with the benzene nucleus, a fused nucleus of naphthalene type.
-32-

23. Cosmetic article according to any one of Claims 17 to 22,
characterized in that the radical R3 of formula (IIIa) represents an amino
group or a nitro group.
24. Cosmetic article according to any one of Claims 17 to 23,
characterized in that the radical R5 of formula (IIIa) represents a
hydrogen atom; a halogen atom, preferably chlorine or fluorine; an
amino group.
25. Cosmetic article according to any one of Claims 17 to 24,
characterized in that the azo direct dye of formula (IIIa) is chosen from
the following direct dyes: Solvent Brown 1 [6416-57-5], Solvent Orange
1 [2051-85-6], Solvent Orange 7 [3118-97-6], Solvent Yellow 2 [60-11-
7], Solvent Yellow 3 [97-56-3], Solvent Yellow 7 [1689-82-3], Solvent
Yellow 14 [842-07-9], Disperse Orange 1 [2581-69-3], Disperse Orange
3 [730-40-5], Disperse Orange 25 [31482-56-1], Disperse Red 1 [2872-
52-8], Disperse Red 13 [3180-81-2], Disperse Red 19 [2734-52-3],
Disperse Red 50 [ 12223-3 5-7] + [40880-5 1 -1 ], Disperse Yellow 3,
Mordant Brown 4 [6247-28-5], Mordant Brown 6 [6247-28-5], Mordant
Brown 24 [6370-46-3], Mordant Brown 48 [6232-53-7], Mordant Orange
1 [2243-76-7], Pigment Red 3 [2425-85-6], 4-dimethylamino-2-
methylazobenzene [54-88-6], 2-(4-diethylaminophenylazo)benzoic acid
[76058-33-8], N-ethyl-N-(2-aminoethyl)-4-(4-nitrophenylazo)aniline,
N,N-hydroxyethyl-4-(4-nitrophenylazo)-2-methylaniline, N,N-hydroxy-
ethyl-4-(4-aminophenylazo)-2-aniline, and mixtures thereof.
26. Cosmetic article according to any one of the preceding
claims, characterized in that the direct dye(s) or direct dye precursor(s)
represent(s) from 0.5% to 50% by weight and more preferentially from
5% to 50% by weight relative to the total weight of the cosmetic article.
27. Process for dyeing keratin materials, characterized in that
the cosmetic article as defined in any one of Claims 1 to 26 is positioned
on or close to the keratin materials, and in that a source of heat is
-33-

applied, resulting in thermal transfer of the dye(s) onto or into the
keratin materials.
28. Process according to the preceding claim, characterized in
that the source of heat is at a temperature of between 100 and 500°C and
preferably between 130 and 250°C.
29. Process according to Claim 27 or 28, characterized in that
the time for applying the source of heat is between 1 second and 5
minutes and preferentially between 30 seconds and 3 minutes.
-34-
30.Use of the cosmetic article as defined in any one of Claims
1 to 26, for dyeing keratin fibres.

The present invention relates to a substantially dry cosmetic
article for dyeing the hair, comprising
- a porous flexible substrate, and
- one or more direct dyes or direct dye precursors in powder
form, which are capable of dyeing the keratin material via heat transfer,
the substrate and the direct dyes or direct dye precursors being
non-covalently bonded to the substrate.
The present invention moreover relates to a process for dyeing
keratin materials using this dry heat-transfer cosmetic article. The
invention also relates to the use of this article for dyeing keratin
materials, especially human keratin materials, via dry heat transfer.