U.S. patent application number 11/339466 was filed with the patent office on 2006-06-08 for composition for dyeing keratin fibres with a cationic direct dye and a thickening polymer.
This patent application is currently assigned to L'OREAL S.A.. Invention is credited to Jean Cotteret, Gerard Lang.
Application Number | 20060117497 11/339466 |
Document ID | / |
Family ID | 9528487 |
Filed Date | 2006-06-08 |
United States Patent
Application |
20060117497 |
Kind Code |
A1 |
Lang; Gerard ; et
al. |
June 8, 2006 |
Composition for dyeing keratin fibres with a cationic direct dye
and a thickening polymer
Abstract
The invention relates to a composition for dyeing fibers such as
the hair, comprising at least one cationic direct dye of given
formula, and which also contains at least one thickening polymer
chosen from the group comprising:--nonionic amphiphilic polymers
comprising at least one hydrophilic unit and at least one unit
containing a fatty chain,--anionic amphiphilic polymers comprising
at least one hydrophilic unit and at least one unit containing a
fatty chain,--cationic amphiphilic polymers comprising at least one
hydrophilic unit and at least one unit containing a fatty chain.
The invention also relates to the dyeing processes and dyeing kits
therefor.
Inventors: |
Lang; Gerard; (Saint Prix,
FR) ; Cotteret; Jean; (Verneuil Sur Seine,
FR) |
Correspondence
Address: |
FINNEGAN, HENDERSON, FARABOW, GARRETT & DUNNER;LLP
901 NEW YORK AVENUE, NW
WASHINGTON
DC
20001-4413
US
|
Assignee: |
L'OREAL S.A.
|
Family ID: |
9528487 |
Appl. No.: |
11/339466 |
Filed: |
January 26, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10869058 |
Jun 17, 2004 |
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11339466 |
Jan 26, 2006 |
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09350579 |
Jul 8, 1999 |
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10869058 |
Jun 17, 2004 |
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Current U.S.
Class: |
8/405 |
Current CPC
Class: |
A61K 8/4953 20130101;
A61K 8/496 20130101; A61K 8/49 20130101; A61K 8/4946 20130101; A61K
8/4926 20130101; A61K 8/8182 20130101; A61Q 5/10 20130101; A61Q
5/065 20130101; A61K 8/731 20130101; A61K 8/494 20130101; A61K 8/86
20130101; A61K 8/737 20130101 |
Class at
Publication: |
008/405 |
International
Class: |
A61K 8/00 20060101
A61K008/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 9, 1998 |
FR |
98 08835 |
Claims
1. A ready-to-use composition for dyeing fibers, comprising: (i) at
least one cationic direct dye chosen from compounds of formulae
(I), (II), (III), (III') and (IV) below, and (ii) at least one
thickening polymer; (a) wherein said compounds of formula (I) are
chosen from compounds of formula: ##STR45## in which: D is chosen
from a nitrogen atom and a --CH group, R.sub.1 and R.sub.2, which
may be identical or different, are chosen from a hydrogen atom; a
4'-aminophenyl radical; and C.sub.1-C.sub.4 alkyl radicals which
can optionally be substituted with a radical chosen from --CN, --OH
and --NH.sub.2 radicals or form, with each other or a carbon atom
of the benzene ring of formula (I), a heterocycle optionally
containing a heteroatom chosen from oxygen and nitrogen, which can
be substituted with at least one radical chosen from
C.sub.1-C.sub.4 alkyl radicals; R.sub.3 and R'.sub.3, which may be
identical or different, are chosen from a hydrogen atom, halogen
atoms, a cyano radical, C.sub.1-C.sub.4 alkyl radicals,
C.sub.1-C.sub.4 alkoxy radicals and acetyloxy radicals, X.sup.- is
chosen from anions, A is chosen from structures A.sub.1 to A.sub.19
below: ##STR46## ##STR47## in which: R.sub.4 is chosen from
C.sub.1-C.sub.4 alkyl radicals which can be substituted with a
hydroxyl radical, and R.sub.5 is chosen from C.sub.1-C.sub.4 alkoxy
radicals, and wherein when D represents --CH, when A represents
A.sub.4 or A.sub.13 and when R.sub.3 is not an alkoxy radical,
R.sub.1 and R.sub.2 are not both a hydrogen atom; (b) wherein said
compounds of formula (II) are chosen from compounds of formula:
##STR48## in which: R.sub.6 is chosen from a hydrogen atom and
C.sub.1-C.sub.4 alkyl radicals, R.sub.7 is chosen from a hydrogen
atom, alkyl radicals which can be substituted with a species chosen
from a --CN radical and an amino group, and a 4'-aminophenyl
radical, or forms, with R.sub.6, a heterocycle optionally
comprising at least one heteroatom chosen from oxygen and nitrogen,
which can be substituted with C.sub.1-C.sub.4 alkyl radicals,
R.sub.8 and R.sub.9, which may be identical or different, are
chosen from a hydrogen atom, halogen atoms, C.sub.1-C.sub.4 alkyl
radicals C.sub.1-C.sub.4 alkoxy radicals and a --CN radical,
X.sup.- is chosen from anions, B is chosen from structures B.sub.1
to B.sub.6 below: ##STR49## in which: R.sub.10 is chosen from
C.sub.1-C.sub.4 alkyl radicals, and R.sub.11 and R.sub.12, which
may be identical or different, are chosen from a hydrogen atom and
C.sub.1-C.sub.4 alkyl radicals; (c) wherein said compounds of
formulae (III) and (III') are chosen from compounds of formulae:
##STR50## in which: R.sub.13 is chosen from a hydrogen atom,
C.sub.1-C.sub.4 alkoxy radicals, halogen atoms and an amino
radical, R.sub.14 is chosen from a hydrogen atom, C.sub.1-C.sub.4
alkyl radicals or forms, with a carbon atom of the benzene ring, a
heterocycle optionally containing an oxygen heteroatom and/or
substituted with at least one to radical chosen from
C.sub.1-C.sub.4 alkyl radicals, R.sub.15 is chosen from a hydrogen
atom and halogen atoms, R.sub.16 and R.sub.17, which may be
identical or different, are chosen from a hydrogen atom and
C.sub.1-C.sub.4 alkyl radicals, D.sub.1 and D.sub.2, which may be
identical or different, are chosen from a nitrogen atom and a --CH
group, m=0 or 1, wherein when R.sub.13 is an unsubstituted amino
group, D.sub.1 and D.sub.2 are both a group and m=0, X.sup.- is
chosen from anions, E is chosen from structures E.sub.1 to E.sub.8
below: ##STR51## in which R' is chosen from C.sub.1-C.sub.4 alkyl
radicals; wherein when m=0 and when D.sub.1 represents a nitrogen
atom, E can be further chosen from structure E9 below: ##STR52## in
which R' is chosen from C.sub.1-C.sub.4 alkyl radicals; (d) wherein
said compounds of formula (IV) are chosen from compounds of
formula: G-N.dbd.N-J (IV) in which: G is chosen from structures
G.sub.1 to G.sub.3 below: ##STR53## in which: R.sub.18 is chosen
from C.sub.1-C.sub.4 alkyl radicals and a phenyl radical which can
optionally be substituted with C.sub.1-C.sub.4 alkyl radicals or a
halogen atom chosen from chlorine, bromine, iodine and fluorine;
R.sub.19 is chosen from C.sub.1-C.sub.4 radicals and a phenyl
radical; R.sub.20 and R.sub.21, which may be identical or
different, are chosen from C.sub.1-C.sub.4 alkyl radicals and a
phenyl radical, or together form, in G.sub.1, a benzene ring
substituted with at least one radical chosen from C.sub.1-C.sub.4
alkyl radicals, C.sub.1-C.sub.4 alkoxy radicals and NO.sub.2
radicals, or together form, in G.sub.2, a benzene ring optionally
substituted with at least one radical chosen from C.sub.1-C.sub.4
alkyl radicals, C.sub.1-C.sub.4 alkoxy radicals and NO.sub.2
radicals; R.sub.20 can be further chosen from a hydrogen atom; Z is
chosen from an oxygen atom, a sulphur atom and --NR.sub.19
radicals; M is chosen from a --CH radical, --C(C.sub.1-C.sub.4
alkyl) radicals and --N.sup.+R.sub.22(X.sup.-).sub.r radicals; K is
chosen from a --CH radical, --C(C.sub.1-C.sub.4 alkyl) radicals and
--N.sup.+R.sub.22(X.sup.-).sub.r radicals; P is chosen from a --CH
radical, --C(C.sub.1-C.sub.4 alkyl) radicals and
--N.sup.+R.sub.22(X.sup.-).sub.r radicals; wherein r denotes zero
or 1; wherein R.sub.22 is chosen from an O.sup.- anion,
C.sub.1-C.sub.4 alkoxy radicals, and C.sub.1-C.sub.4 alkyl
radicals; R.sub.23 and R.sub.24, which may be identical or
different, are chosen from a hydrogen atom, halogen atoms chosen
from chlorine, bromine, iodine and fluorine, C.sub.1-C.sub.4 alkyl
radicals, C.sub.1-C.sub.4 alkoxy radicals and an --NO.sub.2
radical; X.sup.- is chosen from anions; wherein if R.sub.22 is
O.sup.-, r is zero; wherein if K or P or M is
C.sub.1-C.sub.4--N.sup.+-alkyl X.sup.-, either R.sub.23 or R.sub.24
is not a hydrogen atom; wherein if K is
--N.sup.+R.sub.22(X.sup.-).sub.r, M and P are the same and are
chosen from a --CH radical and --C(C.sub.1-C.sub.4 alkyl) radicals;
wherein if M denotes --N.sup.+R.sub.22(X.sup.-).sub.r, K and P are
the same and are chosen from a --CH radical and --C(C.sub.1-C.sub.4
alkyl) radicals; if P is --N.sup.+R.sub.22(X.sup.-).sub.r, K and M
are the same and are chosen from a --CH radical and
--C(C.sub.1-C.sub.4 alkyl) radicals; if Z is a sulphur atom with
R.sub.21 being a radical chosen from C.sub.1-C.sub.4 alkyl
radicals, R.sub.20 is not a hydrogen atom; if Z is --NR.sub.22 with
R.sub.19 being a radical chosen from C.sub.1-C.sub.4 alkyl
radicals, at least one of the radicals R.sub.18, R.sub.20 and
R.sub.21 of G.sub.2 is not chosen from C.sub.1-C.sub.4 alkyl
radicals; J is chosen from: (1) radicals chosen from structure
J.sub.1 below: ##STR54## in which: R.sub.25 is chosen from a
hydrogen atom, halogen atoms chosen from chlorine, bromine, iodine
and fluorine, C.sub.1-C.sub.4 alkyl radicals, C.sub.1-C.sub.4
alkoxy radicals, an --OH radical, an --NO.sub.2 radical,
--NHR.sub.28 radicals, --NR.sub.29R.sub.30 radicals,
--NHCO(C.sub.1-C.sub.4) alkyl radicals, or forms, with R.sub.26, a
5- or 6-membered ring optionally containing at least one heteroatom
chosen from nitrogen, oxygen and sulphur; R.sub.26 is chosen from a
hydrogen atom, halogen atoms chosen from chlorine, bromine, iodine
and fluorine, C.sub.1-C.sub.4 alkyl radicals, C.sub.1-C.sub.4
alkoxy radicals or forms, with R.sub.27 or R.sub.28, a 5- or
6-membered ring optionally containing at least one heteroatom
chosen from nitrogen, oxygen and sulphur; R.sub.27 is chosen from a
hydrogen atom, an --OH radical, --NHR.sub.28 radicals and
--NR.sub.29R.sub.30 radicals; R.sub.28 is chosen from a hydrogen
atom, C.sub.1-C.sub.4 alkyl radicals, C.sub.1-C.sub.4
monohydroxyalkyl radicals, C.sub.2-C.sub.4 polyhydroxyalkyl
radicals and a phenyl radical; R.sub.29 and R.sub.30, which may be
identical or different, are chosen from C.sub.1-C.sub.4 alkyl
radicals, C.sub.1-C.sub.4 monohydroxyalkyl radicals and
C.sub.2-C.sub.4 polyhydroxyalkyl radicals; (2) 5- and 6-membered
nitrogenous heterocyclic groups optionally containing other
heteroatoms and/or carbonyl groups and optionally substituted with
at least one radical chosen from C.sub.1-C.sub.4 alkyl radicals, an
amino radical, a phenyl radical, and wherein said at least one
thickening polymer is chosen from polymers comprising:
(ii).sub.1--nonionic amphiphilic polymers, comprising: at least one
hydrophilic unit and at least one unit comprising a fatty chain;
(ii).sub.2--anionic amphiphilic polymers, comprising: at least one
hydrophilic unit and at least one unit comprising a fatty chain;
and (ii).sub.3--cationic amphiphilic polymers, comprising at least
one hydrophilic unit and at least one unit comprising a fatty
chain.
Description
[0001] The invention relates to a composition for dyeing keratin
fibres, in particular human keratin fibres such as the hair,
comprising, in a medium which is suitable for dyeing, at least one
cationic direct dye of given formula and at least one specific
thickening polymer.
[0002] The invention also relates to the dyeing processes and
dyeing devices using the said composition.
[0003] Two types of dyeing may be distinguished in the haircare
sector.
[0004] The first is semi-permanent or temporary dyeing, or direct
dyeing, which uses dyes capable of giving the hair a natural
coloration, a more or less pronounced colour change which may
withstand shampooing several times. These dyes are also known as
direct dyes; they can be used with or without an oxidizing agent.
In the presence of an oxidizing agent, the aim is to obtain
lightening dyeing. Lightening dyeing is carried out by applying a
mixture, prepared at the time of use, of a direct dye and an
oxidizing agent to the hair, and makes it possible in particular to
obtain, by lightening the melanin in the hair, an advantageous
effect such as a unified colour in the case of grey hair, or to
bring out the colour in the case of naturally pigmented hair.
[0005] The second is permanent dyeing or oxidation dyeing. This is
carried out with so-called "oxidation" dyes comprising oxidation
dye precursors and couplers. Oxidation dye precursors, commonly
known as "oxidation bases", are compounds which are initially
colourless or weakly coloured which develop their dyeing power on
the hair in the presence of oxidizing agents added at the time of
use, leading to the formation of coloured compounds and dyes. The
formation of these coloured compounds and dyes results either from
an oxidative condensation of the "oxidation bases" with themselves
or from an oxidative condensation of the oxidation bases with
coloration-modifying compounds commonly known as "couplers", which
are generally present in the dye compositions used in oxidation
dyeing.
[0006] It is known practice to add direct dyes to oxidation dyes in
order to vary the shades obtained with the said oxidation dyes or
to enrich the shades with glints.
[0007] Among the cationic direct dyes available in the sector of
dyeing keratin fibres, in particular human keratin fibres, the
compounds whose structure is developed in the text hereinbelow are
already known; nevertheless, these dyes lead to colorations which
have characteristics that are still unsatisfactory as regards the
intensity, the homogeneity of the colour distributed along the
fibre, in which case the coloration is said to be too selective,
and as regards the staying power, in terms of the resistance to the
various attacking factors to which the hair may be subjected
(light, bad weather, shampooing).
[0008] After considerable research conducted in this matter, the
Applicant has now discovered that it is possible to obtain novel
compositions for dyeing keratin fibres which are capable of giving
more intense and yet unselective colorations which show good
resistance to the various attacking factors to which the hair may
be subjected, by combining at least one specific thickening polymer
with at least one known cationic direct dye of the prior art, which
have the respective formulae defined below.
[0009] This discovery forms the basis of the present invention.
[0010] A first subject of the present invention is thus a
composition for dyeing keratin fibres, and in particular human
keratin fibres such as the hair, containing, in a medium which is
suitable for dyeing, (i) at least one cationic direct dye whose
structure corresponds to formulae (I) to (IV) defined below,
characterized in that it also contains (ii) at least one specific
thickening polymer.
(i) The cationic direct dye which can be used according to the
present invention is a compound chosen from those of formulae (I),
(II), (III), (III') and (IV) below:
[0011] a) the compounds of formula (I) below: ##STR1## in which: D
represents a nitrogen atom or a --CH group, R.sub.1 and R.sub.2,
which may be identical or different, represent a hydrogen atom; a
C.sub.1-C.sub.4 alkyl radical which can be substituted with a --CN,
--OH or --NH.sub.2 radical or form, with a carbon atom of the
benzene ring, a heterocycle optionally containing oxygen or
nitrogen, which can be substituted with one or more C.sub.1-C.sub.4
alkyl radicals; a 4'-aminophenyl radical, R.sub.3 and R'.sub.3,
which may be identical or different, represent a hydrogen atom, a
halogen atom chosen from chlorine, bromine, iodine and fluorine, a
cyano radical, or a C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy
or acetyloxy radical, X.sup.- represents an anion preferably chosen
from chloride, methyl sulphate and acetate, A represents a group
chosen from the structures A1 to A19 below: ##STR2## ##STR3## in
which R.sub.4 represents a C.sub.1-C.sub.4 alkyl radical which can
be substituted with a hydroxyl radical and R.sub.5 represents a
C.sub.1-C.sub.4 alkoxy radical, with the proviso that when D
represents --CH, when A represents A.sub.4 or A.sub.13 and when
R.sub.3 is other than an alkoxy radical, then R.sub.1 and R.sub.2
do not simultaneously denote a hydrogen atom;
[0012] b) the compounds of formula (II) below: ##STR4## in which:
R.sub.6 represents a hydrogen atom or a C.sub.1-C.sub.4 alkyl
radical, R.sub.7 represents a hydrogen atom, an alkyl radical which
can be substituted with a --CN radical or with an amino group, a
4'-aminophenyl radical or forms with R.sub.6 a heterocycle
optionally containing oxygen and/or nitrogen, which can be
substituted with a C.sub.1-C.sub.4 alkyl radical, R.sub.6 and
R.sub.9, which may be identical or different, represent a hydrogen
atom, a halogen atom such as bromine, chlorine, iodine or fluorine,
a C.sub.1-C.sub.4 alkyl or C.sub.1-C.sub.4 alkoxy radical or a --CN
radical, X.sup.- represents an anion preferably chosen from
chloride, methyl sulphate and acetate, B represents a group chosen
from the structures B1 to B6 below: ##STR5## in which R.sub.10
represents a C.sub.1-C.sub.4 alkyl radical, R.sub.11 and R.sub.12,
which may be identical or different, represent a hydrogen atom or a
C.sub.1-C.sub.4 alkyl radical;
[0013] c) the compounds of formulae (III) and (III') below:
##STR6## in which: R.sub.13 represents a hydrogen atom, a
C.sub.1-C.sub.4 alkoxy radical, a halogen atom such as bromine,
chlorine, iodine or fluorine, or an amino radical, R.sub.14
represents a hydrogen atom, a C.sub.1-C.sub.4 alkyl radical or
forms, with a carbon atom of the benzene ring, a heterocycle
optionally containing oxygen and/or substituted with one or more
C.sub.1-C.sub.4 alkyl groups, R.sub.15 represents a hydrogen atom
or a halogen atom such as bromine, chlorine, iodine or fluorine,
R.sub.16 and R.sub.17, which may be identical or different,
represent a hydrogen atom or a C.sub.1-C.sub.4 alkyl radical,
D.sub.1 and D.sub.2, which may be identical or different, represent
a nitrogen atom or a --CH group, m=0 or 1, it being understood that
when R.sub.13 represents an unsubstituted amino group, then D.sub.1
and D.sub.2 simultaneously represent a --CH group and m=0, X.sup.-
represents an anion preferably chosen from chloride, methyl
sulphate and acetate, E represents a group chosen from the
structures E1 to E8 below: ##STR7## in which R' represents a
C.sub.1-C.sub.4 alkyl radical; when m=0 and when D.sub.1 represents
a nitrogen atom, then E can also denote a group of structure E9
below: ##STR8## in which R' represents a C.sub.1-C.sub.4 alkyl
radical;
[0014] d) the compounds of formula (IV) below: G-N.dbd.N-J (IV) in
which: the symbol G represents a group chosen from the structures
G.sub.1 to G.sub.3 below: ##STR9## in which structures G.sub.1 to
G.sub.3, R.sub.18 denotes a C.sub.1-C.sub.4 alkyl radical, a phenyl
radical which can be substituted with a C.sub.1-C.sub.4 alkyl
radical or a halogen atom chosen from chlorine, bromine, iodine and
fluorine; R.sub.19 denotes a C.sub.1-C.sub.4 alkyl radical or a
phenyl radical; R.sub.20 and R.sub.21, which may be identical or
different, represent a C.sub.1-C.sub.4 alkyl radical, a phenyl
radical or together form, in G.sub.1, a benzene ring substituted
with one or more C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy or
NO.sub.2 radicals or together form, in G.sub.2, a benzene ring
optionally substituted with one or more C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 alkoxy or NO.sub.2 radicals; R.sub.20 can also
denote a hydrogen atom; Z denotes an oxygen or sulphur atom or a
group --NR.sub.19; M represents a --CH, --CR (R denoting
C.sub.1-C.sub.4 alkyl) or --N.sup.+R.sub.22(X.sup.-).sub.r group; K
represents a --CH, --CR (R denoting C.sub.1-C.sub.4 alkyl) or
--N.sup.+R.sub.22(X.sup.-).sub.r group; P represents a --CH, --CR
(R denoting C.sub.1-C.sub.4 alkyl) or
--N.sup.+R.sub.22(X.sup.-).sub.r group; r denotes zero or 1;
R.sub.22 represents an O.sup.- anion, a C.sub.1-C.sub.4 alkoxy
radical or a C.sub.1-C.sub.4 alkyl radical; R.sub.23 and R.sub.24,
which may be identical or different, represent a hydrogen atom, a
halogen atom chosen from chlorine, bromine, iodine and fluorine, a
C.sub.1-C.sub.4 alkyl or C.sub.1-C.sub.4 alkoxy radical or an
--NO.sub.2 radical; X.sup.- represents an anion preferably chosen
from chloride, iodide, methyl sulphate, ethyl sulphate, acetate and
perchlorate; with the proviso that, if R.sub.22 denotes O.sup.-,
then r denotes zero; if K or P or M denote
C.sub.1-C.sub.4--N.sup.+-alkyl X.sup.-, then R.sub.23 or R.sub.24
is other than a hydrogen atom; if K denotes
--N.sup.+R.sub.22(X.sup.-).sub.r, then M=P.dbd.--CH, --CR; if M
denotes --N.sup.+R.sub.22(X.sup.-).sub.r, then K.dbd.P.dbd.--CH,
--CR; if P denotes --N.sup.+R.sub.22(X.sup.-).sub.r, then K=M and
denote --CH or --CR; if Z denotes a sulphur atom with R.sub.21
denoting C.sub.1-C.sub.4 alkyl, then R.sub.20 is other than a
hydrogen atom; if Z denotes --NR.sub.22 with R.sub.19 denoting
C.sub.1-C.sub.4 alkyl, then at least one of the radicals R.sub.1,
R.sub.20 or R.sub.21 of the group of structure G.sub.2 is other
than a C.sub.1-C.sub.4 alkyl radical; the symbol J represents: (a)
a group of structure J.sub.1 below: ##STR10## in which structure
J.sub.1, R.sub.25 represents a hydrogen atom, a halogen atom chosen
from chlorine, bromine, iodine and fluorine, a C.sub.1-C.sub.4
alkyl or C.sub.1-C.sub.4 alkoxy radical, a radical --OH,
--NO.sub.2, --NHR.sub.28, --NR.sub.29R.sub.30,
--NHCO(C.sub.1-C.sub.4) alkyl, or forms with R.sub.26 a 5- or
6-membered ring which may or may not contain one or more hetero
atoms chosen from nitrogen, oxygen and sulphur; R.sub.26 represents
a hydrogen atom, a halogen atom chosen from chlorine, bromine,
iodine and fluorine, a C.sub.1-C.sub.4 alkyl or C.sub.1-C.sub.4
alkoxy radical or forms, with R.sub.27 or R.sub.28, a 5- or
6-membered ring which may or may not contain one or more hetero
atoms chosen from nitrogen, oxygen and sulphur; R.sub.27 represents
a hydrogen atom, an --OH radical, a radical --NHR.sub.28 or a
radical --NR.sub.29R.sub.30; R.sub.28 represents a hydrogen atom, a
C.sub.1-C.sub.4 alkyl radical, a C.sub.1-C.sub.4 monohydroxyalkyl
radical, a C.sub.2-C.sub.4 polyhydroxyalkyl radical or a phenyl
radical; R.sub.29 and R.sub.30, which may be identical or
different, represent a C.sub.1-C.sub.4 alkyl radical, a
C.sub.1-C.sub.4 monohydroxyalkyl radical or a C.sub.2-C.sub.4
polyhydroxyalkyl radical; (b) a 5- or 6-membered nitrogenous
heterocyclic group which can contain other hetero atoms and/or
carbonyl groups and which can be substituted with one or more
C.sub.1-C.sub.4 alkyl, amino or phenyl radicals, and in particular
a group of structure J.sub.2 below: ##STR11## in which structure
J.sub.2, R.sub.31 and R.sub.32, which may be identical or
different, represent a hydrogen atom, a C.sub.1-C.sub.4 alkyl
radical or a phenyl radical; Y denotes the --CO-- radical or the
radical ##STR12## n 0 or 1, with, when n denotes 1, U denoting a
--CO-- radical.
[0015] In the structures (I) to (IV) defined above, the
C.sub.1-C.sub.4 alkyl or alkoxy group preferably denotes methyl,
ethyl, butyl, methoxy or ethoxy.
[0016] The cationic direct dyes of formulae (I), (II), (III) and
(III') which can be used in the dye compositions in accordance with
the invention are known compounds and are described, for example,
in patent applications WO 95/01772, WO 95/15144 and EP-A-0,714,954.
Those of formula (IV) which can be used in the dye compositions in
accordance with the invention are known compounds and are
described, for example, in patent applications FR-2,189,006,
FR-2,285,851 and FR-2,140,205 and its Certificates of Addition.
[0017] Among the cationic direct dyes of formula (I) which can be
used in the dye compositions in accordance with the invention,
mention may be made more particularly of the compounds
corresponding to the structures (I1) to (I54) below: ##STR13##
##STR14## ##STR15## ##STR16## ##STR17## ##STR18## ##STR19##
[0018] Among the compounds of structures (I1) to (I54) described
above, the ones most particularly preferred are the compounds
corresponding to the structures (I1), (I2), (I14) and (I31).
[0019] Among the cationic direct dyes of formula (II) which can be
used in the dye compositions in accordance with the invention,
mention may be made more particularly of the compounds
corresponding to the structures (II1) to (II9) below: ##STR20##
##STR21## ##STR22## ##STR23## ##STR24## ##STR25## ##STR26##
[0020] Among the cationic direct dyes of formula (III) which can be
used in the dye compositions in accordance with the invention,
mention may be made more particularly of the compounds
corresponding to the structures (III1) to (III18) below: ##STR27##
##STR28##
[0021] Among the specific compounds of structures (III1) to (III18)
described above, the ones most particularly preferred are the
compounds corresponding to the structures (III4), (III5) and
(III13).
[0022] Among the cationic direct dyes of formula (III') which can
be used in the dye compositions in accordance with the invention,
mention may be made more particularly of the compounds
corresponding to the structures (III'1) to (III'3) below:
##STR29##
[0023] Among the cationic direct dyes of formula (IV) which can be
used in the dye compositions in accordance with the invention,
mention may be made more particularly of the compounds of
structures (IV).sub.1 to (IV).sub.77 below: ##STR30## ##STR31##
##STR32## ##STR33## ##STR34## ##STR35## ##STR36## ##STR37##
##STR38## ##STR39## ##STR40##
[0024] The cationic direct dye(s) used according to the invention
preferably represent(s) from 0.001 to 10% by weight approximately
relative to the total weight of the dye composition and even more
preferably from 0.005 to 5% by weight approximately relative to
this weight.
(ii) The thickening polymer which can be used according to the
present invention is chosen from the group consisting of:
[0025] (ii).sub.1--nonionic amphiphilic polymers comprising at
least one hydrophilic unit and at least one unit containing a fatty
chain; [0026] (ii).sub.2--anionic amphiphilic polymers comprising
at least one hydrophilic unit and at least one unit containing a
fatty chain; [0027] (ii).sub.3--cationic amphiphilic polymers
comprising at least one hydrophilic unit and at least one unit
containing a fatty chain.
[0028] The nonionic amphiphilic polymers comprising at least one
hydrophilic unit and at least one unit containing a fatty chain
(ii).sub.1, used according to the invention, are preferably chosen
from:
[0029] (ii).sub.1(a) celluloses modified with groups comprising at
least one fatty chain; mention may be made, by way of example, of:
[0030] hydroxyethylcelluloses modified with groups comprising at
least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups
or mixtures thereof, and in which the alkyl groups are preferably
C.sub.8-C.sub.22, such as the product Natrosol Plus Grade 330
CS(C.sub.16 alkyls) sold by the company Aqualon, or the product
Bermocoll EHM 100 sold by the company Berol Nobel, [0031]
hydroxyethylcelluloses modified with groups comprising at least one
polyalkylene glycol alkylphenyl ether group, such as the product
Amercell Polymer HM-1500 (polyethylene glycol (15) nonylphenyl
ether) sold by the company Amerchol. [0032] (ii).sub.1(b)
hydroxypropylguars modified with groups comprising at least one
fatty chain, such as the product Esaflor HM 22 (C.sub.22 alkyl
chain) sold by the company Lamberti, and the products Miracare
XC95-3 (C.sub.14 alkyl chain) and RE205-1 (C.sub.20 alkyl chain)
sold by the company Rhone-Poulenc. [0033] (ii).sub.1(c)
polyurethane ethers comprising at least one fatty chain such as
C.sub.8-C.sub.30 alkyl or alkenyl groups, for instance the products
Dapral T 210 and Dapral T 212 sold by the company Akzo. [0034]
(ii).sub.1(d) copolymers of vinylpyrrolidone and of hydrophobic
monomers containing a fatty chain; mention may be made, by way of
example, of: [0035] the products Antaron V216 or Ganex V216
(vinylpyrrolidone/hexadecene copolymer) sold by the company I.S.P.
[0036] the products Antaron V220 or Ganex V220
(vinylpyrrolidone/eicosene copolymer) sold by the company I.S.P.
[0037] (ii).sub.1(e) copolymers of C.sub.1-C.sub.6 alkyl
methacrylates or acrylates and of amphiphilic monomers comprising
at least one fatty chain, such as, for example, the oxyethylenated
methyl methacrylate/stearyl acrylate copolymer sold by the company
Goldschmidt under the name Antil 208. [0038] (ii).sub.1(f)
copolymers of hydrophilic methacrylates or acrylates and of
hydrophobic monomers comprising at least one fatty chain, such as,
for example, the polyethylene glycol methacrylate/lauryl
methacrylate copolymer.
[0039] The anionic amphiphilic polymers (ii).sub.2, can be chosen
from those: [0040] (ii).sub.2(a) comprising at least one
hydrophilic unit and at least one allyl ether unit containing a
fatty chain, and preferably from those in which the hydrophilic
unit comprising an unsaturated ethylenic anionic monomer, more
particularly of a vinylcarboxylic acid and most particularly of an
acrylic acid, a methacrylic acid or mixtures thereof, and in which
the allyl ether unit containing a fatty chain corresponds to the
monomer of formula (V) below: CH.sub.2.dbd.CR'CH.sub.2OB.sub.nR (V)
in which R' denotes H or CH.sub.3, B denotes an ethylenoxy radical,
n is zero or denotes an integer ranging from 1 to 100, R denotes a
hydrocarbon-based radical chosen from alkyl and cycloalkyl radicals
comprising from 8 to 30 carbon atoms, preferably 10 to 24 and even
more particularly from 12 to 18 carbon atoms, and most particularly
a C.sub.10-C.sub.24 alkyl radical.
[0041] One unit of formula (V) which is more particularly preferred
according to the present invention is a unit in which R' denotes H,
n is equal to 10 and R denotes a stearyl (C.sub.18) radical.
[0042] Anionic amphiphilic polymers of this type are described and
prepared according to an emulsion polymerization process in patent
EP-0,216,479 B2.
[0043] Among the said anionic amphiphilic polymers cited
(ii).sub.2(a) it is particularly preferred according to the
invention to use the polymers formed from 20 to 60% by weight of
acrylic acid and/or methacrylic acid, from 5 to 60% by weight of
lower alkyl (meth)acrylates, from 2 to 50% by weight of allyl ether
containing a fatty chain of formula (I), and from 0 to 1% by weight
of a crosslinking agent which is a well known copolymerizable
polyethylenic unsaturated monomer, such as diallyl phthalate, allyl
(meth)acrylate, divinylbenzene, (poly)ethylene glycol
dimethacrylate and methylenebisacrylamide.
[0044] Among the latter polymers, the ones most particularly
preferred are the crosslinked terpolymers of methacrylic acid, of
ethyl acrylate, of polyethylene glycol (10 EO) stearyl ether
(Steareth-10), in particular those sold by the company Allied
Colloids under the names Salcare SC 80 and Salcare SC 90 which are
aqueous 30% emulsions of a crosslinked terpolymer of methacrylic
acid, of ethyl acrylate and of Steareth-10 allyl ether
(40/50/10).
[0045] The anionic amphiphilic polymers (ii).sub.2 can also be
chosen from those: [0046] (ii).sub.2(b) comprising at least one
hydrophilic unit of unsaturated olefinic carboxylic acid type, and
at least one unit containing a fatty chain exclusively of
(C.sub.10-C.sub.30)alkyl ester of unsaturated carboxylic acid type,
and preferably from those in which the hydrophilic unit of
unsaturated olefinic carboxylic acid type corresponds to the
monomer of formula (VI) below: ##STR41## in which formula R.sup.1
denotes H or CH.sub.3 or C.sub.2H.sub.5, i.e. acrylic acid,
methacrylic acid or ethacrylic acid units, and in which the unit
containing a fatty chain of (C.sub.10-C.sub.30)alkyl ester of
unsaturated carboxylic acid type corresponds to the monomer of
formula (VII) below: ##STR42## in which formula R.sup.1 denotes H
or CH.sub.3 or C.sub.2H.sub.5 (i.e. acrylate, methacrylate or
ethacrylate units) and preferably H (acrylate units) or CH.sub.3
(methacrylate units), R.sup.2 denoting a C.sub.10-C.sub.30 alkyl
and preferably C.sub.12-C.sub.22 alkyl radical.
[0047] (C.sub.10-C.sub.30)alkyl esters of unsaturated carboxylic
acids in accordance with the invention comprise, for example,
lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl
acrylate, dodecyl acrylate and the corresponding methacrylates,
lauryl methacrylate, stearyl methacrylate, decyl methacrylate,
isodecyl methacrylate and dodecyl methacrylate.
[0048] Anionic amphiphilic polymers of this type (ii).sub.2(b) are
described and prepared, for example, according to U.S. Pat. Nos.
3,915,921 and 4,509,949.
[0049] Anionic amphiphilic polymers (ii).sub.2(b) which can be used
in the context of the present invention can more particularly
denote polymers formed from a mixture of monomers comprising:
[0050] (i) essentially acrylic acid and an ester of formula (VII)
described above in which R.sup.1 denotes H or CH.sub.3, R.sup.2
denoting an alkyl radical containing from 12 to 22 carbon atoms,
and a crosslinking agent, such as, for example, those comprising 95
to 60% by weight of acrylic acid (hydrophilic unit), 4 to 40% by
weight of C.sub.10-C.sub.30 alkyl acrylate (unit containing a fatty
chain) and 0 to 6% by weight of crosslinking polymerizable monomer,
or 98 to 96% by weight of acrylic acid (hydrophilic unit), 1 to 4%
by weight of C.sub.10-C.sub.30 alkyl acrylate (unit containing a
fatty chain) and 0.1 to 0.6% by weight of crosslinking
polymerizable monomer, [0051] (ii) essentially acrylic acid and
lauryl methacrylate, such as the polymer formed from 66% by weight
of acrylic acid and 34% by weight of lauryl methacrylate.
[0052] The said crosslinking agent is a monomer containing a group
##STR43## with at least one other polymerizable group whose
unsaturated bonds are not conjugated to each other. Mention may be
made in particular of polyallyl ethers such as, in particular,
polyallylsucrose and polyallylpentaerythritol.
[0053] Among the said polymers cited in class (ii).sub.2(b), the
ones most particularly preferred according to the present invention
are the products sold by the company Goodrich under the trade names
Pemulen TR1, Pemulen TR2, Carbopol 1382 and even more preferably
Pemulen TR1 and the product sold by the company S.E.P.C. under the
name Coatex SX.
[0054] The cationic amphiphilic polymers (ii).sub.3 used according
to the invention are preferably chosen from quaternized cellulose
derivatives and polyacrylates containing amino side groups.
[0055] The quaternized cellulose derivatives are, in particular,
[0056] (ii).sub.3(a) quaternized celluloses modified with groups
comprising at least one fatty chain, such as alkyl, arylalkyl or
alkylaryl groups comprising at least 8 carbon atoms, or mixtures
thereof, [0057] (ii).sub.3(b) quaternized hydroxyethylcelluloses
modified with groups comprising at least one fatty chain, such as
alkyl, arylalkyl or alkylaryl groups comprising at least 8 carbon
atoms, or mixtures thereof.
[0058] The polyacrylates containing amino side groups
(ii).sub.3(c), which may or may not be quaternized, contain, for
example, hydrophobic groups such as Steareth-20 [polyoxyethylenated
(20) stearyl alcohol].
[0059] The alkyl radicals borne by the above quaternized celluloses
or hydroxycelluloses preferably comprise from 8 to 30 carbon
atoms.
[0060] The aryl radicals preferably denote phenyl, benzyl, naphthyl
or anthryl groups.
[0061] As examples of quaternized alkylhydroxyethyl-celluloses
containing C.sub.8-C.sub.30 fatty chains, mention may be made of
the products Quatrisoft LM200, Quatrisoft LM-X529-18-A, Quatrisoft
LM-X529-18-B. (C.sub.12 alkyl) and Quatrisoft LM-X529-8 (C.sub.18
alkyl) sold by the company Amerchol and the products Crodacel QM,
Crodacel QL (C.sub.12 alkyl) and Crodacel QS (C.sub.18 alkyl) sold
by the company Croda.
[0062] As examples of polyacrylates containing amino side chains,
mention may be made of the polymers 8781-124B or 9492-103 from the
company National Starch.
[0063] It is more particularly preferred, according to the present
invention, to use the amphiphilic polymers of nonionic type
(ii).sub.1 and of anionic type (ii).sub.2 described above and even
more particularly the amphiphilic polymers of class (ii).sub.1(a)
and (ii).sub.2(c) and of class (ii).sub.2(a) and (ii).sub.2(b).
[0064] The amphiphilic thickening polymers of nonionic, anionic or
cationic type used in the compositions of the present invention are
preferably present in a proportion of from 0.01 to 10% by weight
approximately, in particular in a proportion of from 0.1 to 5% by
weight approximately, relative to the total weight of the dye
composition applied to the keratin fibres.
[0065] The medium which is suitable for dyeing (or support)
generally comprising water or of a mixture of water and at least
one organic solvent to dissolve the compounds which would not be
sufficiently water-soluble. As organic solvents, mention may be
made, for example, of C.sub.1-C.sub.4 lower alkanols such as
ethanol and isopropanol; aromatic alcohols such as benzyl alcohol,
as well as similar products and mixtures thereof.
[0066] The solvents can be present in proportions preferably of
between 1 and 40% by weight approximately relative to the total
weight of the dye composition, and even more preferably between 5
and 30% by weight approximately.
[0067] The pH of the dye composition in accordance with the
invention is generally approximately between 2 and 11 and
preferably approximately between 5 and 10. It can be adjusted to
the desired value using acidifying or basifying agents usually used
for dyeing keratin fibres.
[0068] Among the acidifying agents, mention may be made, by way of
example, of inorganic or organic acids such as hydrochloric acid,
orthophosphoric acid, sulphuric acid, carboxylic acids such as
acetic acid, tartaric acid, citric acid and lactic acid, and
sulphonic acids.
[0069] Among the basifying agents, mention may be made, by way of
example, of aqueous ammonia, alkaline carbonates, alkanolamines
such as mono-, di- and triethanolamine and derivatives thereof,
sodium hydroxide, potassium hydroxide and the compounds of formula
(VIII) below: ##STR44## in which W is a propylene residue
optionally substituted with a hydroxyl group or a C.sub.1-C.sub.6
alkyl radical; R.sub.33, R.sub.34, R.sub.35 and R.sub.36, which may
be identical or different, represent a hydrogen atom or a
C.sub.1-C.sub.6 alkyl or C.sub.1-C.sub.6 hydroxyalkyl radical.
[0070] In addition to the cationic direct dye(s) (i) defined above,
the dye composition in accordance with the invention can contain
one or more additional direct dyes which can be chosen, for
example, from nitrobenzene dyes, anthraquinone dyes, naphthoquinone
dyes, triarylmethane dyes, xanthene dyes and azo dyes which are
non-cationic.
[0071] When it is intended for oxidation dyeing, the dye
composition in accordance with the invention contains, in addition
to the cationic direct dye(s) (i), one or more oxidation bases
chosen from the oxidation bases conventionally used for oxidation
dyeing and among which mention may be made in particular of
para-phenylenediamines, bis(phenyl)alkylenediamines,
para-aminophenols, ortho-aminophenots and heterocyclic bases.
[0072] When they are used, the oxidation base(s) preferably
represent(s) from 0.0005 to 12% by weight approximately relative to
the total weight of the dye composition, and even more preferably
from 0.005 to 6% by weight approximately relative to this
weight.
[0073] When it is intended for oxidation dyeing, the dye
composition in accordance with the invention can also contain, in
addition to the cationic direct dye (i) and the thickening polymer
(ii) as well as the oxidation bases, one or more couplers so as to
modify the shades obtained or to enrich them with glints, by using
the cationic direct dye(s) (i) and the oxidation base(s).
[0074] The couplers which can be used in the dye composition in
accordance with the invention can be chosen from the couplers used
conventionally in oxidation dyeing and among which mention may be
made in particular of meta-phenylenediamines, meta-aminophenols,
meta-diphenols and heterocyclic couplers.
[0075] When it is (they are) present, the coupler(s) preferably
represent(s) from 0.0001 to 10% by weight approximately relative to
the total weight of the dye composition, and even more preferably
from 0.005 to 5% by weight approximately relative to this
weight.
[0076] The dye composition in accordance with the invention can
also contain various adjuvants conventionally used in compositions
for dyeing the hair, such as antioxidants, penetrating agents,
sequestering agents, fragrances, buffers, dispersing agents,
surfactants, film-forming agents, ceramides, preserving agents,
screening agents and opacifiers.
[0077] Needless to say, a person skilled in the art will take care
to select this (these) optional complementary compound(s) such that
the advantageous properties intrinsically associated with the dye
composition in accordance with the invention are not, or are not
substantially, adversely affected by the addition(s) envisaged.
[0078] The dye composition according to the invention can be in
various forms, such as in the form of liquids, shampoos, creams or
gels or any other form which is suitable for dyeing keratin fibres,
and in particular human hair. It can be obtained by mixing, at the
time of use, a composition, which may be pulverulent, containing
the cationic direct dye(s) with a composition containing the
specific thickening polymer.
[0079] When the combination of the cationic direct dye (i) and the
thickening polymer (ii) according to the invention is used in a
composition intended for oxidation dyeing (in which case one or
more oxidation bases are used, optionally in the presence of one or
more couplers) or when it is used in a composition intended for
lightening direct dyeing, then the dye composition in accordance
with the invention also comprises at least one oxidizing agent
chosen, for example, from hydrogen peroxide, urea peroxide, alkali
metal bromates, persalts such as perborates and persulphates, and
enzymes such as peroxidases, lactases and two-electron
oxidoreductases. It is particularly preferred to use hydrogen
peroxide or enzymes.
[0080] Another subject of the invention is a process for dyeing
keratin fibres, and in particular human keratin fibres such as the
hair, using the dye composition as defined above.
[0081] According to a first variant of this dyeing process in
accordance with the invention, at least one dye composition as
defined above is applied to the fibres, for a period which is
sufficient to develop the desired coloration, after which the
fibres are rinsed, optionally washed with shampoo, rinsed again and
dried.
[0082] The time required to develop the coloration on the keratin
fibres is generally between 3 and 60 minutes and even more
specifically between 5 and 40 minutes.
[0083] According to a second variant of this dyeing process in
accordance with the invention, at least one dye composition as
defined above is applied to the fibres, for a period which is
sufficient to develop the desired coloration, without final
rinsing.
[0084] According to one specific embodiment of this dyeing process,
and when the dye composition in accordance with the invention
comprises at least one oxidation base and at least one oxidizing
agent, the dyeing process comprises a first step which consists in
separately storing, on the one hand, a composition (A1) comprising,
in a medium which is suitable for dyeing, at least one cationic
direct dye (i) as defined above and at least one oxidation base,
and, on the other hand, a composition (B1) comprising, in a medium
which is suitable for dyeing, at least one oxidizing agent, and
then in mixing them together at the time of use, after which this
mixture is applied to the keratin fibres, the composition (A1) or
the composition (B1) containing the thickening polymer (ii) as
defined above.
[0085] According to another specific embodiment of this dyeing
process, and when the dye composition in accordance with the
invention comprises at least one oxidizing agent, the dyeing
process comprises a first step which consists in separately
storing, on the one hand, a composition (A2) comprising, in a
medium which is suitable for dyeing, at least one cationic direct
dye (i) as defined above, and, on the other hand, a composition
(B2) comprising, in a medium which is suitable for dyeing, at least
one oxidizing agent, and then in mixing them together at the time
of use, after which this mixture is applied to the keratin fibres,
the composition (A2) or the composition (B2) containing the
thickening polymer as defined above.
[0086] Another subject of the invention is a multi-compartment
dyeing device or dyeing "kit" or any other multi-compartment
packaging system, a first compartment of which comprises the
composition (A1) or (A2) as defined above and a second compartment
of which comprises the composition (B1) or (B2) as defined above.
These devices can be equipped with means for dispensing the desired
mixture onto the hair, such as the devices described in patent FR
2,586,913 in the name of the Applicant.
[0087] The examples which follow are intended to illustrate the
invention without, however, limiting its scope.
EXAMPLES
Examples 1 to 3
[0088] The three direct dyeing compositions given in the table
below were prepared: (all contents expressed in grams)
TABLE-US-00001 Example Example Example 1 2 3 Cationic direct dye of
0.2 formula (I1) Cationic direct dye of 0.2 formula (I14) Cationic
direct dye of 0.1 formula (IV27) Diurethane (HMD) of oxy- 1.0 AM*
ethylenated (66 EO) and oxy- propylenated (14 PO) C.sub.16-C.sub.18
alcohols, sold under the name Dapral T212 by the company Akzo
Methacrylic acid/ethyl 1.0 AM* acrylate/Steareth 10 allyl ether
crosslinked terpolymer sold as a 30% by weight emulsion under the
name Salcare SC90 by the company Allied Colloid Acrylic
acid/C.sub.10-C.sub.30 alkyl 1.0 AM* acrylate crosslinked copolymer
sold under the name Pemulen TR1 by the company Goodrich Ethanol 10
10 10 2-Amino-2-methyl-1-propanol pH 9 pH 9 pH 9 qs Demineralized
water qs 100 100 100 AM* denotes active material
[0089] The above compositions were each applied for 30 minutes to
locks of natural grey hair containing 90% white hairs. The locks of
hair were then rinsed, washed with a standard shampoo and then
dried.
[0090] were dyed in the following shades: TABLE-US-00002 Examples
Shades obtained 1 Bright red 2 Bright orange 3 Bright purple
* * * * *