Note: Descriptions are shown in the official language in which they were submitted.
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COLORING AGENTS FOR KERATIN FIBERS
FIELD OF THE INVENTION
The present invention relates to agents for coloring keratin fibers, such as,
for example, wool,
furs and, in particular, human hair, based on a developer-coupler combination
and direct dyes,
which compositions make it possible to impart a long-lasting coloring of the
fiber (comparable to
the durability of semipermanent colors) without the addition of an oxidizing
agent, causing
simultaneously a low damage of the fiber (comparable to temporary hair
colors).
BACKGROUND OF THE INVENTION
In the area of the coloring of keratin fibers, in particular the coloring of
hair, oxidative
dyes have attained a substantial importance. The coloration is formed by
reaction of
certain developer substances with certain coupler substances in the presence
of a
suitable oxidizing agent. For very gentle uses, however, the need exists for
colorants
which in the presence of atmospheric oxygen give lasting colorations even
without the
addition of oxidizing agents.
It is known from the EP-A 1 166 748 that the combination of oxidative dyes and
optionally direct dyes can be used to color hair without the addition of
chemical
oxidizing agents. Constant coloring results (namely a coloration that is the
same
directly after use as well as days or weeks later) are not possible with the
colorants
described in EP-A 1 166 748.
SUMMARY OF THE INVENTION
The purpose of the present invention therefore is to provide compositions
which upon
air oxidation do not develop the coloration only after days, but do so
immediately after
application giving a uniform coloring, which remains virtually constant over
aperiod of
up to 20 hair washings.
Surprisingly, it has now been found that brilliant color results, with a
natural gloss and
a long lasting even coloring without color change of the original color can be
achieved
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by the use of a special combination of oxidative dyes and direct dyes, in
which at least
3 direct dyess are contained and the quantitative ratio of oxidative dyes to
direct dyes is
from 5:1 to 0.5:1. The colorant according to the invention colors the fiber in
a very
gentle manner (comparable to the conventionally used readily washed-out non-
oxidative colorants) so that the fiber remains practically undamaged. The
colorant
according to the invention provides a constant coloration which lasts over a
period of
up to 20 washings of the colored fiber.
DETAILED DESCRIPTION OF THE INVENTION
The object of the invention therefore is an agent for coloring keratin fibers,
in
particular human hair, which is free of chemical oxidants and is characterized
in that it
is in the form of an aqueous or aqueous-alcoholic preparation and contains a
combination of oxidative dyes (developers, couplers) and direct dyes, said
combination
containing at least 3 direct dyes, and that the quantitative ratio of
oxidation dyes to
direct dyes equals 5:1 to 0.5:1.
Suitable oxidation dyes are, for example, the following developers and
couplers and
self-coupling compounds:
(i) Developers: p-phenylenediamine derivatives, e.g. benzene-l,4-diamine
(commonly known
as p-phenylenediamine), 2-methyl-benzene-1,4-diamine, 2-chloro-benzene-1,4-
diamine, N-
phenyl-benzene-1,4-diamine, N-(2-ethoxyethyl)benzene-1,4-diamine, 2-[(4-amino-
phenyl)-(2-
hydroxy-ethyl)-amino]-ethanol, (commonly known as N,N-bis(2-hydroxyethyl)-p-
phenylenediamine) (2,5-diamino-phenyl)-methanol, 1-(2'-Hydroxyethyl)-2,5-
diaminobenzene, 2-
(2,5-diamino-phenyl)-ethanol, N-(4-aminophenyl)benzene-1,4-diamine, 2,6-
dimethyl-benzene-
1,4-diamine, 2-isopropyl-benzene-1,4-diamine, 1-[(4-aminophenyl)amino]-propan-
2-ol, 2-
propyl-benzene-1,4-diamine, 1,3-bis[(4-aminophenyl)(2-
hydroxyethyl)amino]propan-2-ol,
N4,N4,2-trimethylbenzene-1,4-diamine, 2-methoxy-benzene-1,4-diamine, 1-(2,5-
diaminophenyl)ethane-1,2-diol, 2,3-dimethyl-benzene-1,4-diamine, N-(4-amino-3-
hydroxy-
phenyl)-acetamide, 2,6-diethylbenzene-1,4-diamine, 2-methoxymethyl-benzene-1,4-
diamine,
2,5-dimethylbenzene-1,4-diamine, 2-thien-2-ylbenzene-1,4-diamine, 2-thien-3-
ylbenzene-1,4-
diamine, 2-pyridin-3-ylbenzene-1,4-diamine, 1,1'-biphenyl-2,5-diamine, 2-
(methoxymethyl)-
benzene-1,4-diamine, 2-(aminomethyl)benzene-1,4-diamine, 2-(2,5-
diaminophenoxy)ethanol,
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N-[2-(2,5-diaminophenoxy)ethyl]-acetamide, N,N-dimethylbenzene-1,4-diamine,
N,N-diethylbenzene-1,4-diamine, N,N-dipropylbenzene- 1,4-diamine, 2-[(4-
aminophenyl)-
(ethyl)amino]ethanol, 2-[(4-amino-3-methyl-phenyl)-(2-hydroxy-ethyl)-amino]-
ethanol, N-(2-
methoxyethyl)-benzene-1,4-diamine, 3-[(4-aminophenyl)amino]propan-l-ol, 3-[(4-
aminophenyl)-amino]propane-1,2-diol, N-{4-[(4-aminophenyl)amino]butyl}benzene-
1,4-
diamine, and 2-[2-(2-{2-[(2,5-diaminophenyl)-oxy]ethoxy}ethoxy)ethoxy]benzene-
1,4-diamine;
1,3-Bis(N(2-Hydroxyethyl)-N-(4-amino-phenyl)amino)-2-propanol; 2,2'-[ 1,2-
Ethanediyl-bis-
(oxy-2,1-ethanediyloxy)]-bis-benzene-1,4-diamine; N,N-Bis(2-hydroxyethyl)-p-
phenylinediamine; p-aminophenol derivatives such as: 4-amino-phenol (commonly
known as
p-aminophenol), 4-methylamino-phenol, 4-amino-3-methyl-phenol, 4-amino-2-
hydroxymethyl-
phenol, 4-amino-2-methyl-phenol, 4-amino-1-hydroxy-2-(2'-
hydroxyethylaminomethyl)benzene,
4-amino-2-methoxymethyl-phenol, 5-amino-2-hydroxy-benzoic acid, 1-(5-amino-2-
hydroxy-
phenyl)-ethane-1,2-diol, 4-amino-2-(2-hydroxy-ethyl)-phenol, 4-amino-3-
(hydroxymethyl)-
phenol, 4-amino-3-fluoro-phenol, 4-amino-2-(aminomethyl)-phenol, 4-amino-2-
fluoro-phenol;
1-Hydroxy-2,4-diaminobenzene; 1-(2'-Hydroxyethyloxy)-2,4-diaminobenzene; 2,4-
Diamino-5-
methylphenetol; o-phenylenediamine derivatives such as: 3,4-Diaminobenzoic
acid and salts
thereof; o-aminophenol derivatives such as: 2-amino-phenol (commonly known as
o-aminophenol), 2,4-diaminophenol, 2-amino-5-methyl-phenol, 2-amino-6-methyl-
phenol,
N-(4-amino-3-hydroxy-phenyl)-acetamide, and 2-amino-4-methyl-phenol; and
heterocyclic
derivatives such as: pyrimidine-2,4,5,6-tetramine (commonly known as 2,4,5,6-
tetraamino-
pyridine), 1 -methyl-1 H-pyrazole-4, 5-diamine, 2-(4, 5-diamino-1 H-pyrazol-1-
yl)ethanol,
N2,N2-dimethyl-pyridine-2,5-diamine, 2-[(3-amino-6-methoxypyridin-2-
yl)amino]ethanol,
6-methoxy-N2-methyl-pyridine-2,3-diamine, 2,5,6-triaminopyrimidin-4(1H)-one,
pyridine-2,5-
diamine, 1-isopropyl-lH-pyrazole-4,5-diamine, 1-(4-methylbenzyl)-1H-pyrazole-
4,5-diamine,
1-(benzyl)-1H-pyrazole-4,5-diamine, 1-(4-chlorobenzyl)-1H-pyrazole-4,5-
diamine, pyrazolo[1,5-
a]-pyrimidine-3,7-diamine, 5,6,7-trimethylpyrazolo[ 1,5-a]pyrimidin-3-ylamine
hydrochloride,
7-methylpyrazolo[ 1,5-a]pyrimidin-3-ylamine hydrochloride, 2,5,6,7-teramethyl-
pyrazolo[1,5-
a]pyrimidin-3-ylamine hydrochloride, 5,7-di-tert-butylpyrazolo[ 1,5-
a]pyrimidin-3-ylamine
hydrochloride, 5,7-di-trifluoromethyl-pyrazolo[1,5-a]pyrimidin-3-ylamine
hydrochloride,
2-methylpyrazolo[1,5-a]pyrimidin-3,7-diamine hydrochloride; 4-hydroxy-2,5,6-
triaminopyrimidine; 1-(2'hydroxyethyl)-amino-3,4-methylene dioxybenzene; and
1-hydroxyethyl-4,5-diaminopyrazole sulphate.
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Additional developers include: N-(3-furylmethyl)benzene-1,4-diamine; N-
Thiophen-3-ylmethyl-
benzene-1,4-diamine;lV-(2-furylmethyl)benzene-1,4-diamine; N-Thiophen-2-
ylmethyl-benzene-
1,4-diamine; 4-Hydroxy-benzoic acid (2,5-diamino-benzylidene)-hydrazide; 3-
(2,5-Diamino-
phenyl)-N-ethyl-acrylamide; 2-[3 -(3 -Amino-phenylamino)-propenyl] -benzene-
1,4-diamine;
2-[3-(4-Amino-phenylamino)-propenyl]-benzene-1,4-diamine; 2-(6-Methyl-pyridin-
2-yl)-
benzene-l,4-diamine; 2-Pyridin-2-yl-benzene-1,4-diamine; 2-[3-(4-Amino-
phenylamino)-
propenyl]-benzene-1,4-diamine; 2-[3-(3-Amino-phenylamino)-propenyl]-benzene-
1,4-diamine;
3-(2,5-Diamino-phenyl)-N-ethyl-acrylamide; 2-Thiazol-2-yl-benzene-1,4-diamine;
4-Hydroxy-
benzoic acid (2,5-diamino-benzylidene)-hydrazide; 3'-Fluoro-biphenyl-2,5-
diamine; 2-Propenyl-
benzene-1,4-diamine; 2'-Chloro-biphenyl-2,5-diamine; N-Thiophen-3-ylmethyl-
benzene-1,4-
diamine; N-(3-furylmethyl)benzene-1,4-diamine; 4'-Methoxy-biphenyl-2,5-
diamine; N-(4-
Amino-benzyl)-benzene-1,4-diamine; 2-Methyl-5-[(1-H-pyrrol-2-ylmethyl)-amino]-
phenol;
5-[(Furan-2-ylmethyl)-amino]-2-methyl-phenol; 5-Isopropylamino-2-methyl-
phenol; Biphenyl-
2,4,4'-triamine hydrochloride; 5-(4-Amino-phenyl)aminomethyl-benzene-l,3-
diamine
hydrochloride; 5-Phenylaminomethyl-benzene-1,3-diamine hydrochloride; 2-[4-
Amino-2-(3,5-
diamino-benzylamino)-phenoxy]-ethanol hydrochloride; 5-(3-Amino-
phenyl)aminomethyl-
benzene- 1,3-diamine hydrochloride; N-(2-Amino-benzyl)-benzene-1,3-diamine
hydrochloride;
N-Furan-2-ylmethyl-benzene-1,3-diamine hydrochloride; 2-[(3-Amino-phenylamino)-
methyl]-
phenol hydrochloride; 4-Amino-2-propylaminomethyl-phenol; hydrochloride;
N-Benzo[1,3]dioxol-5-ylmethyl-benzene-1,3-diamine hydrochloride; N-[4-Amino-2-
(2-hydroxy-
ethyl)-2H-pyrazol-3-yl]-3-(5-amino-2-hydroxy-phenyl)-acrylamide;
hydrochloride; 4-Amino-2-
(isopropylamino-methyl)-phenol; hydrochloride; 4-Thiophen-3-yl-benzene-1,3-
diamine;
hydrochloride hydrochloride; 5-Phenylaminomethyl-benzene- 1,3-diamine
hydrochloride;
5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride; 4-Thiophen-3-
yl-
benzene- 1,3 -diamine; hydrochloride; 2',4'-Diamino-biphenyl-4-ol;
hydrochloride;
5-Cyclobutylamino-2-methyl-phenol; 5-Cyclobutylamino-2-methyl-phenol; 4-Amino-
2-(pyridin-
3-ylaminomethyl)-phenol; 5-(3-Amino-phenyl)aminomethyl-benzene-l,3-diamine
hydrochloride; 5-Allylaminomethyl-benzene-1,3-diamine hydrochloride; N-(4-
Amino-benzyl)-
benzene- 1,3-diamine hydrochloride; N-Benzyl-benzene-1,3-diamine
hydrochloride;
3-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride; N-(4-Methoxy-benzyl)-
benzene-l,3-
diamine hydrochloride; N-Thiophen-2-ylmethyl-benzene-1,3-diamine
hydrochloride; 4-Amino-
2-[(2-hydroxy-5-nitro-phenylamino)-methyl]-phenol; hydrochloride; 2',4'-
Diamino-biphenyl-4-ol
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hydrochloride; Biphenyl-2,4,4'-triamine; 5-(4-Amino-phenyl)aminomethyl-benzene-
1,3-diamine
hydrochloride; 2-[4-Amino-2-(3,5-diamino-benzylamino)-phenoxy] -ethanol
hydrochloride;
5-Allylaminomethyl-benzene-1,3-diamine hydrochloride; 5-(3-Amino-
phenyl)aminomethyl-
benzene- 1,3-diamine hydrochloride; N-(4-Amino-benzyl)-benzene-1,3-diamine
hydrochloride;
5 N-Benzyl-benzene-1,3-diamine hydrochloride; 3-[(3-Amino-phenylamino)-methyl]-
phenol
hydrochloride; N-(2-Amino-benzyl)-benzene-1,3-diamine hydrochloride; N-(4-
Methoxy-
benzyl)-benzene-1,3-diamine hydrochloride; N-Furan-2-ylmethyl-benzene-1,3-
diamine
hydrochloride; 2-[(3 -Amino-phenylamino)-methyl] -phenol hydrochloride; N-
Thiophen-2-
ylmethyl-benzene-1,3-diamine hydrochloride; N-Benzo[1,3]dioxol-5-ylmethyl-
benzene-1,3-
diamine hydrochloride; N-[4-Amino-2-(2-hydroxy-ethyl)-2H-pyrazol-3-yl]-3-(5-
amino-2-
hydroxy-phenyl)-acrylamide hydrochloride; 4-Amino-2-propylaminomethyl-phenol;
hydrochloride; 4-Amino-2-(isopropylamino-methyl)-phenol hydrochloride; 4-Amino-
2-[(2-
hydroxy-5-nitro-phenylamino)-methyl]-phenol hydrochloride; 2-Methyl-5-[(1-H-
pyrrol-2-
ylmethyl)-amino]-phenol; 5-[(Furan-2-ylmethyl)-amino]-2-methyl-phenol; 5-
Isopropylamino-2-
methyl-phenol; 5-Cyclobutylamino-2-methyl-phenol; 4-Amino-2-(pyridin-3-
ylaminomethyl)-
phenol; and 5-Cyclobutylamino-2-methyl-phenol.
The following compounds are especially suitable as developer compounds: 1,4-
diamino-2,6-
dimethylbenzene, 1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,3-
dimethylbenzene, 2-
chloro-1,4-diaminobenzene, 2-methoxy-benzene-1,4-diamine, 4-
phenylaminoaniline, 4-
dimethylaminoaniline, 4-diethylamino-aniline, 4-[di(2-
hydroxyethyl)amino]aniline, 4-[(2-
methoxyethyl)amino]-aniline, 4-[(3 -hydroxypropyl)amino] aniline, 1,4-diamino-
2-(2-
hydroxyethyl)benzene, 1,4-diamino-2-(1-methylethyl)benzene, 1,3-bis-[(4-
aminophenyl)-(2-
hydroxyethyl)amino]-2-propanol, 1,8-bis-(2,5-diaminophenoxy)-3,6-dioxaoctane,
4-
aminophenol, 4-amino-3-methylphenol, 4-methyl-aminophenol, 4-amino-2-
(aminomethyl)phenol, 4-amino-2-[(2-hydroxyethyl)amino]-methylphenol, 4-amino-2-
(methoxymethyl)phenol, 4-amino-2-(2-hydroxyethyl)phenol, 5-amino-salicylic
acid, 2,5-
diaminopyridine, 2,4,5,6-tetraamino-pyrimidine, 2,5,6-triamino-4-(1H)-
pyrimidone, 4,5-
diamino-l-(2-hydroxyethyl)-1H-pyrazole, 4,5-diamino-l-(1-methylethyl)-1H-
pyrazole, 4,5-
diamino-l-[(4-methylphenyl)-methyl]-1H-pyrazole, 1-[(4-chlorophenyl)methyl]-
4,5-diamino-
1H-pyrazole, 4,5-diamino-l-methyl-lH-pyrazole, 4,5-diamino-3-methyl-l-phenyl-
lH-pyrazole,
4,5-diamino-l-(2-hydroxyethyl)-3-methyl-lH-pyrazole, 2-amino-phenol, 2-amino-6-
methylphenol and 2-amino-5-methyl-phenol, or their salts.
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(ii) Cou lers: phenols, resorcinol and naphthol derivatives such as:
naphthalene- 1,7-diol,
benzene- 1,3-diol, 4-chlorobenzene-1,3-diol, naphthalen-l-ol, 2-methyl-
naphthalen-l-ol,
naphthalene- 1,5-diol, naphthalene-2,7-diol, benzene- 1,4-diol, 2-methyl-
benzene-1,3-diol, 7-
amino-4-hydroxy-naphthalene-2-sulfonic acid, 2-isopropyl-5-methylphenol,
1,2,3,4-tetrahydro-
naphthalene- 1,5-diol, 2-chloro-benzene-1,3-diol, 4-hydroxy-naphthalene-l-
sulfonic acid,
benzene-1,2,3-triol, naphthalene-2,3-diol, 5-dichloro-2-methylbenzene-1,3-
diol, 4,6-
dichlorobenzene-1,3-diol, 2,3-dihydroxy-[1,4]naphthoquinone; and 1-Acetoxy-2-
methylnaphthalene; m-phenylenediamines such as: 2,4-diaminophenol, benzene-
1,3-diamine, 2-
(2,4-diamino-phenoxy)-ethanol, 2-[(3 -amino-phenyl)-(2-hydroxy-ethyl)-amino] -
ethanol, 2-
mehyl-benzene-1,3-diamine, 2-[[2-(2,4-diamino-phenoxy)-ethyl]-(2-hydroxy-
ethyl)-amino]-
ethanol, 4- {3-[(2,4-diaminophenyl)oxy]-propoxy} benzene- 1,3 -diamine, 2-(2,4-
diamino-phenyl)-
ethanol, 2-(3-amino-4-methoxy-phenylamino)-ethanol, 4-(2-amino-ethoxy)-benzene-
1,3-
diamine, (2,4-diamino-phenoxy)-acetic acid, 2-[2,4-diamino-5-(2-hydroxy-
ethoxy)-phenoxy]-
ethanol, 4-ethoxy-6-methyl-benzene-1,3-diamine, 2-(2,4-diamino-5-methyl-
phenoxy)-ethanol,
4,6-dimethoxy-benzene-1,3-diamine, 2-[3-(2-hydroxy-ethylamino)-2-methyl-
phenylamino]-
ethanol, 3-(2,4-diamino-phenoxy)-propan-l-ol, N-[3-(dimethylamino)phenyl]urea,
4-methoxy-6-
methylbenzene-1,3-diamine, 4-fluoro-6-methylbenzene-1,3-diamine, 2-( {3-[(2-
hydroxyethyl)amino]-4,6-dimethoxyphenyl}-amino)ethanol, 3-(2,4-diaminophenoxy)-
propane-
1,2-diol, 2-[2-amino-4-(methylamino)-phenoxy] ethanol, 2-[(5-amino-2-ethoxy-
phenyl)-(2-
hydroxy-ethyl)-amino]-ethanol, 2-[(3 -aminophenyl)amino] ethanol, 2,4-Diamino-
5-(2'-
hydroxyethyloxy)toluene; N,N-Dimethyl-3-ureidoaniline; N-(2-aminoethyl)benzene-
1,3-
diamine, 4-{[(2,4-diamino-phenyl)oxy]methoxy}-benzene-1,3-diamine, 1-methyl-
2,6-bis(2-
hydroxyethylamino)benzene; and 2,4-dimethoxy-benzene-l,3-diamine; m-
aminophenols such as:
3-amino-phenol, 2-(3-hydroxy-4-methyl-phenylamino)-acetamide, 2-(3-hydroxy-
phenylamino)-
acetamide, 5-amino-2-methyl-phenol, 5-(2-hydroxyethylamino)-2-methyl-phenol, 5-
amino-2,4-
dichloro-phenol, 3-amino-2-methyl-phenol, 3-amino-2-chloro-6-methyl-phenol, 5-
amino-2-(2-
hydroxy-ethoxy)-phenol, 2-chloro-5-(2,2,2-trifluoro-ethylamino)-phenol, 5-
amino-4-chloro-2-
methyl-phenol, 3-cyclopentylamino-phenol, 5-[(2-hydroxyethyl)amino]-4-methoxy-
2-
methylphenol, 5-amino-4-methoxy-2-methylphenol, 3-(dimethylamino)phenol, 3-
(diethylamino)phenol, 5-amino-4-fluoro-2-methylphenol, 5-amino-4-ethoxy-2-
methylphenol, 3-
amino-2,4-dichloro-phenol, 3-[(2-methoxyethyl)amino]phenol, 3-[(2-
hydroxyethyl)amino]-
phenol, 5-amino-2-ethyl-phenol, 5-amino-2-methoxyphenol, 5-[(3-hydroxy-
propyl)amino]-2-
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methylphenol, 3-[(3-hydroxy-2-methylphenyl)-amino]propane-1,2-diol, 3-[(2-
hydroxyethyl)amino]-2-methylphenol; 1-Methyl-2-hydroxy-4-(2'-
hydroxyethyl)amino-benzene;
1,3-Bis-(2,4-Diaminophenoxy)propane; 1-Hydroxy-2-methyl-5-amino-6-
chlorobenzene; and
heterocyclic derivatives such as: 3,4-dihydro-2H-1,4-benzoxazin-6-ol, 4-methyl-
2-phenyl-2,4-
dihydro-3H-pyrazol-3-one, 6-methoxyquinolin-8-amine, 4-methylpyridine-2,6-
diol, 2,3-dihydro-
1,4-benzodioxin-5-ol, 1,3-benzodioxol-5-ol, 2-(1,3-benzodioxol-5-
ylamino)ethanol, 3,4-
dimethylpyridine-2,6-diol, 5-chloropyridine-2,3-diol, 2,6-dimethoxypyridine-
3,5-diamine, 1,3-
benzodioxol-5-amine, 2-{[3,5-diamino-6-(2-hydroxy-ethoxy)-pyridin-2-yl]oxy}-
ethanol, 1H-
indol-4-ol, 5-amino-2,6-dimethoxypyridin-3-ol, 1H-indole-5,6-diol, 1H-indol-7-
ol, 1H-indol-5-
ol, 1H-indol-6-ol, 6-bromo-1,3-benzodioxol-5-ol, 2-aminopyridin-3-ol, pyridine-
2,6-diamine, 3-
[(3,5-diaminopyridin-2-yl)oxy]propane-1,2-diol, 5-[(3,5-diaminopyridin-2-
yl)oxy]pentane-1,3-
diol, 1H-indole-2,3-dione, indoline-5,6-diol, 3,5-dimethoxypyridine-2,6-
diamine, 6-
methoxypyridine-2,3-diamine; 3,4-dihydro-2H-1,4-benzoxazin-6-amine; 4-hydroxy-
N-
methylindole, 1H-5-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2,6-
dimethylpyrazolo[1,5-b]-1,2,4-triazole, 2,6-dimethyl[3,2-c]-1,2,4-triazole, 6-
methylpyrazolo-
[1,5-a]benzimidazole, 2,6-dihydroxypyridine, 2,6-dihydroxy-3,4-
dimethylpyridine, 5-
methylpyrazolo[5,1-e]-1,2,3-triazole, 5-methyl-6-chloropyrazolo[5,1-e]-1,2,3,-
triazole, 5-
phenylpyrazolo[5,1-e]-1,2,3-triazole and its addition salts, 1H-2,6-
dimethylpyrazolo[1,5-b]-
1,2,4-triazole tosylate, 7,8-dicyano-4-methylimidazolo-[3,2-a]imidazole, 2,7-
dimethylpyrazolo[1,5-a]pyrimidin-5-one, 2,5-dimethylpyrazolo[1,5-a]pyrimidin-7-
one, and 2-
methyl-5-methoxymethyl-pyrazolo[1,5-a]pyrimidin-7-one; 6-
Hydroxybenzomorpholine; and 3-
Amino-2-methylamino-6-methoxypyridine; 1-Phenyl-3-methyl-5-pyrazolone-2,4-
dihydro-5,2-
phenyl-3 H-pyrazole-3 -one.
Preferred coupler substances include: N-(3-dimethylaminophenyl)urea, 2,6-
diaminopyridine,
2-amino-4-[(2-hydroxyethyl)amino]anisole, 2,4-diamino-l-fluoro-5-
methylbenzene,
2,4-diamino-l-methoxy-5-methylbenzene, 2,4-diamino-l-ethoxy-5-methylbenzene,
2,4-diamino-
1-(2-hydroxyethoxy)-5-methylbenzene, 2,4-di-[(2-hydroxyethyl)amino]-1,5-
dimethoxybenzene,
2,3-diamino-6-methoxypyridine, 3-amino-6-methoxy-2-(methylamino)-pyridine, 2,6-
diamino-
3,5-dimethoxypyridine, 3,5-diamino-2,6-dimethoxypyridine, 1,3-diaminobenzene,
2,4-diamino-
1-(2-hydroxyethoxy)benzene, 2,4-diamino-l-(3-hydroxypropoxy)benzene, 1-(2-
aminoethoxy)-
2,4-diaminobenzene, 2-amino-l-(2-hydroxyethoxy)-4-methylaminobenzene, 2,4-
diaminophenoxyacetic acid, 3-[di(2-hydroxyethyl)-amino]aniline, 4-amino-2-
di[(2-
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hydroxyethyl)amino]-1-ethoxybenzene, 5-methyl-2-(1-methylethyl)phenol, 3-[(2-
hydroxyethyl)amino]aniline, 3-[(2-aminoethyl)amino]aniline, 1,3-di(2,4-
diaminophenoxy)propane, di-(2,4-diaminophenoxy)methane, 1,3-diamino-2,4-
dimethoxybenzene, 2,6-bis-(2-hydroxyethyl)aminotoluene, 4-hydroxyindol,
3-dimethylaminophenol, 3-diethylaminophenol, 5-amino-2-methylphenol, 5-amino-4-
fluoro-2-
methylphenol, 5-amino-4-methoxy-2-methylphenol, 5-amino-4-ethoxy-2-
methylphenol,
3-amino-2,4-dichlorophenol, 5-amino-2,4-dichlorophenol, 3-amino-2-
methylphenol, 3-amino-2-
chloro-6-methyl-phenol, 3-amino-phenol, 2-[(3-hydroxyphenyl)amino]acetamide,
5-[(2-hydroxyethyl)amino]-2-methylphenol, 3-[(2-hydroxyethyl)amino]-phenol, 3-
[(2-methoxy-
ethyl)amino]-phenol, 5-amino-2-ethylphenol, 2-(4-amino-2-hydroxyphenoxy)-
ethanol,
5-[(3-hydroxypropyl)amino]-2-methylphenol, 3-[(2,3-dihydroxypropyl)-amino]-2-
methyl-
phenol, 3-[(2-hydroxyethyl)amino]-2-methylphenol, 2-amino-3-hydroxypyridine, 5-
amino-4-
chloro-2-methylphenol, 1-naphthol, 1,5-dihydroxy-naphthalene, 1,7-dihydroxy-
naphthalene,
2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-methyl-l-naphthol
acetate,
1,3-dihydroxy-benzene, 1-chloro-2,4-dihydroxybenzene, 2-chloro-1,3-
dihydroxybenzene,
1,2-dichloro-3,5-dihydroxy-4-methylbenzene, 1,5-dichloro-2,4-dihydroxybenzene,
1,3-dihydroxy-2-methylbenzene, 3,4-methylenedioxyphenol, 3,4-methylenedioxy-
aniline,
5-[(2-hydroxyethyl)amino]-1,3-benzodioxole, 6-bromo-l-hydroxy-3,4-
methylendioxybenzene,
3,4-diaminobenzoic acid, 3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine, 6-amino-
3,4-dihydro-
1,4(2H)-benzoxazine, 3-methyl-l-phenyl-5-pyrazolone, 5,6-dihydroxyindole,
5,6-dihydroxyindoline, 5-hydroxy-indole, 6-hydroxyindole, 7-hydroxy-indole and
2,3-indolindione, or their salts.
(iii) Self-couplingcompounds: 2-amino-5-methylphenol, 2-amino-6-methylphenol,
2-amino-6-ethoxyphenol and 2-propylaminopyridine.
The total amount of oxidative dyes contained inthe agent according to the
invention is
from 0.01 to 12 weight percent particularly from 0.1 to 7 weight percent.
Suitable direct dyes are all common natural and/or synthetic direct dyes, for
example
so-called plant dyes such as henna or indigo, triphenylmethane dyes, aromatic
nitro
dyes, azo dyes, quinone dyes and cationic or anionic dyes.
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9
Suitable synthetic dyes include: 6-hydroxy-5-[(4-sulfophenyl)azo]-2-
naphthalene sulfonic acid
disodium salt (C.I. 15985; Food Yellow No. 3; FD&C Yellow No. 6), 2,4-dinitro-
l-naphthol-7-
sulfonic acid disodium salt (C.I.10316; Acid Yellow No. 1; Food Yellow No. 1),
2-(indan-1,3-
dion-2-yl)quinoline-x,x-sulfonic acid (mixture of mono- and disolfuonic acid)
(C.I.47005;D&C
Yellow No. 10; Food Yellow No. 13, Acid Yellow No. 3), 5-hydroxy-l-(4-
sulfophenyl)-4-[(4-
sulfophenyl)azo]pyrazole-3-carboxylic acid sodium salt (C.I. 19140; Food
Yellow No. 4; Acid
Yellow No. 23), 9-(2-carboxyphenyl)-6-hydroxy-3H-xanthen-3-one (C.I.45350;
Acid Yellow
No. 73; D&C Yellow No. 8), 5-[(2,4-dinitrophenyl)amino]-2-
phenylaminobenzenesulfonic acid
sodium salt (C.I.10385; Acid Orange No. 3), 4-[(2,4-dihydroxyphenyl)azo] -
benzene sulfonic
acid monosodium salt (C.I.14270; Acid Orange No. 6), 4-[(2-hydroxynaphth-1-
yl)azo]benzenesulfonic acid sodium salt (C.I. 15510; Acid Orange No. 7), 4-
[(2,4-dihydroxy-3-
[(2,4-dimethylphenyl)azo]phenyl)azo]-benzene sulfonic acid sodium salt
(C.I.20170; Acid
Orange No. 24), 4-hydroxy-3-[(4-sulfonaphth-l-yl)azo]-1-naphthalene sulfonic
acid disodium
salt (C.I. 14720; Acid Red No. 14), 6-hydroxy-5-[(4-sulfonaphth-l-yl)azo]-2,4-
naphthalene-
disulfonic acid trisodium salt (C.I. 16255; Ponceau 4R; Acid Red No. 18), 3-
hydroxy-4-[(4-
sulfonaphth-1-yl)azo]-2,7-naphthalene-disulfonic acid trisodium salt (C.I.
16185; Acid Red No.
27), 8-amino-1-hydroxy-2-(phenylazo)-3,6-naphthalene disulfonic acid disodium
salt
(C.I. 17200; Acid Red No. 33), 5-(acetylamino)-4-hydroxy-3-[(2-
methylphenyl)azo]-2,7-
naphthalene disulfonic acid disodium salt (C.I.18065; Acid Red No. 35), 2-(3-
hydroxy-2,4,5,7-
tetraiodo-dibenzopyran-6-on-9-yl)-benzene sulfonic acid disodium salt (C.I.
45430; Acid Red
No. 51), N-[6-(diethylamino)-9-(2,4-disulfophenyl)-3H-xanthen-3-yliden]-N-
ethylethanaminium
hydroxide, inner Salt, sodium salt (C.I.45100; Acid Red No. 52), 8-[(4-
(phenylazo)phenyl)azo]-
7-naphthol-1,3-disulfonic acid disodium salt (C.I. 27290; Acid Red No. 73),
2',4',5',7'-tetrabromo-3',6'-dihydroxyspiro[isobenzofuran- 1 -(3 H),9'-
[9H]xanthen] -3 -one disodium
salt (C.I.45380; Acid Red No. 87), 2',4',5',7'-tetrabromo-4,5,6,7-tetrachloro-
3',6'-
dihydroxyspiro[isobenzofuran-1(3H),9'[9H]xanthen]-3-one disodium salt (C.I.
45410; Acid Red
No. 92), 3',6'-dihydroxy-4',5'-diiodospiro[isobenzofuran-1(3H),9'(9H)-xanthen)-
3-one disodium
salt (C.I. 45425; Acid Red No. 95), (2-sulfophenyl)-di-[4-(ethyl-((4-
sulfophenyl)methyl)-
amino)phenyl]carbenium disodium salt, betaine (C.I. 42090; Acid Blue No.9;
FD&C Blue No.1),
1,4-bis-[(2-sulfo-4-methyl-phenyl)amino]-9,10-anthraquinone disodium salt
(C.I. 61570; Acid
Green No. 25), bis-[4-(dimethylamino)phenyl]-(3,7-disulfo-2-hydroxynaphth- 1 -
yl)carbenium
inner salt, monosodium salt (C.I. 44090; Food Green No. 4; Acid Green No. 50),
bis-[4-
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(diethylamino)phenyl](2,4-disulfophenyl)carbenium inner salt, sodium salt
(2:1) (C.I. 42045;
Food Blue No. 3; Acid Blue No. 1), bis[4-(diethylamino)phenyl]-(5-hydroxy-2,4-
disulfophenyl)carbenium inner salt, calcium salt (2:1) (C.I. 42051; Acid Blue
No. 3), 1-amino-4-
(cyclohexylamino)-9,10-anthraquinone-2-sulfonic acid sodium salt (C.1. 62045;
Acid Blue No.
5 62), 2-(1,3-dihydro-3-oxo-5-sulfo-2H-indol-2-yliden)-2,3-dihydro-3-oxo-1 H-
indol-5-sulfonic
acid disodium salt (C.I. 73015; Acid Blue No. 74), 9-(2-carboxyphenyl)-3-[(2-
methylphenyl)-
amino] 6-[(2-methyl-4-sulfophenyl)amino]xanthylium inner salt, monosodium salt
(C.I. 45190;
Acid Violet No. 9), 1 -hydroxy-4-[(4-methyl-2-sulfophenyl)amino] -9, 1 0-
anthraquinone sodium
salt (C.I. 60730; D&C Violet No. 2; Acid Violet No. 43), bis-[3-nitro-4-[(4-
phenylamino)-3-
10 sulfophenylami no]phenyl]-sulfone (C.I. 10410; Acid Brown No. 13), 5-amino-
4-hydroxy-6-[(4-
nitrophenyl)azo]3-(phenylazo)-2,7-naphthalene disulfonic acid disodium salt
(C.I.20470; Acid
Black No. 1), 3-hydroxy-4-[(2-hydroxynaphth-1-yl)azo]-7-
nitronaphthalenesulfonic acid
chromium complex (3:2) (C.I. 15711; Acid Black No. 52), 3-[(2,4-dimethyl-5-
sulfophenyl)azo]-
4-hydroxy-l-naphthalene-sulfonic acid disodium salt (C.I. 14700; Food Red No.
1; Ponceau SX;
FD&C Red No. 4), 4-(acetylamino)-5-hydroxy-6-[(7-sulfo-4-[(4-
sulfophenyl)azo]naphth-1
yl)azo]-1,7-naphthalene disulfonic acid tetrasodium salt (C.I. 28440; Food
Black No. 1),
3 -hydroxy-4-(3 -methyl-5-oxo-l-phenyl-4, 5-dihydro-1 H-pyrazole-4-yl-azo)-
naphthalene-l-
sulfonic acid sodium salt chromium complex (Acid Red No. 195);
9-(dimethylamino)-benzo[a]phenoxazin-7-ium chloride (C.I. 51175; Basic Blue
No. 6), di[4-
(diethylamino)phenyl]-[4-(ethylamino)naphthyl]carbenium chloride (C.I. 42595;
Basic Blue No.
7), 3,7-di(dimethylamino)phenothiazin-5-ium chloride (C.I. 52015; Basic Blue
No. 9), di[4-
dimethylamino)phenyl][4(phenylamino)naphthyl]carbenium chloride (C.I. 44045;
Basic Blue
No. 26), 2-[(4-(ethyl(2-hydroxyethyl )amino)phenyl )azo] -6-methoxy-3 -
methylbenzothiazol ium
methylsulfate (C.I. 11154; Basic Blue No. 41), 8-amino-2-bromo-5-hydroxy-4-
imino-6-[(3-
(trimethylammonio)phenyl)amino]-1 (4H)naphthalenone chloride (C.I.56059; Basic
Blue No.
99), bis-[4-(dimethylamino)phenyl][4-(methylamino)phenyl]carbenium chloride
(C.I. 42535;
Basic Violet No. 1), tris-(4-amino-3-methylphenyl)carbenium chloride (C.I. 425
20; Basic Violet
No. 2), tris-[4-(dimethylamino)phenyl]carbenium chloride (C.I. 42555; Basic
Violet No. 3),
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11
2-[3,6-(diethylamino)dibenzopyranium-9-yl]benzoic acid chloride (C.I. 45170;
Basic Violet No.
10), di(4-aminophenyl)(4-amino-3-methylphenyl)carbenium chloride (C.I. 42510;
Basic Violet
No. 14), 1,3-bis[(2,4-diamino-5-methylphenyl)azo]-3-methylbenzene (C.I.
21010;Basic Brown
No. 4), 1-[(4-aminophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride (C.I.
12250; Basic
Brown No. 16), 1-[(4-amino-2-nitrophenyl)azo]-7-(trimethylammonio)-2-naphthol
chloride (C.I.
12251; Basic Brown No.17), 1-[(4-amino-3-nitrophenyl)azo]-7-(trimethylammonio)-
2-naphthol
chloride (C.I. 12251; Basic Brown No. 17), 3,7-diamino-2,8-dimethyl-5-
phenylphenazinium
chloride (C.I. 50240; Basic Red No. 2), 1,4-dimethyl-5-
[(4(dimethylamino)phenyl)azo]-1,2,4-
triazolium chloride (C.I. 11055; Basic Red No. 22), 2-hydroxy-l-[(2-
methoxyphenyl)azo]-7-
(trimethylammonio)naphthalene chloride (C.I. 12245; Basic Red No. 76), 2-[2-
((2,4-
dimethoxyphenyl)amino)ethenyl]-1,3,3-trimethyl-3H-indol-l-ium-chloride (C.I.
48055; Basic
Yellow No. 11), 3-methyl-l-phenyl-4-[(3-(trimethylammonio)phenyl)azo]-pyrazole-
5-one
chloride (C.I. 12719; Basic Yellow No. 57), bis-[4-
(diethylamino)phenyl]phenylcarbenium
hydrogen sulfate(l:1) (C.I. 42040; Basic Green No. 1); N,N-dimethyl-3-{[4-
(methylamino)-
9, 1 0-dioxo-9, 1 0-dihydro- 1 -anthracenyl]amino} -N-propyl-l-propanaminium
bromide (HC Blue
No. 16);
1-amino-2-[(2-hydroxyethyl)amino]-5-nitrobenzene (HC Yellow No. 5), 1-(2-
hydroxyethoxy)-2-
[(2-hydroxyethyl)amino]-5-nitrobenzene (HC Yellow No. 4), 1-[(2-
hydroxyethyl)amino]-2-
nitrobenzene (HC Yellow No. 2), 2-[(2-hydroxyethyl)amino]-1-methoxy-5-
nitrobenzene,
2-amino-3-nitrophenol, 1-(2-hydroxyethoxy)-3-methylamino-4-nitrobenzene, 2,3-
(dihydroxy-
propoxy)-3-methylamino-4-nitrobenzene, 2-[(2-hydroxyethyl)amino]-5-nitrophenol
(HC Yellow
No. 11), 3-[(2-aminoethyl)amino]-1-methoxy-4-nitrobenzene hydrochloride (HC
Yellow No.9),
1-[(2-ureidoethyl)amino]-4-nitrobenzene, 4-[(2,3-dihydroxypropyl )amino]-3-
nitro-1-
trifluoromethylbenzene (HC Yellow No. 6), 1-chloro-2,4-bis-[(2-
hydroxyethyl)amino]-5-
nitrobenzene (HC Yellow No. 10), 4-[(2-hydroxyethyl)amino]-3-nitro-l-
methylbenzene,
1 -chloro-4-[(2-hydroxyethyl)amino]-3-nitrobenzene (HC Yellow No. 12), 4-[(2-
hydroxyethyl)-
amino]-3-nitro-l-trifluoromethylbenzene (HC Yellow No. 13), 4-[(2-
hydroxyethyl)amino] -3-
nitrobenzonitrile (HC Yellow No. 14), 4-[(2-hydroxyethyl)amino]-3-
nitrobenzamide (HC
Yellow No. 15), 1-amino-4-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Red No.
7), 2-amino-
4,6-dinitrophenol, 2-ethylamino-4,6-dinitrophenol, 4-amino-2-
nitrodiphenylamine (HC Red No.
1), 1-amino-4-[di(2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride (HC Red
No. 13),
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12
1-amino-5-chloro-4-[(2hydroxyethyl)amino]-2-nitrobenzene, 4-amino-l-[(2-
hydroxyethyl)-
amino]-2-nitrobenzene (HC Red No. 3), 4-amino-3-nitrophenol, 4-[(2-
hydroxyethyl)amino]-3-
nitrophenol, 1-[(2-aminoethyl)amino]4-(2-hydroxyethoxy)-2-nitrobenzene (HC
Orange No. 2),
4-(2,3-dihydroxypropoxy)-1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Orange
No. 3),
1-amino-5-chloro-4-[(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC Red No.
10), 5-chloro-
1,4-[di(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC Red No. 11), 2-[(2-
hydroxyethyl)-
amino]4,6-dinitrophenol, 4-ethylamino-3-nitrobenzoic acid, 2-[(4-amino-2-
nitrophenyl)amino]-
benzoic acid, 2-chloro-6-methylamino-4-nitrophenol 2-chloro-6-[(2-
hydroxyethyl)amino]4-
nitrophenol, 2-chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-
nitrophenol,
4-[(3-hydroxypropyl )-amino]-3-nitrophenol, 2,5-diamino-6-nitropyridine,
1,2,3,4-tetrahydro-6-
nitrochinoxalin, 7-amino-3,4-dihydro-6-nitro-2H-1,4-benzoxazine (HC Red No.
14),1,4-bis-[(2-
hydroxyethyl )-amino]-2-nitrobenzene, 1-(2-hydroxyethyl )ami no-2-nitro-4-
[di(2-
hydroxyethyl)amino]benzene (HC Blue No. 2), 1 -amino-3-methyl-4-[(2-
hydroxyethyl)amino]-6-
nitrobenzene (HC Violet No. 1), 4-[ethyl-(2-hydroxyethyl)amino]-1-[(2-
hydroxyethyl)amino]-2-
nitrobenzene hydrochloride (HC Blue No. 12), 4-[di(2-hydroxyethyl)amino]-1-[(2-
methoxyethyl
)amino]-2-nitrobenzene (HC Blue No. 11), 1-[(2,3-dihydroxy-propyl)amino]4-
[methyl-(2-
hydroxyethyl)amino]-2-nitrobenzene (HC Blue No. 10), 1-[(2,3-
dihydroxypropyl)amino]4-
[ethyl-(2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride (HC Blue No. 9),
1-(3-hydroxypropylamino)-4-[di(2-hydroxyethyl)amino]-2-nitrobenzene (HC Violet
No. 2),
1-methylamino-4-[methyl-(2,3-dihydroxypropyl)amino]-2nitrobenzene (HC Blue No.
6),
2-((4-amino-2-nitrophenyl)amino)-5-dimethylamino-benzoic acid (HC Blue No.
13), 1,4-di[(2,3-
dihydroxypropyl)amino]-9,10-anthraquinone, 1-[(2-hydroxyethyl)amino]4-
methylamino-9,10-
anthraquinone (C.I. 61505, disperse Blue No. 3), 2-[(2-aminoethyl)amino]-9,10-
anthraquinone
(HC Orange No. 5),1-hydroxy-4-[(4-methyl-2-sulfophenyl)amino]-9,10-
anthraquinone,
1-[(3-aminopropyl)amino]4-methylamino-9,10-anthraquinone (HC Blue No. 8),
1-[(3-aminopropyl)amino]-9,10-anthraquinone (HC Red No. 8), 1,4-diamino-2-
methoxy-9,10-
anthraquinone (C.I.62015, disperse Red No. 11, Solvent Violet No. 26), 1,4-
dihydroxy-5,8-
bis[(2-hydroxyethyl)amino-9, 1 0-anthraquinone (C.I. 62500, disperse Blue No.
7, Solvent Blue
No. 69), 1-[di-(2-hydroxyethyl)amino]-3-methyl-4-[(4-nitrophenyl)azo]benzene
(C.I. 11210,
disperse Red No. 17), 4-[(4-aminophenyl)azo]-1-[di(2-hydroxyethyl)amino]-3-
methylbenzene
(HC Yellow No. 7), 2,6-diamino-3-[(pyridine-3-yl)azo]pyridine, 2-((4-
(acetylamino)phenyl)-
azo)-4-methylphenol (C.I. 11855; disperse Yellow No. 3);
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13
2-amino-4,6-dinitrophenol, 2-ethylamino-4,6-dinitrophenol, 2-[(2-hydroxyethyl)-
amino]4,6-
dinitrophenol and dye compounds of the following general formula:
OH
CI NHR
NOz
wherein R represents hydrogen, methyl, ethyl or hydroxyethyl.
The following direct dyes -alone or in combination with one another- are
especially preferred:
hydroxyethyl-2-nitro-p-toluidine, 2-hydroxyethyl-picramic acid, 4-nitrophenyl-
aminourea, tri(4-
amino-3-methylphenyl)-carbenium-chloride (Basic Violet 2), 1,4-diamino-9, 1 0-
anthracenedione
(Disperse Violet 1), N,N-dimethyl-3-{[4-(methylamino)-9,10-dioxo-9,10-dihydro-
1-
anthracenyl]amino}-N-propyl-1-propanaminium bromide (HC Blue No. 16); 1-(2-
hydroxyethyl)amino-2-nitro-4-[di(2-hydroxyethyl)-amino]-benzene (HC Blue No.
2), 4-[ethyl-
(2-hydroxyethyl)amino]-1-[(2-hydroxyethyl)amino]-2-nitro-benzene-hydrochloride
(HC Blue
No. 12), 1-amino-4-[di(2-hydroxyethyl)amino]-2-nitrobenzene-hydrochloride (HC
Red No. 13),
3-((2-nitro-4-(trifluorornethyl)phenyl)amino)-1,2-propanediol (HC Yellow No.
6), 4-amino-1 -
[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Red No. 3), 4-amino-3-nitrophenol,
4-[(2-
hydroxyethyl)-amino]-3-nitrophenol, 1-amino-5-chloro-4-[(2,3-
dihydroxypropyl)amino]-2-
nitrobenzene (HC Red No. 10), 5-chloro-1,4-[di(2,3-dihydroxypropyl)amino]-2-
nitrobenzene
(HC Red No. 11), 2-chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-
nitrophenol, 4-[(2-
hydroxyethyl)amino]-3-nitro-l-trifluoromethyl-benzene (HC Yellow No. 13), 8-
amino-2-bromo-
5-hydroxy-4-imino-6-[(3-(trimethylammonio)phenyl)-amino]-1(4H)-naphthalenone
chloride
(C156059; Basic Blue No. 99), 1-[(4-aminophenyl)azo]-7-(trimethylammonio)-2-
naphthol
chloride (CI12250; Basic Brown No. 16), 1-[(4-amino-2-nitrophenyl)azo]-7-
(trimethylammonio)-2-naphthol chloride (Basic Brown No. 17), 2-hydroxy-l-[(2-
methoxyphenyl)azo] -7-(trimethylammonio)-naphthalene chloride (CI12245; Basic
Red No. 76),
3-methyl-1 -phenyl-4-[(3-(trimethylammonio)-phenyl)azo]-pyrazol-5-one chloride
(CI12719;
Basic Yellow No. 57) and 2,6-diamino-3-[(pyridin-3-yl)azo]-pyridine and the
salts thereof.
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The hair dye compositions of the present invention will generally comprise
from 0.001% to 10%
by weight of direct dyes, preferably from 0.1% to 5% by weight, more
preferably from 0.2% to
4% by weight.
Other known and common dyes that can be contained in the coloring agent
according
to the invention are described in, among other publications, E. Sagarin,
"Cosmetics,
Science and Technology", Interscience Publishers Inc., New York (1957), pages
503 ff,
in H. Janistyn; "Handbuch der Kosmetika und Riechstoffe", volume 3 (1973),
pages
388 ff, and in K. Schrader "Grundlagen und Rezepturen der Kosmetika ", 2.
edition
(1989), pages 782-815, which in particular are included herein by reference.
The compositions of the present invention may further comprise additional
ingredients which
include, but are not limited to, thickeners, solvents, enzymes, surfactants,
conditioning agents,
carriers, antioxidants or reducing agents, stabilizers, chelants, perfumes,
hair swelling agents
and/or polymers. Some of these additional components are detailed hereafter.
Thickeners: The composition of the present invention may optionally further
comprise at least
about 0.01 % by weight, especially from 0.05 to 25% by weight, of thickeners.
Thickeners are
preferably comprised in amount sufficient to provide the composition with a
viscosity of from
about 1 Pa.s to 40 Pa.s (1,000 to 40,000 cP) at 26 C in order to provide a
composition that can
be readily applied to the hair without dripping.
The at least one thickener is chosen, for example, from:
(i) associative thickeners;
(ii) crosslinked acrylic acid homopolymers;
(iii) crosslinked copolymers of (meth)acrylic acid and of (C1-C6)alkyl
acrylate;
(iv) nonionic homopolymers and copolymers containing ethylenically unsaturated
monomers
of ester and amide type;
(v) ammonium acrylate homopolymers and copolymers of ammonium acrylate and of
acrylamide;
(vi) polysaccharides;
(vii) C 12-C30 fatty alcohols and
(viii) particulate or crystalline thickeners.
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(i) As used herein, the expression "associative thickener" means an
amphiphilic thickener
comprising both hydrophilic units and hydrophobic units, for example, at least
one C8-C30 fatty
chain and at least one hydrophilic unit. Representative associative thickeners
that may be used
5 are associative polymers chosen from:
(a) nonionic amphiphilic polymers comprising at least one fatty chain and at
least one
hydrophilic unit;
(b) anionic amphiphilic polymers comprising at least one hydrophilic unit and
at least one fatty-
chain unit;
10 (c) cationic amphiphilic polymers comprising at least one hydrophilic unit
and at least one fatty-
chain unit; and
(d) amphoteric amphiphilic polymers comprising at least one hydrophilic unit
and at least one
fatty-chain unit;
The nonionic amphiphilic polymers comprising at least one fatty chain and at
least one
15 hydrophilic unit may, for example, be chosen from:
(1) celluloses modified with groups comprising at least one fatty chain; for
example:
hydroxyethylcelluloses modified with groups comprising at least one fatty
chain chosen from
alkyl, arylalkyl and alkylaryl groups, and in which the alkyl groups are, for
example, C8-C22,
such as the product Natrosol Plus Grade 330 CS(C 16 alkyls) sold by the
company Aqualon, and
the product Bermocoll EHM 100 sold by the company Berol Nobel, and celluloses
modified with
polyalkylene glycol alkylphenyl ether groups, such as the product Amercell
Polymer HM-1500
(polyethylene glycol (15) nonylphenyl ether) sold by the company Amerchol;
(2) hydroxypropyl guars modified with groups comprising at least one fatty
chain, such as the
product Esaflor HM 22 (C22 alkyl chain) sold by the company Lamberti, and the
products
Miracare XC95-3 (C14 alkyl chain) and RE205-1 (C20 alkyl chain) sold by the
company Rhodia
Chimie;
(3) polyether urethanes comprising at least one fatty chain, such as C10-C30
alkyl or alkenyl
groups, for instance the products Elfacos T 210 and Elfacos T 212 sold by the
company Akzo or
the products Aculyn 44 and Aculyn 46 and Aculyn 48 sold by the company Rohm &
Haas;
(4) copolymers of vinylpyrrolidone and of fatty-chain hydrophobic monomers;
examples that
may be mentioned include: the products Antaron V216 and Ganex V216
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16
(vinylpyrrolidone/hexadecene copolymer) sold by the company I.S.P., the
products Antaron
V220 and Ganex V220 (vinylpyrrolidone/eicosene copolymer) sold by the company
I.S.P. ;
(5) copolymers of C1-C6 alkyl acrylates or methacrylates and of amphiphilic
monomers
comprising at least one fatty chain, such as the oxyethylenated methyl
methacrylate/stearyl
acrylate copolymer sold by the company Goldschmidt under the name Antil 208;
(6) copolymers of hydrophilic acrylates or methacrylates and of hydrophobic
monomers
comprising at least one fatty chain, such as polyethylene glycol
methacrylate/lauryl methacrylate
copolymer; and
(7) polymers as described in WO 96/40815 comprising at least one hydrophobbic
group and at
least one hydrophilic group, such as the following polymers according INCI
designation:
Polyether- 1, PEG-180/Laureth-50/TMMG Copolymer and PEG-180/Octoxynol-40/TMMG
Copolymer (sold by the company United Catalysts under the name Pure-Thix 1442,
Pure-Thix
1450, Pure-Thix HH, Pure-Thix L and Pure-Thix M).
The anionic amphiphilic polymers comprising at least one hydrophilic unit and
at least one
fatty-chain unit, may, for example, be chosen from those comprising at least
one fatty-chain allyl
ether unit and at least one hydrophilic unit comprising an ethylenic
unsaturated anionic
monomeric unit, for example, a vinylcarboxylic acid unit and further, for
example, chosen from
units derived from acrylic acids, methacrylic acids and mixtures thereof,
wherein the fatty-chain
allyl ether unit corresponds to the monomer of formula below:
CHz=C(Rl)CHZOBnR (I)
in which R1 is chosen from H and CH3, B is an ethyleneoxy radical, n is chosen
from zero and
integers ranging from 1 to 100, R is chosen from hydrocarbon-based radicals
chosen from alkyl,
arylalkyl, aryl, alkylaryl and cycloalkyl radicals, comprising from 10 to 30
carbon atoms, and,
further, for example, from 10 to 24 carbon atoms and even further, for
example, from 12 to 18
carbon atoms.
In one embodiment, a unit of formula (I) is, for example, a unit in which Rl
may be H, n may
be equal to 10 and R may be a stearyl (C 18) radical.
Anionic amphiphilic polymers of this type are described and prepared,
according to an emulsion
polymerization process, in patent EP-0 216 479 B2.
In one embodiment, anionic amphiphilic polymers are, for example, polymers
formed from 20%
to 60% by weight of acrylic acid and/or of methacrylic acid, from 5% to 60% by
weight of lower
alkyl (meth)acrylates, from 2% to 50% by weight of fatty-chain allyl ether of
formula (I), and
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from 0% to 1% by weight of a crosslinking agent which is a well-known
copolymerizable
unsaturated polyethylenic monomer, for example, diallyl phthalate, allyl
(meth)acrylate,
divinylbenzene, (poly)ethylene glycol dimethacrylate and
methylenebisacrylamide.
Examples of such polymers are crosslinked terpolymers of methacrylic acid, of
ethyl acrylate and
of polyethylene glycol (10 EO) stearyl ether (Steareth-10), such as those sold
by the company
Ciba 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).
The anionic amphiphilic polymers may further be chosen, for example, from
those
comprising at least one hydrophilic unit of unsaturated olefmic carboxylic
acid type, and at least
one hydrophobic unit of the type such as a(C10-C30) alkyl ester of an
unsaturated carboxylic
acid. The hydrophilic unit of unsaturated olefmic carboxylic acid type
corresponds to, for
example, the monomer of formula (II) below:
CHz=CR1-COOH (II)
in which Rl is chosen from H, CH3, and C2H5, i.e. acrylic acid, methacrylic
acid and ethacrylic
acid units. And the hydrophobic unit of the type such as a(C10-C30) alkyl
ester of an
unsaturated carboxylic acid corresponds to, for example, the monomer of
formula (III) below:
CH2=CR'-COOR2 (III)
in which Rl is chosen from H, CH3, and C2H5 (i.e. acrylate, methacrylate and
ethacrylate units)
and is, for example, chosen from, for example, H (acrylate units) and CH3
(methacrylate units),
R2 is chosen from C 10-C30 alkyl radicals, for example, C 12-C22 alkyl
radical.
Examples of (C10-C30)alkyl esters of unsaturated carboxylic acids include
lauryl acrylate,
stearyl acrylate, decyl acrylate, isodecyl acrylate, and dodecyl acrylate, and
the corresponding
methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate,
isodecyl
methacrylate and dodecyl methacrylate.
Anionic amphiphilic polymers of this type are disclosed and prepared, for
example, according to
U.S. Pat. Nos. 3,915,921 and 4,509,949.
Representative anionic amphiphilic polymers that may be used may further be
chosen from
polymers formed from a mixture of monomers comprising:
(1) acrylic acid, an ester of formula (IV) below:
CH2=CR' -COOR2 (IV)
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in which R' is chosen from H and CH3, R2 is chosen from C10-C30 alkyl
radicals, such as alkyl
radicals comprising from 12 to 22 carbon atoms, and a crosslinking agent; such
as polymers
derived from 95% to 60% by weight of the acrylic acid (hydrophilic unit), 4%
to 40% by weight
of C10-C30 alkyl acrylate (hydrophobic unit), and 0% to 6% by weight of
crosslinking
polymerizable monomer, or polymers derived from 98% to 96% by weight of the
acrylic acid
(hydrophilic unit), 1% to 4% by weight of C 10-C30 alkyl acrylate (hydrophobic
unit) and 0.1 %
to 0.6% by weight of crosslinking polymerizable monomer; or
(2) acrylic acid and lauryl methacrylate, such as the polymers formed from 66%
by weight of
acrylic acid and 34% by weight of lauryl methacrylate.
The crosslinking agent may be a monomer comprising a group (V)
I
CH2=C (V)
1
with at least one other polymerizable group whose unsaturated bonds are not
conjugated with
respect to one another. Mention may be made, for example, of polyallyl ethers
such as
polyallylsucrose and polyallyl pentaerythritol.
Among said polymers above mention may be made, for example, of the products
sold by the
company Noveon under the trade names Pemulen TR1, Pemulen TR2, Carbopol 1382,
and
further, for example, Pemulen TR1, and the product sold by the company
S.E.P.C. under the
name Coatex SX.
Suitable anionic amphiphilic fatty-chain polymers, include for example the
methacrylic
acid/methyl acrylate/ethoxylated alkyl dimethyl-meta-
isopropenylbenzylisocyanate copolymer
sold under the name Viscophobe DB 1000 by the company Amerchol.
Further suitable anionic amphiphilic fatty-chain polymers, include polymers
having the INCI
designation Acrylates/Ceteth-20 Itaconate Copolymer (sold by the company
National Starch
under the name Structure 3001) and Acrylates/Steareth-20 Itaconate Copolymer
(sold by the
company National Starch under the name Structure 2001).
The cationic amphiphilic polymers used are, for example, chosen from
quaternized cellulose
derivatives and polyacrylates comprising amino side groups.
The quaternized cellulose derivatives are, for example, chosen from;
quatemized celluloses
modified with groups comprising at least one fatty chain, such as alkyl,
arylalkyl and alkylaryl
groups comprising at least 8 carbon atoms, and mixtures thereof, quaternized
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hydroxyethylcelluloses modified with groups comprising at least one fatty
chain, such as alkyl,
arylalkyl and alkylaryl groups comprising at least 8 carbon atoms, and
mixtures thereof.
Quaternized and non-quaternized polyacrylates comprising amino side groups
having for
example, hydrophobic groups, such as Steareth 20 (polyoxy-ethylenated(20)
stearyl alcohol) and
(C10-C30)alkyl PEG-20 itaconate.
The alkyl radicals borne by the above quaternized celluloses and
hydroxyethylcelluloses, for
example, contain from 8 to 30 carbon atoms. The aryl radicals, for example,
are chosen from
phenyl, benzyl, naphthyl and anthryl groups.
Examples of quaternized alkylhydroxyethyl-celluloses comprising C8-C30 fatty
chains are the
products Quatrisoft LM 200, Quatrisoft LM-X 529-18-A, Quatrisoft LM-X 529-18B
(C12 alkyl)
and Quatrisoft LM-X 529-8 (C18 alkyl) sold by the company Amerchol, and the
products
Crodacel QM, Crodacel QL (C 12 alkyl) and Crodacel QS (C 18 alkyl) sold by the
company
Croda.
Examples of polyacrylates comprising amino side chains is Structure Plus from
the company
National Starch.
Among amphoteric amphiphilic polymers comprising at least one hydrophilic unit
and at
least one fatty-chain unit, mention may be made, for example, of
methacrylamidopropyltrimethylammonium chloride/acrylic acid/C10-C30 alkyl
methacrylate
copolymers, wherein the alkyl radical is, for example, a stearyl radical.
(ii) Among the crosslinked acrylic acid homopolymers that may be mentioned are
those
crosslinked with an allylic alcohol ether of the sugar series, such as the
products sold under the
names Carbopo1980, 981, 954, 2984 and 5984 by the company Noveon or the
products sold
under the names Synthalen M, Synthalen L and Synthalen K by the company 3V
Sigma.
(iii) Crosslinked copolymers of (meth)acrylic acid and of C1-C6 alkyl acrylate
may be chosen
from crosslinked copolymers of methacrylic acid and of ethyl acrylate as an
aqueous dispersion
comprising 38% active material sold, for example, under the name Viscoatex
538C by the
company Coatex, and crosslinked copolymers of acrylic acid and of ethyl
acrylate as an aqueous
dispersion comprising 28% active material sold under the name Aculyn 33 by the
company
Rohm & Haas. Crosslinked copolymers of inethacrylic acid and of ethyl acrylate
include an
aqueous dispersion comprising 30% active material manufactured and sold under
the name
Carbopol Aqua SF-1 by the company Noveon.
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(iv) Among the nonionic homopolymers or copolymers comprising ethylenically
unsaturated
monomers of ester and/or amide type, mention may be made of the products sold
under the
names: Cyanamer P250 by the company Cytec (polyacrylamide); PMMA MBX-8C by the
company US Cosmetics (methyl methacrylate/ethylene glycol dimethacrylate
copolymer);
5 Acryloid B66 by the company Rohm & Haas (butyl methacrylate/methyl
methacrylate
copolymer); BPA 500 by the company Kobo (polymethyl methacrylate).
(v) Ammonium acrylate homopolymers that may be mentioned include the product
sold under
the name Microsap PAS 5193 by the company Hoechst.
Copolymers of ammonium acrylate and of acrylamide include the product sold
under the name
10 Bozepol C Nouveau or the product PAS 5193 sold by the company Hoechst
(which are described
and prepared in documents FR-2 416 723, U.S. Pat. Nos. 2,798,053 and
2,923,692).
(vi) The polysaccharides are, for example, chosen from glucans, modified and
unmodified
starches (such as those derived, for example, from cereals, for instance
wheat, corn or rice, from
vegetables, for instance yellow pea, and tubers, for instance potato or
cassaya), amylose,
15 amylopectin, glycogen, dextrans, celluloses and derivatives thereof
(methylcelluloses,
hydroxyalkylcelluloses, ethyl hydroxyethylcellu loses, and
carboxymethylcelluloses), mannans,
xylans, lignins, arabans, galactans, galacturonans, chitin, chitosans,
glucuronoxylans,
arabinoxylans, xyloglucans, glucomannans, pectic acids and pectins, alginic
acid and alginates,
arabinogalactans, carrageenans, agars, glycosaminoglucans, succinoglucans, gum
arabics, gum
20 tragacanths, ghatti gums, karaya gums, carob gums, galactomannans, such as
guar gums, and
nonionic derivatives thereof (hydroxypropyl guar) and xanthan gums, and
mixtures thereof.
For example, suitable polysaccharides are described in "Encyclopedia of
Chemical Technology",
Kirk-Othmer, Third Edition, 1982, volume 3, pp. 896-900, and volume 15, pp.
439-458, in
"Polymers in Nature" by E. A. MacGregor and C. T. Greenwood, published by John
Wiley &
Sons, Chapter 6, pp. 240-328,1980, and in "Industrial Gums-Polysaccharides and
their
Derivatives", edited by Roy L. Whistler, Second Edition, published by Academic
Press Inc., the
content of these three publications being entirely incorporated by reference.
For example, starches, guar gums and celluloses and derivatives thereof may be
used. Suitable
starches include for example, of macromolecules in the form of polymers
comprising elemental
moieties that are anhydroglucose units. The number of these moieties and their
assembly make it
possible to distinguish between amylose (linear polymer) and amylopectin
(branched polymer).
The relative proportions of amylose and of amylopectin, and also their degree
of polymerization,
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may vary as a function of the botanical origin of the starches. The botanical
origin of the starch
molecules used may be cereals or tubers. Thus, the starches may be, for
example, chosen from
corn starch, rice starch, cassaya starch, tapioca starch, barley starch,
potato starch, wheat stanch,
sorghum starch and pea starch. Starches are generally in the form of a white
powder, which is
insoluble in cold water and which has an elementary particle size ranging from
3 to 100 microns.
The starches may optionally be C1-C6 hydroxyalkylated or C1-C6 acylated (such
as acetylated).
The starches may also have undergone heat treatments. Distarch phosphates or
of compounds
rich in distarch phosphate, for instance the products sold under the
references Prejel VA-70-T
AGGL (gelatinized hydroxypropylated cassaya distarch phosphate) or Prejel TKl
(gelatinized
cassaya distarch phosphate) or Preje1200 (gelatinized acetylated cassaya
distarch phosphate) by
the company Avebe, or Structure ZEA from National Starch (hydroxypropylated
corn distarch
phosphate), Structure XL from National Starch (hydroxypropylated starch
phosphate) may also
be used.
The guar gums may be modified or unmodified. The unmodified guar gums are, for
example, the
products sold under the name Vidogum GH 175 by the company Unipectine and
under the names
Meyro-Guar 50 and Jaguar C by the company Meyhall. The modified nonionic guar
gums are,
for example, modified with C1-C6 hydroxyalkyl groups. Among hydroxyalkyl
groups, mention
may be made, for example, of hydroxymethyl, hydroxyethyl, hydroxypropyl and
hydroxybutyl
groups. These guar gums are well known in the state of the art and may be
prepared, for example,
by reacting corresponding alkene oxides, such aspropylene oxides, with guar
gum so as to obtain
a guar gum modified with hydroxypropyl groups. The degree of
hydroxyalkylation, which
corresponds to the number of alkylene oxide molecules consumed by the number
of free
hydroxyl functions present on the guar gum, may, for example, range from 0.4
to 1.2.
Such nonionic guar gums optionally modified with hydroxyalkyl groups are sold,
for example,
under the trade names Jaguar HP8, Jaguar HP60 and Jaguar HP120, Jaguar DC 293
and Jaguar
HP 105 by the company Rhodia Chimie (Meyhall) or under the name Galactasol
4H4FD2 by the
company Aqualon.
Suitable celluloses include for example, hydroxyethylcellulose and
hydroxypropylcelluloses,
such as the products sold under the names Klucel EF, Klucel H, Klucel LHF,
Klucel MF and
Klucel G by the company Aqualon.
(vii) The C12 - C30 fatty alcohols are, for example, chosen from myristyl
alcohol, cetyl alcohol,
stearyl alcohol, behenyl alcohol or mixture thereof. When fatty alcohols are
used as thickeners, at
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least one additional surfactant with HLB value above about 6 is commonly
included to form bi-
layers with fatty alcohols. The most useful bi-layer structures include gel
network phase where
parallel bi-layers of fatty alcohols are swollen by water forming semi-solid
creams, and vesicle
dispersions where fatty alcohols bi-layers are curved into approximately
spherical uni-lamellar or
multi-lamellar aggregates.
(viii) The particulate and crystalline thickeners are for example, clays,
fumed silica,
microcrystalline cellulose, trihydroxystearin (ThixcinR), ethyleneglycol mono-
and di-stearate or
mixture thereof. The particulate or crystalline thickeners work via mechanisms
well known in the
art, for example particle aggregation, "house of card" particle arrangement or
crystalline fiber
formation.
Conditioning agent: The compositions of the present invention may comprise or
are used in
combination with a composition comprising a conditioning agent in an amount of
at least about
0.01 % by weight, especially from 0.1 % to 10% by weight. Conditioning agents
suitable for use
herein are selected from silicone materials, amino silicones, fatty alcohols,
polymeric resins,
polyol carboxylic acid esters, cationic polymers, cationic surfactants,
insoluble oils and oil
derived materials and mixtures thereof. Additional materials include mineral
oils and other oils
such as glycerin and sorbitol.
The conditioning agent will generally be used at levels of from about 0.05% to
about 20% by
weight of the composition, preferably of from about 0.1 % to about 15% by
weight, more
preferably of from about 0.2% to about 10% by weight, even more preferably of
from about
0.2% to about 2% by weight.
Particularly useful conditioning materials are cationic polymers. Conditioners
of cationic
polymer type may be chosen from those already know by those skilled in the art
as improving at
least one cosmetic properties of keratin fibres treated with a cosmetic
composition. Cationic
polymers may be chosen from those comprising units of at least one amine group
chosen from
primary, secondary, tertiary and quaternary amine groups that may either form
part of the main
polymer chain, or be borne by a side substituant that is directly attached to
the main polymer
chain. Such cationic polymers generally have a number average molecular mass
ranging from
500 to 5,000,000, or more preferably from 1000 to 3,000,000. Polymers of the
polyamine,
polyamino amide and polyquaternary ammonium type that may be used include but
are not
limited to:
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(1) homopolymers and copolymers derived from acrylic or methacrylic esters or
amides.
Copolymers of these polymers may also comprise at least one unit derived from
comonomers
which may be chosen from the family of acrylamides, methacrylamides, diacetone
acylamides,
acrylamides and methacrylicamides substituted on the nitrogen with at least
one group chosen
from lower (C1-C4) alkyls, acrylic and methacrylic acids and esters thereof,
vinlylactams such as
vinlypyrrolidone and vinylcaprolactam, and vinyl esters. Examples of such
polymers include:
Copolymers of acrylamide and of inethacryloyloxyethyltrimethylammonium
methosulfate,
examples of which include polymers known via the INCI nomenclature as
Polquaternium-5,
such as the products sold under the names Reten 210, Reten 220, Reten 230,
Reten 240, Reten
1104, Reten 1105, Reten 1006 by the company Hercules and Merquat 5, Merquat 5
SF by the
company Nalco.
Copolymers of vinylpyrrolidone and dimethylaminopropyl methacrylamide,
examples of which
include polymers known via the INCI nomenclature as Polyquaternium-28, such as
the products
sold under the name Gafquat HS-100 by the company International Speciality
Products (ISP).
Copolymers of vinyl pyrrolidone and dialkyaminoalkyl acrylates or
methactylates, examples of
which include polymers known via the INCI nomenclature as Polquaternium-11,
such as the
products sold under the name Gafquat 440, Gafquat 734, Gafquat 755, Gafquat
755N by the
company International Speciality Products (ISP), and Luviquat PQ11 PM by the
company BASF
and Polyquat-11 SL by the company Sino Lion.
Copolymers vinylpyrrolidone, dimethylaminopropyl methacrylamide and
methacryloylaminopropyl lauryldimonium chloride, examples of which include
polymers known
via the INCI nomenclature as polyquaternium-55, such as the products sold
under the name
Styleze W-20 by the company International Speciality Products (ISP).
Copolymers of acrylic acid, acrylamide and methacrylamidopropyltrimonium
chloride,
examples of which include polymers known via the INCI nomenclature as
Polyquaternium-53,
such as the products sold under the name Merquat 2003 by the company Nalco.
Copolymers of dimethyaminopropylacrylate (DMAPA), acrylic acid and
acrylonitrogens and
diethyl sulfate, examples of which include polymers known via the INCI
nomenclature as
Polyquaternium-31, such as the products sold under the name Hypan QT 100 by
the company
Lipo.
Copolymers of acrylamide, acrylamidopropyltrimonium chloride, 2-
amidopropylacrylamide
sulfonate, and dimethyaminopropylacrylate (DMAPA), examples of which include
polymers
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known via the INCI nomenclature as polyquaternium-43, such as the products
sold under the
name Bozequat 4000 by the company Clairant.
Copolymers of acrylic acid, methylacrylate and methacrylamidopropyltrimonium
chloride,
examples of which include polymers known via the INCI nomenclature as
Polyquaternium-47,
such as the products sold under the name Merquat 2001 and Merquat 2001N sold
commercially
by Nalco.
Copolymes of inethacryloyl ethyl betaine, 2-hydroxyethyl methacrylate and
methacryloyl ethyl
trimethyl ammonium chloride, examples of which include polymers known via the
INCI
nomenclature as Polyquatemium-48, such as the products sold under the name
Plascize L-450
by the company Goo Chemcial.
Copolymers of acrylic acid diallyl dimethyl ammonium chloride and acrylamide,
examples of
which include polymers known via the INCI nomenclature as polyquaternium 39,
such as the
products sold under the name Merquat 3330 and Merquat 3331 by the company
Nalco.
Further examples include copolymers of inethacrylamide methacrylamido-
propyltrimonium and
methacryloylethyltrimethyl ammonium chloride and their derivatives, either
homo or
copolymerised with other monomers, examples of which include polymers known
via the INCI
nomenclature as: Polyquaternium-8, Polyquaternium-9, Polyquaternium-12,
Polyquaternium-13
Polyquaternium-14, Polyquaternium-15, such as the products sold under the name
Rohagit KF
720 F by the company Rohm, Polyquaternium-30, such as the products sold under
the name
Mexomere PX by the company Chimex, Polyquaternium-33, Polyquaternium-35,
Polyquatemium-36, such as the products sold under the name Plex 3074 L by the
company
Rhon, Polyquaternium 45, such as the products sold under the name Plex 3073L
by the company
Rohn, Polyquaternium 49, such as the products sold under the name Plascize L-
440 by the
company Goo Chemicals, Polyquaternium 50 such as the products sold under the
name Plascize
L-441 by the company Goo Chemicals, Polyquatemium-52.
(2) Cationic polysaccharides, such as cationic celluloses and cationic
galactomannan gums.
Among the cationic polysaccharides that maybe mentioned, for example, are
cellulose ether
derivatives comprising quatemary ammonium groups and cationic cellulose
copolymers or
cellulose derivatives grafted with a water-soluble quatemary ammonium monomer
and cationic
galactomannan gums. Examples include but are not limited to:
Copolymers of hydroxyethylcelluloses and diallyldimethyl ammonium chlorides,
examples of
which include polymers known via the INCI nomenclature as Polyquaternium-4,
such as the
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products sold under the name Celquat L 200 and Celquat H 100 by the company
National
Starch.
Copolymers of hydroxyethylcelluloses and a trimethyl ammonium substituted
epoxide,
examples of which include polymers known via the INCI nomenclature as
Polyquaternium-10,
5 such as the products sold under the name AEC Polyquaternium-l0 by the
company A&E
Connock, Catinal C-100 Catinal HC-35 Catinal HC-100 Catinal HC-200 Catinal LC-
100
Catinal LC-200 by the company Toho, Celquat SC-240C Celquat SC-230M, by the
company
National Starch, Dekaquat 400,'Dekaquat 3000 by the company Dekker, Leogard GP
by the
company Akzo Nobel, RITA Polyquta 400 RITA, Polyquta 3000 by the company RITA,
10 UCARE Polymer JR-125 UCARE Polymer JR-400 UCARE Polymer JR-30M UCARE
Polymer
LK UCARE Polymer LR 400 UCARE Polymer LR 30M by the company Amerchol.
Copolymers of hydroxyethylcelluloses and lauryl dimethyl ammonium substituted
epoxides,
examples of which include polymers known via the INCI nomenclature as
Polyquaternium-24,
such as the products sold under the name Quatrisoft polymer LM-200 by the
company
15 Amerchol.
Derivatives of Hydroxypropyl Guar, examples of which include polymers known
via the INCI
nomenclature as Guar Hydroxypropyltrirnonium Chloride, such as the products
sold under the
name Catinal CG-100, Catinal CG-200 by the company Toho, Cosmedia Guar C-261N,
Cosmedia Guar C-261N, Cosmedia Guar C-261N by the company Cognis, DiaGum P
5070 by
20 the company Freedom Chemical Diamalt, N-Hance Cationic Guar by the company
Hercules/Aqualon, Hi-Care 1000, Jaguar C-17, Jaguar C-2000, Jaguar C-13S,
Jaguar C-14S,
Jaguar Excel by the company Rhodia, Kiprogum CW, Kiprogum NGK by the company
Nippon
Starch.
Hydroxypropyl derivatives of Guar Hydroxypropyltrimonium Chloride, examples of
which
25 include polymers known via the INCI nomenclature as Hydroxypropyl Guar
Hydroxypropyltrimonium Chloride, such as the products sold under the name
Jagaur C-162 by
the company Rhodia.
(3) Polyamino amide derivatives resulting from the condensation of
polyalkylene polyamines
with polycarboxylic acids followed by alkylation with difunctional agents.
Among the
derivative, mention may be made for example to adipic acid /
dimethylaminohydroxypropyl /
diethylenetriamine.
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(4) Polymers obtained by reaction of a polyalkylene polyamine comprising two
primary amines
groups and at last one secondary amine group with a decarboxylic acid chosen
from diglycolic
acids and saturated aliphatic dicarboxylic acids comprising from 3 to 8 carbon
atoms. Non-
limiting examples of such derivatives include the adipic acid / epxoypropyl /
diethylenetriamine.
(5) Cyclopolymers of dialkdiallylamine or of dialkyldiallyammonium, among
which polymers
mention may be made of:
Dimethyldiallyammonium chloride polymers, examples of which include polymers
known via
the INCI nomenclature as Polyquaternium-6, such as the products sold under the
name Merquat
100 by the company Nalco, Mirapol 100 by the company Rhodia, Rheocare CC6 by
the
company Cosmetic Rheologies, AEC polyquaternium-6 by the company A&E Connock,
Agequat 400 by the company CPS, Conditioner P6 by the company 3V Inc., Flocare
C106 by
the company SNF, Genamin PDAC by the company Clariant, Mackernium 006 by the
company
McIntyre.
Copolymers of acrylamides and dimethyldiallylammonium chlorides monomers,
examples of
which include polymers known via the INCI nomenclature as Polyquaternium-7,
such as the
products sold under the name AEC Polyquaternium-7 by the company A&E Connock,
Agequat-
5008, Agequat C-505 by the company CPS, Conditioner P7 by the company 3V Inc.
Flocare C
107 by the company SNF Mackernium 007, Mackernium 007S by the company
McIntyre, ME
Polymer 09W by the company Toho, Merquat 550, Merquat 2200, Merquat S by the
company
Nalco, Mira.po1550 by the company Rhodia, Rheocare CC7, Rheocare CCP7 by the
company
Cosmetic Rheologies, Salcare HSP-7, Salcare SC 10, Salcare Super 7 by the
company Ciba.
Copolymers of dimethyldiallylammoniumchlorides and acrylic acids, examples of
which include
polymers known via the INCI nomenclature as polyquaternary-22, such as the
products sold
under the name Merquat 280 and Merquat 295 by the company Nalco.
(6) Quaternary diammonium polymers comprising repeating units of formula
[-N+(Rl)(R2) -AI-N+(R3)(R)-B1-] [2X-], in which Rl, R2, R3 and R4, which may
be identical or
different, are chosen from aliphatic, alicyclic and arylaliphatic radicals
comprising from 1 to 20
carbon atoms and from lower hydroxyalkylaliphatic radicals, or Rl, R2, R3 and
R4, together or
separately, constitute, with the nitrogen atoms to which they are attached,
heterocycles
optionally comprising a second heteroatom other then nitrogen, or R', R2, R3
and R4, are choen
from liner or branched C1-C6 alkyl radicals substituted with at least one
group chosen from
nitrile, ester, acyl and amide groups and groups of -CO-O-R5-D and -CO-NH-R5-D
wherein
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R5 is chosen from alkylene groups and D is chosen from quatemary ammonium
groups. A' and
B1, which may be identical or different, are chosen from linear and branched,
saturated or
unsaturated polymethylene groups comprising 2 to 20 carbon atoms. The
polymethylene groups
may comprise, linked to or intercalated in the main ring, at least one entity
chosen from aromatic
rings, oxygen and sulphur atoms and sulphoxide, sulphone, disulphide, amino,
alkylamino,
hydroxyl, quaternary, ammonium, ureido, amide and ester groups, and X is an
anion derived
from inorganic and organic acids. D is chosen from a glycol residue, a bis-
secondary diamine
residue, a bis-primary diamine residue or a ureylene group. An examples of
which include
polymers known via the INCI nomenclature as Hexadimethrine chloride, where R',
R2, R3 and
R4 are each methyl radicals, A' is (CH2)3 and B' is (CH2)6 and X = Cl. Further
examples of
which include polymers known via the INCI nomenclature as polyquatemium-34
where Rland
R2 are ethyl radicals and R3 and R~ are methyl radicals and Al is (CH2)3 and
B1 is (CH2)3 and
X = Br, such as the products sold under the name Mexomere PAX by the company
Chimax.
(7) Polyquatemary ammonium polymers comprising repeating units of formula
[-N+(R6)(R')-(CH2)r-NH-CO-(CH2)q-(CO)t-NH-(CH2)s-N+(R8)(R9)-A-][2X"], in which
R6,
R~, R8 and R9 which may be identical or different, are chosen from a hydrogen
atom and a
methyl, ethyl, propyl, hydroxyethyl, hydroxypropyl, and -CH2CH2(OCH2CH2)pOH
radicals,
wherein p is equal to 0 or an integer ranging from 1 to 6, wherein R6, R~, R8
and R9 do not all
simultaneously represent a hydrogen atom. R and s which maybe identical or
different are each
an integer ranging from 1 to 6, q is equal to 0 or an integer ranging from 1
to 34 and X is an
anion such as a halide. T is an integer chosen to be equal to 0 or 1. A is
chosen from divalent
radicals such as -CH2-CH2-O-CH2-CH2-. Examples of which include
Polymers known via the INCI nomenclature as polyquaternium-2, where r=s=3,
q=0,t=0, R6, IC,
R8 and R9 are methyl groups, and A is -CH2-CH2-0-CH2-CH2, such as the products
sold
under the name Ethpol PQ-2 from Ethox and Mirapol A-15 by the company Rhodia.
Polymers known via the INCI nomenclature as polyquaternium-17 where r=s=3,
q=4, t=1, R6,
R7, R$ and R9 are methyl groups, and A is -CH2-CH2-O-CH2-CH2.
Polymers known via the INCI nomenclature as Polyquaternium 18, where r=s=3,
q=7, t=1, R6,
R7, R8 and R9 are methyl groups, and A is -M-CH2-O-CH2-CH2
Polymers known via the INCI nomenclature as the block copolymer formed by the
reaction of
Polyquaternium-2 with Polyquaternium-17, known as Polyquaternium 27, such as
the products
sold under the name Mirapol 175 by the company Rhodia.
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(8) Copolymers of vinylpyrrolidones and of vinylimidazoles and optionally
vinylcaprolactums,
examples of which include polymers known via the INCI nomenclature as
Polyquaternary-16
formed from methylvinylimidazolium chlorides and vinylpyrrolidones, such as
the products sold
under the name Luviquat FC370, Luviquat FC550, Luviquat FC905, Luviquat HM-552
by the
company BASF. Or copolymers of vinylcaprolactams and vinylpyrrolidones with
methylvinylimidazolium methosulfates, examples of which include polymers known
via the
INCI nomenclature as Polyquatemium-46, such as the products sold under the
name Luviquat
Hold by the company BASF. Or copolymers of vinylpyrrolidones and quatemized
imidazolines,
examples of which include polymers known via the INCI nomenclature
poylquaterary 44, such
as the products sold under the name Luviquat Care by the company BASF
(9) Polyamines such as the product Polyquart H sold by Cognis under the
reference name
polyethylene glycol (15) tallow polyamine in the CTFA dictionary.
(10) Cross linked methacryloyloxy(C 1-C4)alkyltri(C 1 -C4)alkylammonium salt
polymers such as
the polymers obtained by homopolymerisation of dimethylaminoethyl
methacrylates quatemized
with methyl chloride, or by copolymerisation of acrylamides with
dimethylaminoethyl
methacrylates quaternized with methyl chloride, the homo or copolymerisation
being followed
by crosslinking with a compound comprising olefmic unsaturation, such as
methylenebisacrylamides, examples of which include polymers known via the INCI
nomenclature as Polyquatemium-37, such as the products sold under the name
Synthalen, CN
Synthalen CR, Synthalen CU, sold by 3V sigma, or as a dispersion in another
media such as the
products sold under the name Salcare SC95 and Salcare SC96 by the company Ciba
or Rheocare
CTH(E) by the company Cosmetic Rheologies. Or in another example of which
include
polymers known via the INCI nomenclature as Polyquaternium-32, or when sold as
a dispersion
in mineral oil such as the products sold under the name Salcare SC92 by the
company Ciba.
(11) Further examples of cationic polymers include polymers known via the INCI
nomenclature
as Polyquatemium 51, such as the products sold under the name Lipidure-PMB by
the company
NOF, via the INCI nomenclature as Polyquaternium 54, such as the products sold
under the
name Qualty-Hy by the company Mitsui, and via the INCI nomenclature as
Polyquatemium 56
such as the products sold under the name Hairrol UC-4 by the company Sanyo
chemicals.
(12) silicone polymers comprising cationic groups and/or groups which may be
ionised into
cationic groups. For example: cationic silicones of the general formula
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(R10-N+(CH3)2)-R11-(Si(CH3)2-0)x-Rl'-(N+(CH3)2)-R10), where RI0 is an alkyl
derived from
coconut oil, and R' 1 is (CH2CHOCH2O(CH2)3 and x is a number between 20 and
2000,
examples of which include polymers known by the INCI nomenclature as
Quaternium 80, such
as the products sold under the name as Abil Quat 3272 and Abil Quat 3474 sold
commercially by
Goldschmidt.
Silicones containing groups which may be ionised into cationic groups, for
example
aminosilicones containing at least 10 repeating siloxane -(Si(CH3)2-0) units
within the polymer
chain, with either terminal, graft or a mixture of terminal and graft
aminofunctional groups.
Example functional groups are not limited to aminoethylaminopropyl,
aminoethylaminoisobutly,
aminopropyl. In the case of graft polymers, the terminal siloxane units may
either be (CH3)3Si-
0 or R12(CH3)2Si-O, where R12 may be either OH or OR13, where R13 is a CI-C8
alky group, or
a mixture of both functional terminal groups. These silicones are also
available as preformed
emulsions. Polymer with terminal siloxane units of (CH3)3Si-O examples of
which include
polymers known by the INCI nomenclature as trimethylsilylamodimethicone, such
as the
products sold under the name as DC-2-8566, DC 7224 and DC-2-8220 sold
commercially by
Dow Coming and SF1708 and SM 2125 sold commercially by GE Silicones and Wacker
Belsil
ADM 653 sold commercially by Wacker silicones. Further examples include
polymers with
terminal siloxane units of (R12O)(CH3)2Si-O where R12 may be either OH or
OR13, where R13 is
a C 1-C8 alky group, or a mixture of both functional terminal groups, known by
the INCI
nomenclature as amodimethicone, such as the products sold under the name as
Wacker Belsil
ADM 1100, Wacker Belsil ADM 1600, Wacker Belsil ADM 652, Wacker Belsil ADM
6057E,
Wacker Belsil ADM 8020 sold commercial by Wacker Silicones, DC929, DC939 and
DC949
sold commercially by Dow Corni.ng and SM2059 sold commercially by GE
silicones.
Silicones containing groups which may be ionised into cationic groups - for
example silicones
containing at least 10 repeating siloxane -(Si(CH3)2-O) units within the
polymer chain, with
either terminal, graft or a mixture of terminal and graft aminofunctional
groups, together with
additional functional groups. Additional functional groups may include
polyoxyalkylene, the
reaction product of amines and carbinols, alky chains. For example products
know by the INCI
nomenclature as methoxy PEG/PPG-7/3 Aminopropyl Dimethicone, such as the
product sold
under the name of Abil Soft AF100 sold commercially by Degussa. For example
products know
by the INCI nomenclature as Bis (C13-15 Alkoxy) PG Amodimethicone, such as the
product
sold under the name of DC 8500 sold commercially by Dow Corning.
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Surfactants: The compositions according to the present invention may further
comprise one or
more surfactants. Surfactants suitable for use herein generally have a
lipophilic chain length of
from about 8 to about 30 carbon atoms and may be selected from anionic,
nonionic, amphoteric
5 and cationic surfactants and mixtures thereof. The total level of surfactant
is from about 0.5% to
about 60% by weight, preferably from about 2% to about 30% by weight, more
preferably from
about 8% to about 25% by weight and especially from about 10% to about 20% by
weight.
The compositions of the invention preferably comprise a mixture of anionic and
amphoteric
surfactants with one or more nonionic surfactants. Anionic components, where
may be present
10 in the range of from about 0.1 % to about 20% by weight, preferably from
about 0.1 % to about
15% by weight, and more preferably from about 5% to about 15% by weight of the
composition;
amphoteric or nonionic components, may independently be present is in the
range from about
0.1% to about 15% by weight, preferably from about 0.5% to about 10% by
weight, more
preferably from about 1% to about 8% by weight.
15 As examples of anionic surfactants, which may be used, alone or as
mixtures, mention may be
made, for example, of salts (such as alkaline salts, for example, sodium
salts, ammonium salts,
amine salts, amino alcohol salts and magnesium salts) of the following
compounds: alkyl
sulphates, alkyl ether sulphates, alkylamido ether sulphates,
alkylarylpolyether sulphates,
monoglyceride sulphates; alkyl sulphonates, alkyl phosphates, alkylamide
sulphonates, alkylaryl
20 sulphonates, a-olefin sulphonates, paraffin sulphonates; alkyl
sulphosuccinates, alkyl ether
sulphosuccinates, alkylamide sulphosuccinates; alkyl sulphosuccinamates; alkyl
sulphoacetates;
alkyl ether phosphates; acyl sarcosinates; acyl isethionates and N-
acyltaurates. The alkyl or acyl
radical of all of these various compounds, for example, comprises from 8 to 24
carbon atoms,
and the aryl radical, for example, is chosen from phenyl and benzyl groups.
Among the anionic
25 surfactants, which may also be used, mention may also be made of fatty acid
salts such as the
salts of oleic, ricinoleic, palmitic and stearic acids, coconut oil acid or
hydrogenated coconut oil
acid; acyl lactylates in which the acyl radical comprises from 8 to 20 carbon
atoms. Weakly
anionic surfactants may also be used, such as alkyl-D-galactosiduronic acids
and their salts, as
well as polyoxyalkylenated (C6-C24) alkyl ether carboxylic acids,
polyoxyalkylenated (C6-C24)
30 alkylaryl ether carboxylic acids, polyoxyalkylenated (C6-C24) alkylamido
ether carboxylic acids
and their salts, for example, those comprising from 2 to 50 ethylene oxide
groups, and mixtures
thereof. Anionic derivatives of polysaccharides, for example carboxyalkyl
ether of alkyl
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polyglucosides, may be also used.
The nonionic surfactants are compounds that are well known (see, for example,
in this respect
"Handbook of Surfactants" by M. R. Porter, published by Blackie & Son (Glasgow
and London),
1991, pp. 116-178). They may be chosen, for example, from polyethoxylated,
polypropoxylated
and polyglycerolated fatty acids, alkyl phenols, a-diols and alcohols
comprising a fatty chain
comprising, for example, from 8 to 18 carbon atoms, it being possible for the
number of ethylene
oxide or propylene oxide groups to range, for example, from 2 to 200 and for
the number of
glycerol groups to range, for example, from 2 to 30. Mention may also be made
of copolymers of
ethylene oxide and of propylene oxide, condensates of ethylene oxide and of
propylene oxide
with fatty alcohols; polyethoxylated fatty amides preferably having from 2 to
30 mol of ethylene
oxide and their momoethanolamine and diethanolamine derivatives,
polyglycerolated fatty
amides, for example, comprising on average from 1 to 5, and such as from 1.5
to 4, glycerol
groups; polyethoxylated fatty amines such as those containing from 2 to 30 mol
of ethylene
oxide; oxyethylenated fatty acid esters of sorbitan having from 2 to 30 mol of
ethylene oxide;
fatty acid esters of sucrose, fatty acid esters of polyethylene glycol,
alkylpolyglycosides,
N-alkylglucamine derivatives, amine oxides such as (Clo-C14)alkylamine oxides
or
N-acylaminopropylmorpholine oxides.
The amphoteric surfactants may be chosen, for example, from aliphatic
secondary and
tertiary amine derivatives in which the aliphatic radical is chosen from
linear and branched
chains comprising from 8 to 22 carbon atoms and comprising at least one water-
soluble anionic
group (for example carboxylate, sulphonate, sulphate, phosphate or
phosphonate); mention may
also be made of (C8-C20)alkylbetaines, sulphobetaines, (C$-C20)alkylamido(C1-
C6)alkylbetaines
or (Cg-C20)alkylamido(Cl-C6)alkylsulphobetaines.
Among the amine derivatives, mention may be made of the products sold under
the name
Miranol, as described, for example, in U.S. Pat. Nos. 2,528,378 and 2,781,354
and having the
structures of: R2-CON HCHZCHZ N+(R3)(R4)(CH2COO-) (VI)
in which: R2 is chosen from alkyl radicals derived from an acid R2-COOH
present in hydrolysed
coconut oil, and heptyl, nonyl and undecyl radicals, R3 is a(3-hydroxyethyl
group and R4 is a
carboxymethyl group; and of RS-CONHCH2CH2 N(B)(C) (VII)
wherein B represents ---CH2CHZOX', C represents -(CH2)Z Y', with z=1 or 2, X'
is chosen
from the -CH2CH2-COOH group and a hydrogen atom, Y' is chosen from -COOH and
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-CH2-CHOH-SO3H radicals, RS is chosen from alkyl radicals of an acid R5-COOH
present
in coconut oil or in hydrolysed linseed oil, alkyl radicals, such as C7, C9,
Cl l and C13 alkyl
radicals, a C17 alkyl radical and its iso form, and unsaturated C17 radical.
These compounds are
classified in the CTFA dictionary, 5th edition, 1993, under the names disodium
cocoamphodiacetate, disodium lauroamphodiacetate, disodium
caprylamphodiacetate, disodium
capryloamphodiacetate, disodium cocoamphodipropionate, disodium
lauroamphodipropionate,
disodium caprylamphodipropionate, disodium capryloamphodipropionate,
lauroamphodipropionic acid, and cocoa.mphodipropionic acid. Salts of diethyl
aminopropyl
cocoaspartamid may be also used.
The cationic surfactants may be chosen from: A) the quaternary ammonium salts
of general
formula (VIII): LNR1R2R3R4]+ X" (VIII)
wherein X is an anion chosen from halides (chloride, bromide and iodide), (C2-
C6)alkyl
sulphates, such as methyl sulphate, phosphates, alkyl and alkylaryl
sulphonates, and anions
derived from organic acids, such as acetate and lactate, and
(i) the radicals R' to R3, which may be identical or different, are chosen
from linear and branched
aliphatic radicals comprising from I to 4 carbon atoms, and aromatic radicals
such as aryl and
alkylaryl. The aliphatic radicals may comprise at least one hetero atom such
as oxygen, nitrogen,
sulphur and halogens. The aliphatic radicals are chosen, for example, from
alkyl, alkoxy and
alkylamide radicals, R4 is chosen from linear and branched alkyl radicals
comprising from 16 to
30 carbon atoms.
The cationic surfactant is, for example, a behenyltrimethylammonium salt (for
example a
chloride or bromide).
(ii) the radicals R' and R2, which may be identical or different, are chosen
from linear and
branched aliphatic radicals comprising from 1 to 4 carbon atoms, and aromatic
radicals such as
aryl and alkylaryl. The aliphatic radicals may comprise at least one hetero
atom such as oxygen,
nitrogen, sulphur and halogens. The aliphatic radicals are chosen, for
example, from alkyl,
alkoxy, alkylamide and hydroxyalkyl radicals comprising from about 1 to 4
carbon atoms;
R3 and R4, which may be identical or different, are chosen from linear and
branched alkyl
radicals comprising from 12 to 30 carbon atoms, the said alkyl radicals
comprise at least one
function chosen from ester and amide functions.
R3 and R4 are chosen, for example, from (C12-C22)alkylamido(C2-C6)alkyl and
(C12-
C22)alkylacetate radicals.
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The cationic surfactant is, for example, a dicetyldimethyl ammonium salt (for
example chloride);
B) the quaternary ammonium salts of imidazolinium, such as that of formula
(IX) below:
+
R6
/CH2-CH2-N(R$)-CO-R5 X
N N'
R7
(IX)
in which R5 is chosen from alkenyl and alkyl radicals comprising from 8 to 30
carbon atoms, for
example fatty acid derivatives of tallow,
R6 is chosen from a hydrogen atom, Ct-C4 alkyl radicals and alkenyl and alkyl
radicals
comprising from 8 to 30 carbon atoms, R7 is chosen from C1-C4 alkyl radicals,
R8 is chosen from
a hydrogen atom and C1-C4 alkyl radicals, and X is an anion chosen from
halides, phosphates,
acetates, lactates, alkyl sulphates, alkyl sulphonates and alkylaryl
sulphonates.
In one embodiment, R5 and R6 are, for example, a mixture of radicals chosen
from alkenyl and
alkyl radicals comprising from 12 to 21 carbon atoms, such as fatty acid
derivatives of tallow,
R7 is methyl and R8 is hydrogen. Such a product is, for example, Quatemium-27
(CTFA 1997)
or Quaternium-83 (CTFA 1997), which are sold under the names "Rewoquat " W75,
W90,
W75PG and W75HPG by the company Witco,
C) the diquatemary ammonium salts of formula (X):
[(R9)(R10)(Rl l)-N-(CH2)3-N(R12)(R13)(Rl4)]++ 2X- (X)
in which R9 is chosen from aliphatic radicals comprising from about 16 to 30
carbon atoms,
R10, Rl 1, R12, R13 and R14, which may be identical or different, are chosen
from hydrogen and
alkyl radicals comprising from 1 to 4 carbon atoms, and
X is an anion chosen from halides, acetates, phosphates, nitrates and methyl
sulphates. Such
diquatemary ammonium salts, for example, include propanetallowdiammonium
dichloride; and
D) the quatemary ammonium salts comprising at least one ester function, of
formula (XI) below:
(CrH2rO)z R18
1
R17-CO-(OCnH2n)y- i -(CpH2pO)XR16 X-
R15 (XI)
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in which:
R15 is chosen from C1-C6 alkyl radicals and C1-C6 hydroxyalkyl and
dihydroxyalkyl radicals;
R16 is chosen from: a radical R19C(O)-, linear and branched, saturated and
unsaturated C1-C22
hydrocarbon-based radicals R20, and a hydrogen atom, R18 is chosen from: a
radical R21C(O)-,
linear and branched, saturated and unsaturated C1-C6 hydrocarbon-based
radicals R22, and
a hydrogen atom, R17, R19 and R21, which may be identical or different, are
chosen from linear
and branched, saturated and unsaturated C7-C21 hydrocarbon-based radicals; n,
p and r, which
may be identical or different, are chosen from integers ranging from 2 to 6; y
is chosen from
integers ranging from 1 to 10; x and z, which may be identical or different,
are chosen from
integers ranging from 0 to 10; X- is an anion chosen from simple and complex,
organic and
inorganic anions; with the proviso that the sum x+y+z is from 1 to 15, that
when x is 0, then R16
is R20 and that when z is 0, then R18 is R22.
In one embodiment, the ammonium salts of formula (XI) may be used, in which:
R15 is chosen from methyl and ethyl radicals, x and y are equal to 1; z is
equal to 0 or 1; n, p and
r are equal to 2; R16 is chosen from: a radical R19C(O)-,methyl, ethyl and C14-
C22
hydrocarbon-based radicals, and a hydrogen atom; R17, R19 and R21, which may
be identical or
different, are chosen from linear and branched, saturated and unsaturated C7-
C2 1, hydrocarbon-
based radicals; Rl8 is chosen from: a radical R21C(O)- and a hydrogen atom.
Such compounds
are sold, for example, under the names Dehyquart by the company Cognis,
Stepanquat by the
company Stepan, Noxamium by the company Ceca, and Rewoquat WE 18 by the
company
Rewo-Witco.
Chelants: According to the present invention the compositions may comprise
chelants.
Chelants are well known in the art and refer to a molecule or a mixture of
different molecules
each capable of forming a chelate with a metal ion. Chelants are well known in
the art and a non-
exhaustive list thereof can be found in AE Martell & RM Smith, Critical
Stability Constants,
Vol. 1, Plenum Press, New York & London (1974) and AE Martell & RD Hancock,
Metal
Complexes in Aqueous Solution, Plenum Press, New York & London (1996) both
incorporated
herein by reference.
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Chelants suitable for use herein are carboxylic acids (in particular
aminocarboxylic acids),
polyamines, phosphonic acids (in particular aminophosphonic acids) and
polyphosphoric acids
(in particular linear polyphosphoric acids), their salts and derivatives.
Examples of preferred chelants include ethylenediaminotetraacetic acid (EDTA),
nitrilotriacetic
5 acid, diethylenetriamine pentaacetic acid (DTPA), ethylenediamine disuccinic
acid (EDDS),
ethylenediamine diglutaric acid (EDGA), 2-hydroxypropylenediamine disuccinic
acid (HPDS),
glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid
(EDDG),
2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS), salts thereof and
derivatives
thereof.
10 Chelants may be incorporated into the composition of the present invention
as stabilizers and or
preservatives. In addition it has also been found that chelants provide hair
fibre damage benefits
and thus they may be utilized in order to further improve the hair damage
profile of the present
invention. Levels of chelants in the present invention may be as low as about
0.1 % by weight,
preferably at least about 0.25% by weight, more preferably about 0.5% by
weight, for the most
15 effective chelants such as diamine-N,N'-dipolyacid chelants and monoamine
monoamide-N,N'-
dipolyacid chelants (for example EDDS). Less effective chelants will be more
preferably used at
levels of at least about 1% by weight, even more preferably above about 2% by
weight of the
composition, depending of the efficiency of the chelant. Levels as high as
about 10% by weight
may be used, but above this level significant formulation issues may arise.
Solvents: Suitable solvents for use in the compositions of the present
invention include, but
are not limited to, water, butoxydiglycol, 1,2-propylene glycol, glycerol,
lower aliphatic alcohols
(e.g. ethanol, n-propanol or isoproanol), ethoxydiglycol, isopropylalcohol,
hexylene glycol,
benzyl alcohol and dipropylene glycol.
Antioxidants or reducinga agents: Suitable antioxidants or reducing agents for
use in the
compositions of the present invention include, but are not limited to,
ascorbic acid, thioglycolic
acid and sodium sulfite.
The form of the hair dye composition may be, for example, a solution,
especially an aqueous or
aqueous-alcoholic solution, a cream, a gel, an emulsion or an aerosol
composition. Its
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36
composition comprises a mixture of the dye ingredients with the conventional
additive
ingredients usually used in this type of preparation.
According to an embodiment of the present invention dye powders or granules
are mixed with an
appropriate dye carrier mass prior to use to form the hair dye composition.
Particularly preferred
is the use of the dye-containing pellets according to WO 2005/044208 which are
mixed with an
appropriate dye carrier mass prior to use to form the hair dye composition. WO
2005/044208
herewith is explicitly incorporated herein by reference.
The pH of the hair dye composition according to the invention is from 5 to 11
and preferably
from 7 to 9.
Depending on the composition and the desired pH value of the hair dye
composition, the pH
value may be adjusted with an alkalizing agent or an organic or inorganic
acid.
Any agent known in the art may be used as alkalizing agent, for example
ammonia or organic
aniines, such as glucami.ne, aminomethylpropanol, monoethanolamine,
diethanolamine,
triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, 2-amino-
2-methyl-1,
3-propanediol, 2-ami.no-2-methyl-l-propanol, and 2-amino-2-hydroxymethyl-1,3-
propanediol
and guanidium salts, or ammonium salts, such as ammonium chloride, ammonium
sulphate,
ammonium nitrate, ammonium phosphate, ammonium acetate, ammonium carbonate,
ammonium hydrogen carbonate, ammonium carbamate, ammonium hydroxide,
percarbonate
salts, or mixtures thereof.
As organic or inorganic acid may be used for example lactic acid, citric acid,
tartaric acid, acetic
acid or phosphoric acid and mixtures thereof.
The compositions of the present invention may comprise from 0.1% to 10% by
weight,
preferably from 0.5% to 5% by weight, most preferably from 1% to 3% by weight,
of an
alkalizing agent and/or organic or inorganic acid.
The agent according to invention is applied to the dry or previously washed
fiber and
after an exposure time of from 5 to 60 minutes, preferably from 10 to 45
minutes, it is
rinsed out with water ans optionally washed out with a shampoo. The keratin
fiber can
then optionally be post-treated in the usual manner and finally dried.
CA 02621871 2008-02-20
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37
An object of the present invention is the use of an aqueous or aqueous-
alcoholic
preparation, which contains a combination of oxidative dyes and direct dyes,
said
combination containing at least 3 direct dyes and the quantitative ratio of
oxidation
dyes to direct dyes equals 5:1 to 0.5:1, for the preparation of an agent for
coloring
keratin fibers, especially human hair, said agent being free of chemical
oxidizing
agents and upon air oxidation (i.e. without the addition of chemical oxidizing
agents)
gives a uniform and stable coloration immediately after application.
The following examples will explain in greater detail the object of the
invention
without limiting it to these examples:
EXAMPLES
Example 1A to 121A: Aerosol Colorant in Cream Form
1.2 g cetylstearyl alcohol
0.6 g sodium laurylsulfat
0.1 g disodium ethylenediaminetetraacetate
0.2 g ascorbic acid
2.5 g 1,2 propylene glycol
2.5 g ethanol
4.5 g ammonia
2.5 g monoethanolamine
X g Dyes (according to No. 1 to 121 of the below table 1)
0.3 g perfume oil
to 100.0 g water
The dye compositions prepared by the hot emulsification method were introduced
into
appropriate compressed-gas containers with propane/butane and F 152 (ratio of
1:1) in a ratio of
active ingredient to propellant of 95:5 %.
CA 02621871 2008-02-20
W-236FQ/CB
38
The aerosol foam was applied to dry hair and after an exposure time of 20
minutes rinsed out
with water. The hair was then dried.
Example 1B to 121B: Aerosol Colorant in Gel Form
2.00 g hydroxyethylcellulose
20.00 g cocamidopropylbetain
1.50 g D-panthenol
10.00'g ethanol
0.10 g disodium tetraborate
0.10 g disodium ethylenediaminotetraacetate
0.20 g ascorbic acid
4.50 g monoethanolamine
X g Dyes (according to No. I to 121 of the below table 1)
3.10 g sodium hydroxide, 20% aqueous solution
0.50 g perfume oil
to 100.00 g water
The gel base prepared by the cold-mixing method was combined with hot-
dissolved dyes and
introduced into an appropriate compressed-gas container with propane/butane
and F 152 (ratio of
1:1) in a ratio of active ingredient to propellant of 95:5 %.
The aerosol foam was applied to washed hair and after an exposure time of 15
minutes rinsed out
with water. The hair was then washed with a mild shampoo, again rinsed with
water and then
dried.
Example 1C to 121C: Cationic Aerosol Colorant in Gel Form
1.300 g hydroxyethylcellulose
6.000 g cocamidopropylbetaine
2.000 g polyethylene glycol 300 capryl glyceride (Softigen 767)
3.000 g decyl glucoside (Plantaren(D 2000)
1.500 g cetylrimethylammonium chloride
5.000 g isopropanol
CA 02621871 2008-02-20
W-236FQ/CB
39
0.200 g ascorbic acid
0.100 g disodium ethylenediaminetetraacetate
5.800 g monoethanolamine
X g Dyes (according to No. 1 to 121 of the below table 1)
0.500 g perfume oil
ad 100.000 g water
The gel base prepared by the cold-mixing method was combined with hot-
dissolved dyes and
introduced into an appropriate compressed-gas container with propane/butane
and F 152 (ratio of
1:1) in a ratio of active ingredient to propellant of 95:5 %.
The aerosol foam was applied to dry hair and after an exposure time of 30
minutes rinsed out
with water. The hair was then dried.
Example 1D to 121D: Liquid Air Oxidation Colorant
2.50 g oleic acid
2.00 g cetearyl alcohol
4.00 g Undeceth-3
5.00 g ethanol
X g Dyes (according to No. 1 to 121 of the below table 1)
ad 100.00 g water
The colorant was applied to dry hair and after an exposure time of 20 minutes
rinsed out with
water. The hair was then dried.
Unless otherwise indicated, all percentages are by weight.
Dye List:
A. Developer substances
El hydroxyethyl-p-phenylenediamine-sulfate
CA 02621871 2008-02-20
W-236FQ/CB
E2 n,n-bis(2-hydroxyethyl)-p-phenylenediamine-sulfate
E3 2-amino-5-ethylphenol-HC1
E4 toluene-2,5-diamine-sulfate
E5 methoxymethyl-ppd-sulfate
E6 4-amino-m-cresol
E7 p-aminophenol
E8 p-phenylenediamine
E9 1-hydroxyethyl4, 5 -diamino-pyrazole-sulfate
B. Coupler Substances
K 1 1 , 5-naphthalenedio 1
K2 3-amino-2,4-dichlorophenol
K3 1-naphthol
K4 hydroxyethyl-3,4-methylenedioxyaniline-HCl
K5 2,4-diaminophenoxyethanol-sulfate
K6 m-aminophenol
K7 4-chlororesorcinol
K8 4-amino-2-hydroxytoluene
K9 2-amino-4-hydroxyethylaminoanisole-sulfate
K10 2,4-diaminophenoxyethanol-HCl
K12 m-phenylenediamine
K13 Phenyl-methyl-pyrazolone
K14 6-methoxy-2-methylamino-3-aminopyridine-HCl
K15 2-methyl-5-hydroxyethylaminophenol
K16 2,6-dimethoxy-3,5-pyridinediamine-HCl
K17 resorcinol
K18 2-methylresorcinol
C. Non-oxidative Dyes (=Direct Dyes)
D 1 Acid Violet 43
D2 Basic Yellow 57
CA 02621871 2008-02-20
W-236FQ/CB
41
D3 2,6-diamino-3-((pyridin-3-yl)azo)pyridine
D4 Basic Violet 2
D5 HC Blue 16
D6 HC Yellow No. 12
D7 2-amino-6-chloro-4-nitrophenol
D8 Basic Blue 99
D9 Basic Brown 16
D 10 Basic Brown 17
D 11 Hc Yellow No. 13
D12 picramic acid (65%)
D13 HC Blue No. 2
D14 HC Red No. 13
D15 HC Red No. 3
D 16 3-nitro-p-hydroxyethylaminophenol
D17 HC Yellow No. 6
D18 hydroxyethyl-2-nitro-p-toluidine
D19 Disperse Violet 1
D20 Acid Black 52
D21 HC Blue No. 12
D22 4-nitrophenyl aminoethylurea
D23 4-amino-3-nitrophenol
D24 2-hydroxyethyl picramic acid
D25 4-hydroxypropylamino-3-nitrophenol
D26 2-chloro-6-ethylamino-4-nitrophenol
D27 HC Red No. 10 HC Red No. 11 (70:30)
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