Note: Descriptions are shown in the official language in which they were submitted.
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A 5-AMINO-1,2,3,4-TETRAHYDROQUINOLINE DERIVATIVE AND 4,5-DIAMINO-
PYRAZOLE DERIVATIVE FOR OXIDATIVE DYEING OF KERATIN FIBERS
FIELD OF THE INVENTION
The present invention relates to a composition for the oxidative dyeing of
keratin fibers,
in particular human keratin fibers, comprising (A) a 5-amino-1,2,3,4-
tetrahydroquinoline
derivative as defined in formula (I) hereafter, a physiologically compatible
water-soluble salt
thereof, or mixtures thereof, (B) a 4,5-diamino-pyrazole derivative as defined
in formula (II)
hereafter, a physiologically compatible water-soluble salt thereof, or
mixtures thereof, and (C) an
oxidizing agent.
BACKGROUND OF THE INVENTION
The oxidative dyeing process using one or more oxidative hair coloring
precursors in
combination with one or more oxidizing agent is the most extensively used
method to color hair.
Commonly, a peroxy oxidizing agent is used in combination with one or more
primary
intermediates and/or couplers, generally small molecules capable of diffusing
into hair. A wide
variety of primary intermediates and couplers have been employed in such
oxidative hair
coloring systems and compositions. Selection of specific combination of
couplers and primary
intermediates has also shown to provide some additional color benefits.
Besides providing the desired colour, these dye precursors used for oxidative
hair
coloring have to also meet some additional requirements. Indeed, the
combination of couplers
and primary intermediates used in this coloration process should deliver the
desired intensity
together with good light fastness, permanent wave fastness, acid fastness, and
rubbing fastness
and remain stable over a period of at least 4 to 6 weeks.
Compositions of the prior art comprising 5-amino-1,2,3,4-tetrahydroquinoline
derivatives
do not satisfy the above mentioned requirements in all aspects. Oxidative
dyeing compositions
comprising 5-amino-1,2,5,4-tetrahydroquinoline as coupler component is known,
see DE
2441895. However, this disclosure does not exemplify a combination of 5-amino-
1,2,3,4-
tetrahydroquinoline derivative and 4,5-diamino-pyrazole derivative.
The oxidative dyeing composition of the invention overcomes known color
intensity-
drawbacks together with color-rich shades, good resistance against shampooing
and rubbing- It
has surprisingly been found that the composition of the invention provides
color-rich shades,
which are resistant against shampooing and rubbing.
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SUMMARY OF THE INVENTION
According to a first aspect the present invention relates to a composition for
the oxidative
dyeing of keratin fibers, in particular human keratin fibers, comprising (A) a
5-amino-l,2,3,4-
tetrahydroquinoline compound of general formula (I), a physiologically
compatible water-soluble
salt thereof, or mixtures thereof; (B) a 4,5-diamino-pyrazole compound of
general formula (II), a
physiologically compatible water-soluble salt thereof, or mixtures thereof;
and (C) an oxidizing
agent;
NH2
R R4 NR5R6
CN R N N\ NR7R8
H 2
R3 R9
(I) (II)
wherein R1, R2, R3, R4, R5., R6, R7, Rg, R9 are further defined hereinafter.
According to a second aspect the present invention relates to a method of
dyeing hair
comprising the steps of:
(i) providing a tint component comprising (A) a 5 -amino- 1,2,3,4-
tetrahydroquinoline
derivative compound of the general formula (I), a physiologically compatible
water-soluble salt
thereof, or mixtures thereof; and (B) a 4,5-diamino-pyrazole derivative of the
general formula
(II), a physiologically compatible water-soluble salt thereof, or mixtures
thereof;
(ii) providing a developer component comprising (C) an oxidizing agent;
(iii) mixing the tint component and the developer component to obtain a
composition for
the oxidative dyeing of keratin fibers; and
(iv) applying said composition for the oxidative dyeing of keratin fibers onto
the hair.
According to a third aspect, the present invention relates to a kit
comprising: (i) a tint
component comprising (A) a 5 -amino- 1,2,3,4-tetrahydroqu inoline compound of
general formula
(I), a physiologically compatible water-soluble salt thereof, or mixtures
thereof; (B) a 4,5-
diamino-pyrazole compound of general formula (II), a physiologically
compatible water-soluble
salt thereof, or mixtures thereof; and (ii) a developer component comprising
(C) an oxidizing
agent.
DETAILED DESCRIPTION OF THE INVENTION
As used herein, the term "composition for the oxidative dyeing of keratin
fibers" means a
ready-to-use composition in a suitable carrier medium for dyeing keratin
fibers, in particular
human hair, comprising oxidative dye precursors (primary intermediates and
couplers) and an
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oxidizing agent. These compositions can typically be the result of a mixture
of two compositions
namely a tint component comprising the dye precursors and usually an
alkalizing agent such as
ammonia and a developer component comprising the oxidizing agent.
As used herein, the term "keratin" refers to a scleroprotein found in
epidermal tissues and
modified into hard structures such as horns, hair, and nails. As used herein,
the term "hair" refers
to keratinous fibers on a living, e.g. a person, or non-living body, e.g. in a
wig, hairpiece, or other
aggregation of non-living keratinous fibers. Mammalian, preferably human, hair
is preferred.
Notably, hair, wool, fur, and other keratinous fibers are suitable substrates
for coloring by the
compounds and compositions described herein.
As used herein, the term "dye precursors" refers to compounds that may be used
in the
composition to act as primary intermediates, couplers, or both, in order to
provide color to
ketatinous fibers.
It is to be understood that when this development refers to a particular
structure, all of the
reasonable additional tautomeric structures are included. In the art,
tautomeric structures are
frequently represented by one single structure and the invention follows this
general practice.
The 5-amino-1,2,3,4-tetrahydroquinoline compound of general formula (I), a
physiologically compatible water-soluble salt, or mixtures thereof are defined
as following:
NH2
CN Rr
H R2
R3
(1)
R1, R2 and R3 are substituents selected independently of each other from the
group
consisting of:
(a) C-linked substituents selected from the group consisting of-
(i) mono- or poly- substituted or unsubstituted, straight or branched,
saturated or mono-or
poly- unsaturated, alkyl or heteroalkyl systems,
(ii) mono- or poly- substituted or unsubstituted, straight or branched,
saturated or mono-
or poly- unsaturated, aryl systems, and
(iii) mono- or poly- substituted or unsubstituted, straight or branched,
saturated or mono-
or poly- unsaturated, heteroaryl systems, and
wherein said systems of (i), (ii) and (iii) comprise from 1 to 10 carbon atoms
and from 0
to 5 heteroatoms selected from the group consisting of 0, F, N, P and Si;
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(b) S -linked substituents selected from the group consisting of SA', S02A',
SO3A', SSA',
SOA', SO2NA'A2, SNA'A2, and SONA'A2;
(c) O-linked substituents selected from the group consisting of OA', ONA'A2;
(d) N-linked substituents selected from the group consisting of NA'A2,
(NA'A2A3)+
NA'SA2, NO2, NA'A2;
(e) substituents selected from the group consisting of COOA', CONA',
CONA'COA2,
C(=NA')NA2A3, CN, and X;
(f) fluoroalkyl substituents selected from the group consisting of mono-, poly-
, and per-
fluoro alkyl systems comprising from 1 to 12 carbon atoms and from 0 to 4
heteroatoms; and
(g) H;
wherein A', A2, and A' are selected independently of each other from the group
consisting of. H; mono- or poly- substituted or unsubstituted, straight or
branched, saturated or
mono-or poly- unsaturated, alkyl or heteroalkyl systems; mono- or poly-
substituted or
unsubstituted, straight or branched, saturated or mono-or poly- unsaturated,
aryl or heteroaryl
systems; and substituted or unsubstituted, mono-, poly-, or per-fluoro alkyl
systems; or A' and A2
together with nitrogen atoms to which they are bound form a ring; wherein said
systems
comprise from I to 10 carbon atoms and from 0 to 5 heteroatoms selected from
the group
consisting of 0, S, N, P, and Si; and wherein X is a halogen selected from the
group consisting of
F, Cl, Br, and I.
Suitable physiologically compatible water soluble salts of formula (I) are
also included
such as chlorides, bromides, sulfates, such as hemisulfates, tartrates,
lactates, malates and
acetates.
In a preferred embodiment, R,, R2 and R3 are selected independently of each
other from
the group consisting of a hydrogen atom; a halogen atom; an amino substituent,
a hydroxyl
substituent; a cyano substituent; a Cl-C4 alkyl substituent; a trifluoromethyl
substituent; an
alkylamino substituent; a hydroxyalkylamino substituent; an acetylamido
substituent; a carboxyl
substituent or its esters; an alkoxy substituent; an alkoxyalkyl substituent;
a carbamoyl
substituent; an alkylcarbamoyl substituent; a hydroxyalkylcarbamoyl
substituent; an amido
substituent; an alkylamido substituent; an alkylcarbonyl substituent; an
alkoxycarbonyl
substituent; an aryloxy substituent; an acyloxy substituent; an alkylthio
substituent; an arylthio
substituent; a heteroarylthio substituent; a heteroaryloxy substituent; a
thiocyano substituent; a
3-, 4-, 5-, 6-, or 7-membered heterocycle having at least one nitrogen, oxygen
or sulfur atom; an
aryl substituent which is optionally substituted; a sulfonyl substituent; a
sulfinyl substituent; a
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phosphonyl substituent; a sulfamoyl substituent; a siloxy substituent; an
acyloxy substituent; a
carbamoyloxy substituent; a sulphonamide substituent; an imide substituent; a
ureido substituent;
a sulfamoylamino substituent; an alkoxycarbonylamino substituent; an
aryloxycarbonylamino
substituent; an aryloxycarbonyl substituent; and a benzenesulfonamido
substituent.
5 The 5-amino-1,2,3,4-1:etrahydroquinoline derivative (I) may be a compound
with formula
NH2
N
H
(LI)
The 5-amino-1,2,3,4-tetrahydroquinoline derivative (I) may be a compound with
formula
NH2
H NH2
(1.2)
The 5-amino-1,2,3,4-tetrahydroquinoline derivative (I) may be a compound with
formula
(1.3):
NH2
N
H OH
(1.3)
The 5-amino-1,2,3,4-tetrahydroquinoline derivative (I) may be a compound with
formula
(1.4):
NH2
N
H
(1.4)
In order to reach the desired hair color, the 5-amino-1,2,3,4-
tetrahydroquinoline
derivative of formula (I) needs to be combined with a primary intermediate, in
particular but not
limited to an 4,5-diamino-pyrazole derivative of general formula (II)
hereafter, a physiologically
compatible water-soluble salt thereof, or mixtures thereof:
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R4 NR5R6
N' N NR7R8
R9
(II)
wherein R4 has the same definition given above for R1, R2, R3 of the 5-amino-
1,2,3,4-
tetrahydroquinoline compound of general formula (I);
wherein R5, R6, R7, R8 and R9 are substituents selected independently of each
other from
the group consisting of.
(h) C-linked substituents selected from the group consisting of-
(i) mono- or poly- substituted or unsubstituted, straight or branched,
saturated or mono-or
poly- unsaturated, alkyl or heteroalkyl systems,
(ii) mono- or poly- substituted or unsubstituted, straight or branched,
saturated or mono-
or poly- unsaturated, aryl systems, and
(iii) mono- or poly- substituted or unsubstituted, straight or branched,
saturated or mono-
or poly- unsaturated, heteroaryl systems, and
wherein said systems of (i), (ii) and (iii) comprise from about 1 to 10 carbon
atoms and
from about 0 to 5 heteroatoms selected from the group consisting of 0, F, N, P
and Si;
(i) substituents selected from the group consisting of COOA', CONA',
CONA'COA2,
C(=NA')NA'A2, CN; and
(j) H;
Preferably R4, R5, R6. R7, R8 and R9 are substituents selected independently
of each other
from the group consisting of hydrogen, C1-C6 alkyl, C2-C6 hydroxalkyl, C2-C4
alkoxy and
mixtures thereof.
In a preferred embodiment the 4,5-diamino pyrazole derivative (II) is a
compound with
formula (11.1):
NH2
N_N\ NH2
OH
(I1.l)
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Oxidizing Agent
The compositions of the invention comprise an oxidizing agent. Typical
suitable
oxidizing agents for the oxidative dyeing of keratin fibers may be selected
from hydrogen
peroxide, sodium periodate, urea peroxide, melamine peroxide, perborates,
percarbonates,
perphosphates, persilicates, persulfates, oxidizing enzymes such as uricases,
oxidases, and
peroxidases, and mixtures thereof. Hydrogen peroxide, perborates, or
percarbonates may be
preferred. Another potential oxidizing agent for use herein is a source of
peroxymonocarbonate
ions. Preferably, such a source is formed in situ from a source of hydrogen
peroxide and a
hydrogen carbonate ion source. Such an oxidizing agent has been found to be
particularly
effective at a pH of up to and including 9.5, preferably from about 7.5 to
about 9.5 more
preferably about pH 9. Moreover, this system is also particularly effective in
combination with a
source of ammonia or ammonium ions.
Accordingly, any source of these peroxymonocarbonate ions may be utilized.
Suitable
sources for use herein include sodium, potassium, guanidine, arginine,
lithium, calcium,
magnesium, barium or ammonium salts of carbonate, carbamate and hydrocarbonate
ions and
mixtures thereof. In particular, sodium carbonate, sodium hydrogen carbonate,
potassium
carbonate, potassium hydrogen carbonate, guanidine carbonate, guanidine
hydrogen carbonate,
lithium carbonate, calcium carbonate, magnesium carbonate, barium carbonate,
ammonium
carbonate, ammonium hydrogen carbonate and mixtures thereof may be preferred.
Percarbonate
salts may also be utilized to provide both the source of carbonate ions and as
an oxidizing agent.
Preferred sources of carbonate ions, carbamate and hydrocarbonate ions are
sodium
hydrogen carbonate, potassium hydrogen carbonate, ammonium carbonate, ammonium
carbamate, and mixtures thereof.
The hair dyeing composition may usually comprise from about 1% to about 15% by
total
weight of the composition, typically from about 1.5% to about 10% by weight,
and more
typically from about 2% to about 8% by weight of the oxidizing agent relative
to the total weight
of the composition.
The oxidizing agent may be provided in a developer component which is mixed to
a tint
component to obtain the composition of the invention. The developer component
may be based
on any desired formulation chassis, including any commercial product, for
example an oil-in-
water emulsion. Typical developer components comprise about 6% or about 9% of
H202 by total
weight of the composition. A commercial example is the Welloxon Emulsion with
respectively
about 6% and about 9% H2O2, marketed by Wella and comprising as INCI
ingredients: Water,
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Hydrogen Peroxide, Cetearyl Alcohol, Ceteareth-25, Salicylic Acid, Phosphoric
Acid, Disodium
Phosphate, Etidronic Acid.
The hair dyeing composition of the invention may be formed as thick liquid,
cream, gel,
emulsion, foam, aerosol mousse or as a solid form to which water is added to
generate the
oxidant and form a thickened vehicle suitable for hair coloring. They may
comprise in addition to
the ingredients indicated above further ingredients in order to further
enhance the properties of
the composition, including but not limited to: solvents; oxidative dyes,
direct dyes; oxidizing
agents; radical scavengers; thickeners and or rheology modifiers; chelants; pH
modifiers and
buffering agents; carbonate ion sources; peroxymonocarbonate ion sources;
anionic, cationic,
nonionic, amphoteric or zwitterionic surfactants, or mixtures thereof;
anionic, cationic, nonionic,
amphoteric or zwitterionic polymers, or mixtures thereof; fragrances; enzymes;
dispersing
agents; peroxide stabilizing agents; antioxidants; natural ingredients, e.g.
proteins and protein
compounds, and plant extracts; conditioning agents including silicones and
cationic polymers,
ceramides, preserving agents; and opacifiers and pearling agents (such as
titanium dioxide and
mica). Some adjuvants referred to above, but not specifically described below,
which are suitable
are listed in the International Cosmetics Ingredient Dictionary and Handbook,
(8th ed.; The
Cosmetics, Toiletry, and Fragrance Association). Particularly, vol. 2,
sections 3 (Chemical
Classes) and 4 (Functions) are useful in identifying specific adjuvants to
achieve a particular
purpose or multipurpose. A few of these ingredients are discussed hereinbelow,
whose disclosure
is of course non-exhaustive.
Alkalizing agent
The composition for the oxidative dyeing of keratin fibers may further
comprise,
generally in the tint component, an alkalizing agent as known in the art. Any
alkalizing agent
known in the art may be used such as ammonia, alkanolamines for example
monoethanolamine,
diethanolamine, triethanolamine, monopropanolamine, dipropanolamine,
tripropanolamine, 2-
amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-l-propanol, and 2-amino-2-
hydroxymethyl-
1,3-propanediol, guanidium salts, alkali metal and ammonium hydroxides such as
sodium
hydroxide, alkali metal and ammonium carbonates, and mixtures thereof. Typical
alkalizing
agents are ammonia and/or monoethanolamine.
Typically, the compositions for the oxidative dyeing of keratin fibers
comprise from
about 0.1% to about 10%, preferably from about 0.5% to about 6%, more
preferably from about
1% to about 4% by weight of the alkalizing agent relative to the total weight
of the composition.
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Primary intermediates
In addition to the pyrazole compounds of the invention, the hair dyeing
compositions of
the invention may comprise further primary intermediates. Suitable primary
intermediates for use
in the compositions described herein include, but are not limited to: toluene-
2,5-diamine, p-
phenylenediamine, N-phenyl-p-phenylenediamine, N,N-bis(2-hydroxyethyl)-p-
phenylenediamine, 2-hydroxyethyl-p-phenylenediamine, hydroxypropyl-bis-(N-
hydroxyethyl-p-
phenylenediamine), 2-methoxymethyl-p-phenylenediamine, 2-(1,2-dihydroxyethyl)-
p-
phenylenediamine, 2,2'-(2-(4-arninophenylamino)ethylazanediyl)diethanol, 2-
(2,5-diamino-4-
methoxyphenyl)propane- 1,3 -diol, 2-(7-amino-2H-benzo[b][I,4]oxazin-4(3H)-
yl)ethanol, 2-
chloro-p-phenylenediamine, p-aminophenol, p-methylaminophenol, 4-amino-m-
cresol, 6-amino-
m-cresol, 5-ethyl -o-aminophenol, 2-methoxy-p-phenylenediamine, 2,2'-
methylenebis-4-
aminophenol, 2,4,5,6-tetraminopyrimidine, 2,5,6-triamino-4-pyrimidinol, 1-
hydroxyethyl-4,5-
diaminopyrazole sulfate, 4,5-diamino-l-methylpyrazole, 4,5-diamino-l-
ethylpyrazole, 4,5-
diamino-l-isopropylpyrazole, 4,5-diamino-l-butylpyrazole, 4,5-diamino-l-
pentylpyrazole, 4,5-
diamino-l-benzylpyrazole, 2,3-diamino-6,7-dihydropyrazolo[1,2-a]pyrazol-1(5H)-
one
dimethosulfonate, and mixtures thereof.
Typically, the compositions for the oxidative dyeing of keratin fibers
comprise from
about 0.1% to about 10%, preferably from about 0.3% to about 6%, more
preferably from about
0.5% to about 4% by weight of the primary intermediates relative to the total
weight of the
composition.
Couplers
In addition to the quinoline compounds of the invention, the hair dyeing
compositions of
the invention may comprise couplers to obtain various shades. Suitable
couplers for use in the
compositions described herein include, but are not limited to: resorcinol, 4-
chlororesorcinol, 2-
chlororesorcinol, 2-methylresorcinol, 4,6-dichlorobenzene-1,3-diol, 2,4-
dimethylbenzene-1,3-
diol, m-aminophenol, 4-amino-2-hydroxytoluene, 2-methyl-5-
hydroxyethylaminophenol, 3-
amino-2,6-dim ethyl phenol, 3-amino-2,4-dichlorophenol, 5-amino-6-chloro-o-
cresol, 5-amino-4-
chloro-o-cresol, 6-hydroxybenzomorpholine, 2-amino-5-ethylphenol, 2-amino-5-
phenylphenol,
2-amino-5-methylphenol, 2-am ino-6-methylphenol, 2-am ino-5-ethoxyphenol, 5-
methyl-2-
(methylamino)phenol, 2,4-diaminophenoxyethanol, 2-amino-4-
hydroxyethylaminoanisole, 1,3-
bis-(2,4-d iaminophenoxy)-propane, 2,2'-(2-methyl-1,3-
phenylene)bis(azanediyl)diethanol,
benzene- l,3-diamine, 2,2'=(4,6-diamino-1,3-phenylene)bis(oxy)diethanol, 3-
(pyrrolidin-l-
yl)aniline, 1-(3-(dimethylamino)phenyl)urea, 1-(3-aminophenyl)urea, 1-
naphthol, 2-methyl-l-
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naphthol, 1,5-naphthalenediol, 2,7-naphthalenediol or 1-acetoxy-2-
methylnaphthalene, 4-chloro-
2-methylnaphthalen-1-ol, 4-methoxy-2-methylnaphthalen-l-ol, 2,6-dihydroxy-3,4-
dimethylpyridine, 2,6-dimethoxy-3,5-pyridinediamine, 3-amino-2-methylamino-6-
methoxypyridine, 2-amino-3-hydroxypyridine, 2,6-diaminopyridine, pyridine-2,6-
diol, 5,6-
5 dihydroxyindole, 6-hydroxyindole, 5,6-dihydroxyindoline, 3-methyl-l-phenyl-
lH-pyrazol-
5(4H)-one, 1,2,4-trihydroxybenzene, 2-(benzo[d][1,3]dioxol-5-ylamino)ethanol
(also known as
hydroxyethyl-3,4-methylene(lioxyaniline), and mixtures thereof. When the
composition is
obtained by mixing a tint component and a developer component, additional
primary
intermediates and couplers may be preferably incorporated in the tint
component.
10 Typically, the compositions for the oxidative dyeing of keratin fibers
comprise from
about 0.1% to about 10%, preferably from about 0.3% to about 6%, more
preferably from about
0.5% to about 4% by weight of the couplers relative to the total weight of the
composition.
Direct Dyes
The compositions of the present invention may also comprise compatible direct
dyes, in
an amount sufficient to provide additional coloring, particularly with regard
to intensity.
Typically, such an amount will range from about 0.05% to about 4%, by weight
of the direct dyes
relative to the total weight of the composition. When the composition is
obtained by mixing a tint
component and a developer component, the direct dyes are usually incorporated
in the tint
component.
The following direct dyes are commonly used: Acid dyes such as Acid Yellow 1,
Acid
Orange 3, Acid Black 1, Acid Black 52, Acid Orange 7, Acid Red 33, Acid Yellow
23, Acid
Blue 9, Acid Violet 43, HC Blue 16, Acid Blue 62, Acid Blue 25, Acid Red 4,
Basic Dyes such
as Basic Brown 17, Basic Red 118, Basic Orange 69, Basic Red 76, Basic Brown
16, Basic
Yellow 57, Basic Violet 14, Basic Blue 7, Basic Blue 26, Basic Red 2, Basic
Blue 99, Basic
Yellow 29, Basic Red 51, Basic Orange 31, Basic Yellow 87, 4-(3-(4-amino-9,10-
dioxo-9,10-
dihydroanthracen-l-ylamino)propyl)-4-methylmorpholin-4-ium-methylsulfate, (E)-
1-(2-(4-(4,5-
dimethylthiazol-2-yl)diazenyl)phenyl)(ethyl)amino)ethyl)-3-methyl-1H-imidazol-
3-ium chloride,
(E)-4-(2-(4-(dimethylamino)phenyl)diazenyl)-1-methyl-1 H-imidazol-3-ium-3-
yl)butane-l -
sulfonate, (E)-4-(4-(2-methyl -2-phenyl hydrazono)methyl)pyridinium-l-
yl)butane-l-suIfonate,
N,N-dimethyl-3-(4-(methylamino)-9,10-dioxo-4a,9,9a,I0-tetrahydroanthracen-1-
ylamino)-N-
propylpropan-l-aminium bromide, Disperse Dyes such as Disperse Red 17,
Disperse Violet 1,
Disperse Red 15, Disperse Violet 1, Disperse Black 9, Disperse Blue 3,
Disperse Blue 23,
Disperse Blue 377, Nitro Dyes such as 1-(2-(4-nitrophenylamino)ethyl)urea, 2-
(4-methyl-2-
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11
nitrophenylamino)ethanol, 4-nitrobenzene-1,2-diamine, 2-nitrobenzene-1,4-
diamine, Picramic
acid, HC Red No. 13, 2,2'-(2-nitro-1,4-phenylene)bis(azanediyl)diethanol, HC
Yellow No. 5, HC
Red No. 7, HC Blue No.2, HC Yellow No. 4, HC Yellow No. 2, HC Orange No. 1, HC
Red No.
1, 2-(4-amino-2-chloro-5-nitrophenylamino)ethanol, HC Red No. 3, 4-amino-3-
nitrophenol, 4-(2-
hydroxyethylamino)-3-nitrophenol, 2-amino-3-nitrophenol, 2-(3-(methylamino)-4-
nitrophenoxy)ethanol, 3-(3-amino-4-nitrophenyl)propane-1,2-diol, HC Yellow No.
11, HC Violet
No. 1, HC Orange No. 2, HC Orange No. 3, HC Yellow No. 9, HC Red No. 10, HC
Red No. 11,
2-(2-hydroxyethylamino)-4,6-dinitrophenol, HC Blue No. 12, HC Yellow No. 6, HC
Yellow No.
12, HC Blue No. 10, HC Yellow No. 7, HC Yellow No. 10, HC Blue No. 9, 2-chloro-
6-
(ethylamino)-4-nitrophenol, 6-nitropyridine-2,5-diamine, HC Violet No. 2, 2-
amino-6-chloro-4-
nitrophenol, 4-(3-hydroxypropylamino)-3-nitrophenol, HC Yellow No. 13, 6-nitro-
1,2,3,4-
tetrahydroquinoxaline, HC Red No. 14, HC Yellow No. 15, HC Yellow No. 14, N2-
methyl-6-
nitropyridine-2,5-diamine, N 1-allyl-2-nitrobenzene-l,4-diamine, HC Red No. 8,
HC Green No.1,
HC Blue No. 14, and Natural dyes such as Annato, Anthocyanin, Beetroot,
Carotene, Capsanthin,
Lycopene, Chlorophyll, Henna, Indigo, Cochineal.
Thickeners
The hair dyeing compositions of the present invention may comprise a thickener
in an
amount sufficient to provide the composition with a viscosity so that it can
be readily applied to
the hair without unduly dripping off the hair and causing mess. Typically,
such an amount will be
at least 0.05%, preferably at least 0.5%, more preferably at least 1%, by
weight of thickener
relative to the total weight of the composition. When the composition is
obtained by mixing
several components, the thickener may be present in any of the components.
Preferred for use
herein are salt tolerant thickeners, including but not limited to: xanthan,
guar, hydroxypropyl
guar, scleroglucan, methyl cellulose, ethyl cellulose (available as
AQUACOTE(TM)),
hydroxyethyl cellulose (NATROSOL(TM)), carboxymethyl cellulose,
hydroxypropylmethyl
cellulose, microcrystalline cellulose, hydroxybutylmethyl cellulose,
hydroxypropyl cellulose
(available as KLUCEL(TM)), hydroxyethyl ethyl cellulose, cetyl hydroxyethyl
cellulose
(available as NATROSOL(TM)) Plus 330), N-vinylpyrollidone (available as
POVIDONE(TM)),
Acrylates/Ceteth-20 Itaconate Copolymer (available as STRUCTURE(TM) 3001),
hydroxypropyl starch phosphate (available as STRUCTURE(TM) ZEA),
polyethoxylated
urethanes or polycarbamyl polyglycol ester (e.g. PEG-150/Decyl/SMDI copolymer
(available as
ACULYN(TM) 44), PEG-150/Stearyl/SMDI copolymer available as ACULYN(TM) 46),
Acrylates/Beheneth-25 Methacrylate Copolymer (available as ACULYN(TM) 28),
CA 02754959 2011-10-07
12
Acrylates/Vinyl Neodecanoate Crosspolymer (available as ACULYN(TM) 38),
Acrylates/Steareth-20 Methacrylate Crosspolymer (available as ACULYN(TM) 88),
PEG-150
Distearate (available as ACULYN(TM) 60), trihydroxystearin (available as
THIXCIN(TM)),
acrylates copolymer (e.g. available as ACULYN(TM) 33) or hydrophobically
modified acrylate
copolymers (e.g. Acrylates/Steareth-20 Methacrylate Copolymer (available as
ACULYN(TM)
22), non-ionic amphophilic polymers comprising at least one fatty chain and at
least one
hydrophilic unit selected from polyether urethanes comprising at least one
fatty chain.
Also preferred for use herein are thickeners based on lamellar gel network
systems,
comprising at least one surfactant or amphophile having an HLB of 6 or less
and a melting point
of at least 30 C, preferably selected from fatty alcohols comprising from 14
to 30 carbon atoms,
or oxyethylenated fatty alcohols comprising from 16 to 30 carbon atoms and 2
units or less of
ethylene oxide, and further comprising at least one ionic or nonionic
surfactant, preferably
selected from:
anionic surfactants selected from C8-C30 alkyl sulfates, preferably C12-C18
alkyl
sulfates,
anionic surfactants according to the formula RfX,,,YM, wherein R is
independently selected from alkyl, alkenyl or alkylaryl groups having from 8
to 30 carbon atoms,
X is independently selected from polar groups comprising at least one carbon
atom and at least
one oxygen or nitrogen atom, Y is an anionic group selected from carboxylates,
sulfates,
sulfonates or phosphates, n and m are independently 1 or 2, and M is hydrogen
or a salt forming
cation and mixture thereof, most preferably selected from C8-C30 alkyl ether
phosphates having
from 1 to 20, preferable 2 to 10 ethylene oxide units (e.g. available as
CRODAFOS(TM) CES);
non-ionic surfactant comprising one or more polyethyleneoxide chains,
preferably each polyethyleneoxide chain has on average at least 50 ethylene
oxide units and most
preferably 100 to 200 ethylene oxide units (e.g. available as VOLPO(TM) S200),
cationic surfactants selected from quaternary ammonium salts or amido-amines
having at least one fatty chain, preferably comprising at least 16 carbon
atoms and most
preferably at least 20 carbon atoms,
- and mixture thereof.
Examples of such lamellar gel network systems are disclosed in EPI,832,273 and
EP2,103,299.
The composition preferably comprises a mixture of cetearyl alcohol and dicetyl
phosphate and ceteth-10 phosphate (e.g. available as CRODAFOS(TM) CES).
CA 02754959 2011-10-07
13
Chelants
The compositions of the present invention may comprise chelants in an amount
sufficient
to reduce the amount of metals available to interact with formulation
components, particularly
oxidizing agents, more particularly peroxides and percarbonates. Typically,
such an amount
range from at least 0.15%, preferably at least 0.25%, by weight of the
chelants relative to the
total weight of the composition. Suitable chelants for use herein include but
are not limited to:
diethylenetriamine-N,N',N"-polyacids, diethylenetriaminepentaacetic acid
(DTPA),
diethylenetriaminepenta(methylene phosphonic acid) (DTPMP), diamine-N,N'-
dipolyacids,
monoamine monoamide-N,N'-dipolyacids, a N,N'-bis(2-
hydroxybenzyl)ethylenediamine-N,N'-
diacetic acid, preferably EDDS (ethylenediaminedisuccinic acid), carboxylic
acids (preferably
aminocarboxylic acids), phosphonic acids (preferably aminophosphonic acids)
and
polyphosphoric acids (in particular straight polyphosphoric acids), their
salts and derivatives.
When the composition is obtained by mixing a tint component and a developer
component, the
chelants may be incorporated in the tint component or in the developer
component or in both. A
chelant is usually present in developer components for stability reason.
pH Modifiers
The compositions of the present invention may comprise in addition to the
alkalizing
agent discussed above a pH modifier and/or buffering agent in an amount that
is sufficiently
effective to adjust the pH of the composition to fall within a range from
about 3 to about 13,
preferably from about 8 to about 12, more preferably from about 9 to about 11.
Radical Scavengers
According to the present invention, the compositions may comprise a radical
scavenger.
As used herein the term radical scavenger refers to a species that can react
with a radical, to
convert the radical species by a series of fast reactions to an unreactive or
less reactive species.
The radical scavenger is also preferably selected such that it is not an
identical species as
the alkalising agent and is present in an amount sufficient to reduce the
damage to the hair during
the colouring /bleaching process. The compositions of the present invention
comprise a radical
scavenger from about 0.1 % to about 10%, preferably from about l % to about 7%
by weight of
the radical scavenger relative to the total weight of the composition.
Suitable radical scavengers for use herein may be selected from the classes of
alkanolamines, amino sugars, amino acids, esters of amino acids and mixtures
thereof. Suitable
compounds include 3-substituted-pyrazol-5 -ones, 3 -carboxy- I H-pyrazol-5 -
one, 3-methyl-l-
phenyl-pyrazol-5-one, 3-methyl-l-p-tolyl-pyrazol-5-one, 3-methyl-l-(4-
sulfophenyl)-pyrazol-5-
CA 02754959 2011-10-07
14
one, 3-methyl-l-(4-suI foam idophenyl)-pyrazol-5-one, 3-methyl-l-(3-
sulfophenyl)-pyrazol-5-one,
3-methyl -l -(3-suI foamidophenyl)-pyrazol-5-one, 3-methyl-l -(2-chloro-5-
sulfophenyl)-pyrazol-
5-one, 3-methyl-1 -(2,5-dichloro-4-sulfophenyl)-pyrazol-5-one, 3-methyl-l-(4-
chlorophenyl)-
pyrazol-5-one, 3-methyl- 1-(4-carboxyphenyl)-pyrazol-5-one, 3 -carboxy- I -
phenyl-pyrazol-5 -one,
3 -carboxy- I -(4-sul fophenyl)-pyrazol-5 -one, 1,3 -diphenyl-pyrazol-5 -one,
methyl pyrazol-5-one-
3-carboxylate, 3-amino-l-propanol, 4-amino-l-butanol,5-amino-l-pentanol, I-
amino-2-propanol,
I-amino-2-butanol, 1-amino-2-pentanol, I-amino-3-pentanol, I-amino-4-pentanol,
3-amino-2-
methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol,
glucosamine, N-
acetylglucosamine, glycine, arginine, lysine, proline, glutamine, histidine,
sarcosine, serine,
glutamic acid, tryptophan, or mixtures thereof, or the salts, such as the
potassium, sodium, or
ammonium salts thereof, or mixtures thereof. In some embodiments, the
inventive compositions
may comprise glycine, sarcosine, lysine, serine, 2-methoxyethylamine,
glucosamine, glutamic
acid, morpholine, piperidine, ethylamine, 3-amino-l-propanol, or mixtures
thereof.
Method of hair dyeing
In order to use the dyeing composition, the tint component and developer
component are
usually mixed immediately prior to use and a sufficient amount of the mixture
is applied to the
hair, according to the hair abundance, generally from about 60 to about 250
grams. Upon such
preparation the composition is applied to the hair to be dyed and remains in
contact with the hair
for an amount of time effective to dye the hair. Typically, the hair dye
composition is allowed to
act on the hair from about 2 to about 60, preferably about 15 to about 45,
more preferably about
minutes, at a temperature ranging from 15 C to about 50 C. Thereafter, the
hair is rinsed
with water to remove the composition and dried. If necessary, the hair is
washed with a shampoo
and rinsed, e.g., with water or a weakly acidic solution, such as a citric
acid or tartaric acid
solution, and dried. Optionally, a separate conditioning product may also be
provided.
25 The method of dyeing hair with the composition may therefore comprise the
steps of-
(i) providing a tint component comprising (A) a 5-amino-1,2,3,4-
tetrahydroquinoline
derivative compound of the general formula (I) as defined above, a
physiologically compatible
water-soluble salt thereof or mixtures thereof and; (B) a 4,5-diamino-pyrazole
derivative as
defined in formula (II) of the general formula (II) as defined above, a
physiologically compatible
30 water-soluble salt thereof or mixtures thereof;
(ii) providing a developer component comprising (C) an oxidizing agent;
(iii) mixing the tint component and the developer component to obtain a
composition for
the oxidative dyeing of keratin fibers;
CA 02754959 2011-10-07
(iv) applying said composition for the oxidative dyeing of keratin fibers onto
the hair.
The method may further comprise waiting a period of time, typically between 2
minutes
and 60 minutes, and then rinsing the composition from the hair.
The compositions can be applied on hair via applicator bottle or brush. It can
be used on
5 full head or partly on single strands (highlight application) as common
highlight applicator foils,
caps and special applicators can be used, but also freehand techniques such as
balayage, with
brush and/or combs can be possible. The composition can also be applied as a
mousse via a
manual spray, a pressurized container or an aerosol mousse.
The composition may be dispensed as a solid form to which water is added to
generate
10 the oxidant and form a thickened vehicle suitable for hair coloring.
The dye combination of the invention may also be used in three components
system. See
for example disclosed US2010/0223739A2 assigned to L'Oreal. Such a process and
kit for
lightening or dyeing keratin fibers may comprise the following composition
applied to the hair
fibers: an aqueous cosmetic composition (A) comprising at least one fatty
substance and at least
15 one surfactant; a cosmetic composition (B) comprising at least one alkaline
agent and the
oxidative dyes of the invention and if present direct dyes and other oxidative
dyes, a cosmetic
composition (C) comprising at least one oxidizing agent, wherein the amount of
the at least one
fatty substance in composition (A) is greater than 20% by weight relative to
the total weight of
composition (A).
Methods of making - Kit
The composition, and its tint component and developer component, may be
manufactured
by conventional processes known in the art for manufacturing oxidative dyeing
products, and ad-
mixing the ingredients of each component composition in suitable vessels,
followed by
packaging in appropriate individual containers. The components may be for
example packaged in
plastic or aluminium bottles.
In particular, the present invention may be provided as a kit comprising
different
components to be mixed by the consumer or salon stylist to obtain a hair
dyeing composition
according to the invention. Such a kit may comprise:
(i) a tint component comprising (A) a 5-amino-1,2,3,4-tetrahydroquinoline
derivative of
general formula (1), a physiologically compatible water-soluble salt thereof,
or mixtures thereof,
(B) a 4,5-diamino-pyrazole derivative of general formula (II), a
physiologically compatible
water-soluble salt, or mixtures thereof, and
ii) a developer component comprising (C) an oxidizing agent.
CA 02754959 2011-10-07
16
The kit may be presented in a single package comprising separate containers
for the tint
component, the developer component, and optionally a conditioner, a color
refresher or other hair
treatment product, instructions for use, gloves. The instructions for use
include the steps of the
method described above and optionally provide visual cues or pictures for the
desired steps of the
method. Kits are usually sold in retail products with enough material in each
component for
preparing a hair dyeing composition for one use.
The composition may be dispensed as a foam using for example manually-
actuable, non-
aerosol dispenser such as a pump or squeeze foamers, aerosol mousse. See for
example EP
613,728 BI, WO 97/013585 Al, EP 1,716,933A1, US 3,709,437, US 3,937,364, US
4,022,351,
US 4,147,306, US 4,184,615, US 4,615,467 and FR 2,604,622. One particular
example of a
squeeze foamer useful herein is able to dispense from an upright or inverted
position such as the
one discussed in US 6,604,693 assigned to Taplast, and more specifically, at
column 2, line 65,
through column 4, line 67 of that patent.
EXAMPLES
The following are non-limiting examples of the compositions of the present
invention.
The examples are given solely for the purpose of illustration and are not to
be construed as
limitations of the present invention, as many variations thereof are possible
without departing
from the spirit and scope of the invention, which would be recognized by one
of ordinary skill in
the art.
The 5-amino-1,2,3,4-tetrahydroquinoline derivatives of the formula (I) can be
synthesized
following the experimental protocol described by D. Roberts, J.A. Joule in
Journal of Organic
Chemistry, 62 (1997) pages 568-577.
The synthesis of 5-amino-1,2,3,4-tetrahydroquinoline derivatives of the
formula (I) as
shown in the following scheme.
NH2 NH2
~ R1
R1 NiC12/NaBH4
C
N R2 N / R2
R3 H R3
(1)
CA 02754959 2011-10-07
17
Examples I to 4: Hair dyes (1:1 combinations)
1.25 mmol 5-amino-1,2,3,4-tetrahydroquinoline of the formula (I) as described
in examples I to 4.
1.25 mmol primary intermediate substance (II.1)
10.0 g lauryl ether sulfate (28 percent aqueous solution)
9.0 g ammonia (22 percent aqueous solution)
7.8 g ethanol
0.3 g ascorbic acid
0.3 g ethylenediaminotetraacetic acid disodium salt hydrate
ad 100.0 g water, demineralized
10 g of the above dye solution were mixed directly prior to application with
10 g of a 6 percent
hydrogen peroxide solution. The mixture was then applied to bleached hair.
After a contact time
of 30 minutes at 40 C, the hair was rinsed with water, washed with a standard
commercial
shampoo and dried. The resulting colorations are summarized in table 1.
Table 1:
Example No Coupler substance of the formula (I) Shade obtained
NH2
1 N C ICI darkest burgundy red
H
(1.1)
5-amino-1,2,3,4-tetrahydroquinoline
NH2
2 CN~ NH2 red
H
(1.2)
5,7-dlamino-1,2,3,4-tetrahydroquinoline
CA 02754959 2011-10-07
18
NH2
3 H C pink
OH
(1.3)
5-am ino-8-hydroxy- 1,2,3,4-
tetrahydroquinoline
NH2
C &1:
4 H violet
(1.4)
5-am ino-6-methyl-1,2,3,4-tetrahydroqu inol ine
Unless stated otherwise, all of the percentages given in the present
application are
percentages by weight.
Except as otherwise noted, all amounts including part, percentages, and
proportions are
understood to be modified by the word "about", and amounts are not intended to
indicate
significant digits. Except as otherwise noted, the articles "a", "an", and
"the" mean "one or more".
All percentages, parts and ratios are based upon the total weight of the
compositions of
the present invention, unless otherwise specified. All such weights as they
pertain to listed
ingredients are based on the active level and, therefore, do not include
solvents or by-products
that may be included in commercially available materials, unless otherwise
specified. The term
"weight percent" may be denoted as "wt. %" herein.
The dimensions and values disclosed herein are not to be understood as being
strictly
limited to the exact numerical values recited. Instead, unless otherwise
specified, each such
dimension is intended to mean both the recited value and a functionally
equivalent range
surrounding that value. For example, a dimension disclosed as "40 mm" is
intended to mean
"about 40 mm."
Every document cited herein, including any cross referenced or related patent
or
application is hereby incorporated herein by reference in its entirety unless
expressly excluded or
otherwise limited. The citation of any document is not an admission that it is
prior art with
respect to any invention disclosed or claimed herein or that it alone, or in
any combination with
any other reference or references, teaches, suggests or discloses any such
invention. Further, to
the extent that any meaning or definition of a term in this document conflicts
with any meaning
CA 02754959 2011-10-07
19
or definition of the same term in a document incorporated by reference, the
meaning or definition
assigned to that term in this document shall govern.
While particular embodiments of the present invention have been illustrated
and
described, it would be obvious to those skilled in the art that various other
changes and
modifications can be made without departing from the spirit and scope of the
invention. It is
therefore intended to cover in the appended claims all such changes and
modifications that are
within the scope of this invention.
