(Table & Formula Not Copy)

FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
&
THE PATENTS RULES, 2003
COMPLETE SPECIFICATION
(See section 10 and rule 13)
1. Title of the Invention
COMPOSITION COMPRISING TWO ANIONIC SURFACTANTS, A NONIONIC SURFACTANT, AN
AMPHOTERIC SURFACTANT, AND A DIRECT DYE
2. Applicant(s)
Name Nationality Address
L'OREAL French 14, rue Royale 75008 Paris, France
3. Preamble to the description
The following specification particularly describes the invention and the manner in which it is to be performed
2
5 The present invention relates to a composition for the cosmetic treatment of keratin fibres, in particular of human keratin fibres such as the hair, comprising at least
two different anionic surfactants, at least one nonionic surfactant, at least one amphoteric surfactant and at least one direct dye. The invention also relates to a
cosmetic process for treating keratin fibres using such a composition and also to a
10 use of said composition.
It is known practice to dye keratin fibres by direct dyeing or semi-permanent dyeing. Direct dyeing or semi-permanent dyeing consists in introducing the colour via
a coloured molecule which becomes adsorbed at the surface of the individual hair
15 or which penetrates into the individual hair. Thus, the process conventionally used
in direct dyeing consists in applying to keratin fibres direct dyes, which are coloured and colouring molecules that have affinity for the fibres, leaving the fibres in
contact with the colouring molecules and then rinsing the fibres. Generally, this
technique leads to chromatic colourings.
20
These dyeing hair compositions do, admittedly, have good dyeing power, but the
cosmetic properties thereby imparted still remain to be improved, especially when
they are applied to sensitized hair, i.e. hair that is generally damaged or embrittled
by the action of external atmospheric agents, such as light and bad weather,
25 and/or mechanical or chemical treatments, such as brushing, combing, dyeing,
bleaching, permanent waving and/or relaxing.
Thus, it is often common practice to resort to care compositions using complementary cosmetic agents known as conditioning agents in order to improve the cosmetic properties of sensitized hair. These conditioning agents may, of course, also
30 improve the cosmetic behaviour of natural hair.
However, these hair dyeing compositions are not necessarily entirely satisfactory
and can still be improved, especially as regards the deposition of direct dyes onto
keratin fibres.
35 Moreover, the hair compositions of the prior art are not entirely satisfactory either
as regards the working qualities (speed of start of foaming and foam abundance,
but also easy distribution of the composition and good rinseability) or as regards
the persistence with respect to various external agents (for example shampoos,
light, pollution).
40
There is thus a real need to develop hair dye compositions which have good dyeing properties, which are also capable of cleansing and/or conditioning keratin fibres and of giving the hair improved cosmetic properties, after one or more applications, without making the head of hair charged or lank, while at the same time
45 maintaining good washing power, especially good foaming power (abundant foam,
generated rapidly) and satisfactory working qualities (ease of spreading of the
composition on the hair, especially on wet hair, and good rinseability).
3
5
This aim is achieved by the present invention, one subject of which is especially a
cosmetic composition, preferably a hair composition, which is especially intended
for the cosmetic treatment of keratin fibres, in particular of human keratin fibres
such as the hair, comprising:
10 (i) one or more anionic surfactants chosen from polyoxyalkylenated alkyl(amido)ether carboxylic acids and/or salts thereof;
(ii) one or more anionic surfactants other than the polyoxyalkylenated alkyl(amido)ether carboxylic acid anionic surfactants (i);
(iii) one or more nonionic surfactants;
15 (iv) one or more amphoteric surfactants; and
(v) one or more direct dyes.
It was found that the composition according to the invention has satisfactory foaming power. It allows the production of an abundant, rapidly-generated foam, which
20 spreads easily on keratin fibres and is easy to remove on rinsing.
Certain users of dye compositions may have more or less sensitized hair, i.e. hair
that is damaged or embrittled by the action of external atmospheric agents such as
light and bad weather, and/or the action of mechanical or chemical treatments
such as brushing, combing, dyeing, bleaching, permanent-waving and/or relaxing.
25 Thus, the composition according to the invention also makes it possible to improve
the cosmetic properties imparted to the keratin fibres, especially to the hair, preferably sensitized hair. In particular, the composition according to the invention
makes it possible to improve the disentangling, the suppleness and also the feel of
the hair, without a build-up effect.
30 Moreover, the compositions according to the invention have a sparingly aggressive
nature, since their application to the hair fibre in the long run causes little damage
associated in particular with the gradual removal of the lipids or proteins contained
in or at the surface of said fibre.
In addition, the composition according to the invention allows good deposition, or
35 even good penetration, of direct dyes on/in keratin fibres and thus makes it possible to obtain improved dyeing action.
Furthermore, the composition according to the invention may impart cosmetic
properties that are shampoo-resistant.
40 The composition according to the invention also has the advantage of being stable
on storage both at room temperature (20-25°C) and at 45°C, especially as regards
its visual aspect and/or its viscosity.
For the purposes of the present invention, the term "stable" refers to a composition
which, after two months of storage, shows no change in appearance, colour,
45 odour, pH or viscosity.
In the text hereinbelow, and unless otherwise indicated, the limits of a range of
4
5 values are included within that range, especially in the expressions “between” and
“ranging from ... to ...”.
Moreover, the expression "at least one" used in the present description is equivalent to the expression "one or more", and may be replaced therewith.
10 Anionic surfactants
As indicated above, the composition according to the invention comprises at least
one anionic surfactant of polyoxyalkylenated alkyl(amido)ether carboxylic acid type
(i) and at least one anionic surfactant (ii) other than the anionic surfactant(s) (i).
Thus, for the purposes of the invention, the cosmetic composition comprises at
15 least two different anionic surfactants.
The term "anionic surfactant" means a surfactant comprising, as ionic or ionizable
groups, only anionic groups.
In the present description, a species is termed "anionic" when it bears at least one
permanent negative charge or when it can be ionized into a negatively charged
20 species, under the conditions of use of the composition of the invention (for example the medium or the pH) and not comprising any cationic charge.
Polyoxyalkylenated alkyl(amido)ether carboxylic acids (i)
The composition of the invention contains at least one anionic surfactant chosen
25 from polyoxyalkylenated alkyl(amido)ether carboxylic acids and salts thereof, in
particular those comprising from 2 to 50 alkylene oxide and in particular ethylene
oxide groups.
The polyoxyalkylenatedalkyl(amido)ether carboxylic acids that may be used are
30 preferably chosen from those of formula (1):
in which:
- R1 represents a linear or branched C6-C24 alkyl or alkenyl radical, an alkyl(C8-
35 C9)phenyl radical, a radical R2CONH-CH2-CH2- with R2 denoting a linear or
branched C9-C21 alkyl or alkenyl radical,
preferably R1 is a C8-C20 and preferably C8-C18 alkyl radical,
- n is an integer or decimal number (average value) ranging from 2 to 24 and preferably from 2 to 10,
40 - A denotes H, ammonium, Na, K, Li, Mg, Ca or a monoethanolamine or triethanolamine residue.
It is also possible to use mixtures of compounds of formula (1), in particular mixtures of compounds containing different groups R1.
45 The polyoxyalkylenated alkyl(amido)ether carboxylic acids that are particularly preferred are those of formula (1) in which:
- R1 denotes a C12-C14 alkyl, cocoyl, oleyl, nonylphenyl or octylphenyl radical,
R1
(OC2H4
)n
OCH2COOA (1)
5
5 - A denotes a hydrogen or sodium atom, and
- n ranges from 2 to 20, preferably from 2 to 10.
Even more preferentially, use is made of compounds of formula (1) in which R1
denotes a C12 alkyl radical, A denotes a hydrogen or sodium atom and n ranges
from 2 to 10.
10
Use is preferably made of polyoxyalkylenated (C6-C24)alkyl ether carboxylic acids
and salts thereof, polyoxyalkylenated (C6-C24)alkylamido ether carboxylic acids, in
particular those comprising from 2 to 15 alkylene oxide groups, salts thereof, and
mixtures thereof.
15 When the anionic surfactant is in salt form, said salt may be chosen from alkali
metal salts, such as the sodium or potassium salt, ammonium salts, amine salts
and in particular amino alcohol salts, and alkaline-earth metal salts, such as the
magnesium salt.
Examples of amino alcohol salts that may be mentioned include monoethanola20 mine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2-methyl-1-propanol salts, 2-
amino-2-methyl-1,3-propanediol salts and tris(hydroxymethyl)aminomethane salts.
Alkali metal or alkaline-earth metal salts and in particular the sodium or magnesium salts are preferably used.
25
Among the commercial products that may preferably be used are the products sold
by the company KAO under the names:
Akypo® NP 70 (R1 = nonylphenyl, n = 7, A = H)
Akypo® NP 40 (R1 = nonylphenyl, n = 4, A = H)
30 Akypo® OP 40 (R1 = octylphenyl, n = 4, A = H)
Akypo® OP 80 (R1 = octylphenyl, n = 8, A = H)
Akypo® OP 190 (R1 = octylphenyl, n = 19, A = H)
Akypo® RLM 38 (R1 = (C12-C14)alkyl, n = 4, A = H)
Akypo® RLM 38 NV (R1 = (C12-C14)alkyl, n = 4, A = Na)
35 Akypo® RLM 45 CA (R1 = (C12-C14)alkyl, n = 4.5, A = H)
Akypo® RLM 45 NV (R1 = (C12-C14)alkyl, n = 4.5, A = Na)
Akypo® RLM 100 (R1 = (C12-C14)alkyl, n = 10, A = H)
Akypo® RLM 100 NV (R1 = (C12-C14)alkyl, n = 10, A = Na)
Akypo® RLM 130 (R1 = (C12-C14)alkyl, n = 13, A = H)
40 Akypo® RLM 160 NV (R1 = (C12-C14)alkyl, n = 16, A = Na)
or by the company Sandoz under the names:
Sandopan DTC-Acid (R1 = (C13)alkyl, n = 6, A = H)
Sandopan DTC (R1 = (C13)alkyl, n = 6, A = Na)
Sandopan LS 24 (R1 = (C12-C14)alkyl, n = 12, A = Na)
45 Sandopan JA 36 (R1 = (C13)alkyl, n = 18, A = H),
and more particularly the products sold under the following names:
Akypo® RLM 45 (INCI: Laureth-5 carboxylic acid)
6
5 Akypo® RLM 100
Akypo® RLM 38.
The composition according to the invention preferably comprises said polyoxyalkylenated alkyl(amido)ether carboxylic acid(s) and/or salts thereof in a total
10 amount ranging from 0.05% to 30% by weight, preferably from 0.1% to 25% by
weight, better still from 0.5% to 20% by weight and preferentially from 1% to 10%
by weight, relative to the total weight of the composition.
Additional anionic surfactants (ii)
15 As indicated above, the composition according to the invention comprises at least
one additional anionic surfactant other than the polyoxyalkylenated alkyl(amido)ether carboxylic acids and/or salts thereof (i) described above.
Preferably, the additional anionic surfactants (ii) used in the composition according
20 to the invention are chosen from anionic surfactants comprising in their structure
one or more sulfate and/or sulfonate and/or phosphate and/or carboxylate groups,
and/or mixtures thereof, preferably sulfate groups.
The anionic surfactant(s) (ii) may be oxyethylenated and/or oxypropylenated. The
total average number of ethylene oxide (EO) and/or propylene oxide (PO) groups
25 may then range from 1 to 50 and especially from 1 to 10.
The carboxylic anionic surfactants that may be used thus comprise at least one
carboxylic or carboxylate function.
They may be chosen from the following compounds: acylglycinates, acyllactylates,
30 acylsarcosinates, acylglutamates; alkyl-D-galactoside uronic acids; and also the
salts of these compounds;
the alkyl and/or acyl groups of these compounds comprising from 6 to 30 carbon
atoms, especially from 12 to 28, better still from 14 to 24 or even from 16 to 22
carbon atoms; these compounds possibly being polyoxyalkylenated, especially
35 polyoxyethylenated, and then preferably comprise from 1 to 50 ethylene oxide
units, better still from 1 to 10 ethylene oxide units.
Use may also be made of the C6-C24 alkyl monoesters of polyglycosidepolycarboxylic acids, such as C6-C24 alkyl polyglycoside-citrates, C6-C24 alkyl
40 polyglycoside-tartrates and C6-C24 alkyl polyglycoside-sulfosuccinates, and salts
thereof.
Preferentially, the carboxylic anionic surfactants are chosen, alone or as a mixture,
from:
45 - acylglutamates, especially of C6-C24 or even C12-C20, such as stearoylglutamates, and in particular disodium stearoylglutamate;
- acylsarcosinates, in particular of C6-C24 or even C12-C20, such as palmitoylsar-
7
5 cosinates, and in particular sodium palmitoylsarcosinate;
- acyllactylates, in particular of C12-C28 or even C14-C24, such as behenoyllactylates, and in particular sodium behenoyllactylate;
- C6-C24 and in particular C12-C20 acylglycinates;
in particular in the form of alkali metal or alkaline-earth metal, ammonium or amino
10 alcohol salts.
The sulfonate anionic surfactants that may be used comprise at least one sulfonate function.
They may be chosen from the following compounds: alkylsulfonates, alkyla15 midesulfonates, alkylarylsulfonates, α-olefinsulfonates, paraffin sulfonates, alkylsulfosuccinates, alkyl ether sulfosuccinates, alkylamidesulfosuccinates, alkylsulfoacetates, N-acyltaurates, acylisethionates; alkylsulfolaurates; and also the
salts of these compounds;
the alkyl groups of these compounds comprising from 6 to 30 carbon atoms, in
20 particular from 12 to 28, better still from 14 to 24 or even from 16 to 22 carbon atoms; where the aryl group preferably denotes a phenyl or benzyl group;
these compounds possibly being polyoxyalkylenated, in particular polyoxyethylenated, and then preferably comprising from 1 to 50 ethylene oxide units and better
still from 2 to 10 ethylene oxide units.
25
Preferentially, the sulfonate anionic surfactants are chosen, alone or as a mixture,
from:
- C6-C24 and in particular C12-C20 alkylsulfosuccinates, in particular laurylsulfosuccinates;
30 - C6-C24 and in particular C12-C20 alkyl ether sulfosuccinates;
- (C6-C24)acylisethionates and preferably (C12-C18)acylisethionates;
in particular in the form of alkali metal or alkaline-earth metal, ammonium or amino
alcohol salts.
35 The sulfate anionic surfactants that may be used comprise at least one sulfate
function.
They may be chosen from the following compounds: alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates; and the salts of these compounds;
40 the alkyl groups of these compounds comprising from 6 to 30 carbon atoms, in
particular from 12 to 28, better still from 14 to 24 or even from 16 to 22 carbon atoms; where the aryl group preferably denotes a phenyl or benzyl group;
these compounds possibly being polyoxyalkylenated, in particular polyoxyethylenated, and then preferably comprising from 1 to 50 ethylene oxide units and better
45 still from 2 to 10 ethylene oxide units.
Preferentially, the sulfate anionic surfactants are chosen, alone or as a mixture,
8
5 from:
- alkyl sulfates, in particular of C6-C24 or even C12-C20,
- alkyl ether sulfates, in particular of C6-C24 or even C12-C20, preferably comprising from 2 to 20 ethylene oxide units;
in particular in the form of alkali metal or alkaline-earth metal, ammonium or amino
10 alcohol salts.
When the anionic surfactant is in salt form, said salt may be chosen from alkali
metal salts, such as the sodium or potassium salt, ammonium salts, amine salts
and in particular amino alcohol salts, and alkaline-earth metal salts, such as the
15 magnesium or calcium salt.
Examples of amino alcohol salts that may be mentioned include monoethanolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2-methyl-1-propanol salts, 2-
amino-2-methyl-1,3-propanediol salts and tris(hydroxymethyl)aminomethane salts.
20 Alkali metal or alkaline-earth metal salts and in particular the sodium or magnesium salts are preferably used.
Preferentially, the additional anionic surfactants (ii) are chosen, alone or as a mixture, from:
25 - C6-C24 and in particular C12-C20 alkyl sulfates;
- C6-C24 and in particular C12-C20 alkyl ether sulfates; preferably comprising from 2
to 20 ethylene oxide units;
- C6-C24 and in particular C12-C20 alkylsulfosuccinates, in particular laurylsulfosuccinates;
30 - C6-C24 and in particular C12-C20 alkyl ether sulfosuccinates;
- (C6-C24)acylisethionates and preferably (C12-C18)acylisethionates;
- C6-C24 and in particular C12-C20 acylsarcosinates; in particular palmitoylsarcosinates;
- C6-C24 and in particular C12-C20 acylglutamates;
35 - C6-C24 and in particular C12-C20 acylglycinates;
in particular in the form of alkali metal or alkaline-earth metal, ammonium or amino
alcohol salts.
Among the anionic surfactants (ii), use is preferably made of one or more sulfate
40 anionic surfactants, preferentially chosen from C8-C14 and more particularly C12-
C14 alkyl sulfates and alkyl ether sulfates, and more particularly lauryl (ether) sulfates.
Preferably, the anionic surfactant(s) (ii) are in the form of salts, and in particular
alkaline salts, especially sodium salts, ammonium salts, amine salts, including
45 amino alcohol salts, and/or magnesium salts. These salts preferably comprise
from 2 to 5 ethylene oxide groups.
9
5 Among these salts, sodium, triethanolamine, magnesium or ammonium (C12-
C14)alkyl sulfates and/or sodium, ammonium or magnesium (C12-C14)alkyl ether
sulfates, which are oxyethylenated, for example with 1 to 10 mol of ethylene oxide,
are more preferably used.
Better still, the anionic surfactant(s) (ii) are chosen from sodium, ammonium or
10 magnesium (C12-C14)alkyl ether sulfates oxyethylenated with 2.2 mol of ethylene
oxide, as sold under the name Texapon N702 by the company Cognis.
The anionic surfactant(s) (ii) may be present in the composition according to the
invention in a total content ranging from 0.05% to 30% by weight, preferably in a
15 content ranging from 0.1% to 25% by weight and better still from 0.5% to 20% by
weight, even better still from 1% to 15% by weight, relative to the total weight of
the composition.
According to a particular embodiment, the total content of anionic surfactants (i)
20 and (ii) in the composition according to the invention is between 0.1% and 35% by
weight, preferably between 1% and 25% by weight, and preferentially between 5%
and 15% by weight, relative to the total weight of the composition.
Nonionic surfactants (iii)
25 The composition comprises one or more nonionic surfactants, chosen from:
(a) oxyethylenated alcohols comprising at least one saturated or unsaturated, linear or branched C8 to C40 alkyl chain, and comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50 and more particularly from 2 to 40 mol of ethylene oxide and comprising one or two fatty chains;
30 (b) nonionic surfactants of alkyl(poly)glycoside type, represented especially by the
following general formula: R1O-(R2O)t-(G)v
in which:
- R1 represents a linear or branched alkyl or alkenyl radical comprising 6 to 24
carbon atoms and especially 8 to 18 carbon atoms, or an alkylphenyl radical
35 whose linear or branched alkyl radical comprises 6 to 24 carbon atoms and especially 8 to 18 carbon atoms,
- R2 represents an alkylene radical comprising 2 to 4 carbon atoms,
- G represents a sugar unit comprising 5 to 6 carbon atoms,
- t denotes a value ranging from 0 to 10 and preferably 0 to 4,
40 - v denotes a value ranging from 1 to 15 and preferably 1 to 4; and/or
(c ) polyethoxylated fatty acid esters of sorbitan, preferably containing from 2 to 40
mol of ethylene oxide and comprising at least one saturated or unsaturated, linear
or branched C8 to C40 alkyl chain, preferably C10-C28 alkyl chain (fatty acid);
(d) fatty acid esters of sucrose, preferably comprising at least one saturated or un45 saturated, linear or branched C8 to C40 alkyl chain, preferably C10-C28 alkyl
chain (fatty acid), such as sucrose cocoate and sucrose palmitate; and/or
(e ) polyglycerolated fatty esters, the number of glycerol groups possibly ranging
10
5 from 2 to 30 and comprising at least one saturated or unsaturated, linear or
branched C8 to C40 alkyl chain, preferably C10-C28 alkyl chain (fatty acid), such
as polyglyceryl-5 laurate, polyglyceryl-4 laurate, polyglyceryl-10 laurate, polyglyceryl-6 dicaprate.
10 Preferably, the alkyl(poly)glycoside surfactants are compounds of the formula described above in which:
- R1 denotes a linear or branched, saturated or unsaturated alkyl radical comprising from 8 to 18 carbon atoms,
- R2 represents an alkylene radical comprising 2 to 4 carbon atoms,
15 - t denotes a value ranging from 0 to 3 and preferably equal to 0,
- G denotes glucose, fructose or galactose, preferably glucose;
- the degree of polymerization, i.e. the value of v, possibly ranging from 1 to 15
and preferably from 1 to 4; the mean degree of polymerization more particularly
being between 1 and 2.
20 The glucoside bonds between the sugar units are generally of 1-6 or 1-4 type and
preferably of 1-4 type. Preferably, the alkyl(poly)glycoside surfactant is an alkyl(poly)glucoside surfactant. C8/C16 alkyl(poly)glucosides 1,4, and in particular
decyl glucosides and caprylyl/capryl glucosides, are most particularly preferred.
Among commercial products, mention may be made of the products sold by the
25 company Cognis under the names Plantaren® (600 CS/U, 1200 and 2000) or
Plantacare® (818, 1200 and 2000); the products sold by the company SEPPIC
under the names Oramix CG 110 and Oramix® NS 10; the products sold by the
company BASF under the name Lutensol GD 70, or else the products sold by the
company Chem Y under the name AG10 LK.
30 Preferably, use is made of C8/C16-alkyl (poly)glycosides 1,4, in particular as an
aqueous 53% solution, such as those sold by Cognis under the reference
Plantacare® 818 UP.
Preferentially, the nonionic surfactants are chosen, alone or as a mixture, from:
35 - saturated or unsaturated, linear or branched, oxyethylenated C8 to C40, especially
C8-C20 and better still C10-C18 fatty alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50, more particularly from 2 to 40 mol, or even
from 3 to 20 mol of ethylene oxide; especially lauryl alcohol containing 4 mol of
ethylene oxide (INCI name: Laureth-4) and lauryl alcohol containing 12 mol of eth40 ylene oxide (INCI name: Laureth-12); and
- (C6-C24 alkyl)(poly)glycosides, and more particularly (C8-C18 alkyl)(poly)glycosides.
Better still, the nonionic surfactants are preferentially chosen from oxyethylenated
alcohols comprising at least one C8-C20 and better still C10-C18 alkyl chain, com45 prising from 2 to 50 and in particular from 3 to 20 mol of ethylene oxide.
According to a preferred embodiment of the invention, the composition comprises
11
5 at least two nonionic surfactants chosen from oxyethylenated alcohols comprising
at least one C8-C20 and better still C10-C18 alkyl chain, comprising from 2 to 50 and
in particular from 3 to 20 mol of ethylene oxide and (C6-C24 alkyl)(poly)glycosides,
and more particularly (C8-C18 alkyl)(poly)glycosides.
10 Preferably, the nonionic surfactant(s) are present in the composition according to
the invention in a total content ranging from 0.05% to 30% by weight, preferentially
ranging from 0.1% to 25% by weight, in particular ranging from 0.5% to 20% by
weight, especially from 1% to 15% by weight and better still from 2% to 10% by
weight, relative to the total weight of the composition.
15
Amphoteric surfactants (iv)
As indicated above, the composition comprises one or more amphoteric surfactants, preferably present in a total content of greater than or equal to 3% by weight
relative to the total weight of the composition.
20 In particular, the amphoteric or zwitterionic surfactant(s) are non-silicone surfactants. They may especially be optionally quaternized secondary or tertiary aliphatic
amine derivatives, in which the aliphatic group is a linear or branched chain comprising from 8 to 22 carbon atoms, said amine derivatives containing at least one
anionic group, for instance a carboxylate, sulfonate, sulfate, phosphate or phos25 phonate group.
Mention may in particular be made of (C8-C20)alkylbetaines, (C8-
C20)alkylsulfobetaines, (C8-C20)alkylamido(C3-C8)alkylbetaines and (C8-
C20)alkylamido(C6-C8)alkylsulfobetaines.
30
Among the optionally quaternized derivatives of secondary or tertiary aliphatic
amines that may be used, as defined above, mention may also be made of the
compounds having the respective structures (II) and (III) below:
Ra-CONHCH2CH2-N
+
(Rb)(Rc)-CH2COO-
, M+
, X35 (II)
in which:
- Ra represents a C10 to C30 alkyl or alkenyl group derived from an acid RaCOOH
preferably present in hydrolysed coconut oil, or a heptyl, nonyl or undecyl group;
- Rb represents a beta-hydroxyethyl group; and
40 - Rc represents a carboxymethyl group;
- M
+
represents a cationic counterion derived from an alkali metal or alkaline-earth
metal, such as sodium, an ammonium ion or an ion derived from an organic
amine; and
- X
-
represents an organic or mineral anionic counterion, such as that chosen from
45 halides, acetates, phosphates, nitrates, (C1-C4)alkyl sulfates, (C1-C4)alkyl- or (C1-
C4)alkylarylsulfonates, in particular methyl sulfate and ethyl sulfate; or alternatively
M
+
and Xare absent;
12
5
Ra'-CONHCH2CH2-N(B)(B') (III)
in which:
- B represents the group -CH2CH2OX';
- B' represents the group -(CH2)zY', with z = 1 or 2;
10 - X' represents the group -CH2COOH, -CH2-COOZ’, -CH2CH2COOH or -CH2CH2-
COOZ’, or a hydrogen atom;
- Y' represents the group -COOH, -COOZ' or -CH2-CH(OH)SO3H or the group
CH2CH(OH)SO3-Z';
- Z' represents a cationic counterion resulting from an alkali metal or alkaline-earth
15 metal, such as sodium, an ammonium ion or an ion resulting from an organic
amine;
- Ra’ represents a C10 to C30 alkyl or alkenyl group of an acid Ra’-COOH which is
preferably present in coconut oil or in hydrolysed linseed oil, or an alkyl group, especially a C17 group, and its iso form, or an unsaturated C17 group.
20
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 caprylamphodi25 propionate, disodium capryloamphodipropionate, lauroamphodipropionic acid and
cocoamphodipropionic acid.
By way of example, mention may be made of the cocoamphodiacetate sold by the
company Rhodia under the trade name Miranol® C2M Concentrate.
30 Use may also be made of compounds of formula (IV):
Ra''-NHCH(Y'')-(CH2)nCONH(CH2)n'-N(Rd)(Re) (IV)
in which:
- Y'' represents the group -COOH, -COOZ'' or -CH2-CH(OH)SO3H or the group
35 CH2CH(OH)SO3-Z'';
- Rd and Re represent, independently of each other, a C1 to C4 alkyl or hydroxyalkyl
radical;
- Z’’ represents a cationic counterion derived from an alkali metal or alkaline-earth
metal, such as sodium, an ammonium ion or an ion derived from an organic
40 amine;
- Ra'' represents a C10 to C30 alkyl or alkenyl group of an acid Ra''-COOH which is
preferably present in coconut oil or in hydrolysed linseed oil;
- n and n' denote, independently of each other, an integer ranging from 1 to 3.
Mention may be made, among the compounds of formula (II), of the compound
45 classified in the CTFA dictionary under the name sodium diethylaminopropyl cocoaspartamide and sold by Chimex under the name Chimexane HB.
These compounds may be used alone or as mixtures.
13
5
Among the amphoteric or zwitterionic surfactants, use is preferably made of (C8-
C20)alkylbetaines such as cocoylbetaine, (C8-C20)alkylamido(C3-C8)alkylbetaines
such as cocamidopropylbetaine, and mixtures thereof, and the compounds of formula (IV) such as the sodium salt of diethylaminopropyl laurylaminosuccinamate
10 (INCI name: sodium diethylaminopropyl cocoaspartamide).
Preferentially, the amphoteric or zwitterionic surfactants are chosen from (C8-
C20)alkylamido(C3-C8)alkylbetaines such as cocamidopropylbetaine.
Preferably, the amphoteric surfactant(s) are present in the composition according
to the invention in a total content ranging from 0.1% to 25% by weight, preferential15 ly in a content ranging from 1% to 20% by weight, especially from 3% to 15% by
weight and better still from 3.5% to 10% by weight, relative to the total weight of
the composition.
Direct dyes
20 The direct dyes that may be used in the compositions according to the invention
are preferably chosen, alone or as a mixture, from synthetic or natural, anionic,
cationic or nonionic direct dyes.
Examples of suitable direct dyes that may be mentioned include azo direct dyes;
25 (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes;
azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes;
phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures.
Among the cationic direct dyes that may be used according to the invention, men30 tion may be made of the hydrazono cationic dyes of formulae (IIIa) and (III’a), the
azo cationic dyes (IVa) and (IV’a) and the diazo cationic dyes (Va) below:
Het+
-C(Ra
)=N-N(Rb
)-Ar,
An-
(IIIa)
Het+
-N(Ra
)-N=C(Rb
)-Ar, An-
(III'a)
Het+
-N=N-Ar, An-
(IVa)
Ar+
-N=N-Ar'', An-
(IV'a)
and Het+
-N=N-Ar'-N=N-Ar,
An-
(Va)
in which:
• Het+
35 represents a cationic heteroaryl radical, preferably bearing an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, optionally substituted preferably with one or more (C1-C8)alkyl groups such as methyl;
• Ar+
represents an aryl radical, such as phenyl or naphthyl, bearing an exocyclic cationic charge, preferably ammonium, particularly tri(C1-C8)alkylammonium
40 such as trimethylammonium;
14
5 • Ar represents an aryl group, especially phenyl, which is optionally substituted, preferably with one or more electron-donating groups such as i) optionally substituted (C1-C8)alkyl, ii) optionally substituted (C1-C8)alkoxy, iii) (di)(C1-
C8)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group,
iv) aryl(C1-C8)alkylamino, v) optionally substituted N-(C1-C8)alkyl-N-aryl(C1-
10 C8)alkylamino or, as a variant, Ar represents a julolidine group;
• Ar’ represents an optionally substituted divalent (hetero)arylene group such
as phenylene, particularly para-phenylene, or naphthalene, which is optionally
substituted, preferably with one or more (C1-C8)alkyl, hydroxyl or (C1-C8)alkoxy
groups;
15 • Ar’’ represents an optionally substituted (hetero)aryl group such as phenyl
or pyrazolyl, which is optionally substituted, preferably with one or more (C1-
C8)alkyl, hydroxyl, (di)(C1-C8)(alkyl)amino, (C1-C8)alkoxy or phenyl groups;
• R
a
and Rb
, which may be identical or different, represent a hydrogen atom
or a (C1-C8)alkyl group, which is optionally substituted, preferably with a hydroxyl
20 group;
or, as a variant, the substituent Ra with a substituent of Het+
and/or Rb with a substituent of Ar and/or Ra with Rb
form, together with the atoms that bear them, a
(hetero)cycloalkyl;
particularly, Ra
and Rb
represent a hydrogen atom or a (C1-C4)alkyl group, which is
25 optionally substituted with a hydroxyl group;
• Anrepresents an anionic counterion, such as mesylate or halide.
Mention may be made in particular of azo and hydrazono cationic dyes bearing an
endocyclic cationic charge of formulae (IIIa), (III’a) and (IVa) as defined previously.
More particularly those of formulae (IIIa), (III’a) and (IVa) derived from the dyes
30 described in patent applications WO 95/15144, WO 95/01772 and EP-714954.
Preferably, the cationic part is derived from the following derivatives:
, An-
, An-
(IIIa-1) (IVa-1)
in which:
- R
1
35 , which may be identical different, represents a (C1-C4)alkyl group such as methyl;
- R
2
and R3
, which may be identical or different, represent a hydrogen atom or a
(C1-C4)alkyl group, such as methyl; and
- R
4
represents a hydrogen atom or an electron-donating group such as optionally
40 substituted (C1-C8)alkyl, optionally substituted (C1-C8)alkoxy, or (di)(C1-
C
H
R N
1 N N
R
2
R
4
+
N N N
R
3
R
2 N
N
R
1
R
1
z
+
15
5 C8)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group;
in particular, R4
represents a hydrogen atom;
- Z represents a CH group or a nitrogen atom, preferably CH;
- Anrepresents an anionic counterion, such as mesylate or halide.
10 In particular, the dye of formulae (IIIa-1) and (IVa-1) is chosen from Basic Red 51,
Basic Yellow 87 and Basic Orange 31 or corresponding derivatives:
AnAnAnBasic Red 51 Basic Orange 31 Basic Yellow 87
Among the natural direct dyes that may be used according to the invention, men15 tion may be made of hennotannic acid, juglone, alizarin, purpurin, carminic acid,
kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orcein. Extracts or decoctions containing these natural dyes
and in particular henna-based poultices or extracts may also be used.
20 Preferentially, the direct dyes according to the invention are chosen, alone or as a
mixture, from anionic direct dyes.
The anionic direct dyes of the invention are dyes commonly referred to as "acid
direct dyes" owing to their affinity for alkaline substances. The term "anionic direct
dyes" means any direct dye comprising in its structure at least one CO2R or SO3R
25 substituent with R denoting a hydrogen atom or a cation originating from a metal or
an amine, or an ammonium ion. The anionic dyes may be chosen from direct nitro
acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine
acid dyes, anthraquinone acid dyes, indigoid dyes and natural acid dyes.
30 As acid dyes according to the invention, mention may be made of the dyes of formulae (II), (II’), (III), (III’), (IV), (IV’), (V), (V’), (VI), (VII), (VIII) and (IX) below:
a) the diaryl anionic azo dyes of formula (II) or (II'):
N
N
N
H3C
CH3
N
N
H3C
CH3
+
N
N
NH2
N
N
H3C
CH3
+
CH
N
H3C
N
N
H3C
+
16
N
N
R9
R7
R'
7
R'
9
R8
R'
8
R10
R'
10
(II)
A
B
5
R9
R7
R'
7
R8
R10
N
N
N
N
W
R9
R7
R'
7
R8
R10
A A
(II') C C
in which formulae (II) and (II'):
 R7, R8, R9, R10, R’7, R’8, R’9 and R’10, which may be identical or different,
represent a hydrogen atom or a group chosen from:
10 - alkyl;
- alkoxy, alkylthio;
- hydroxyl, mercapto;
- nitro, nitroso;
- R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X’’- with R° representing a hydrogen
15 atom or an alkyl or aryl group; X, X’ and X’’, which may be identical or different,
representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom
or an alkyl group;
- (O)2S(O-
)-, M+ with M+
representing a hydrogen atom or a cationic counterion;
- (O)CO-
-, M+ with M+
20 as defined previously;
- R’’-S(O)2-, with R’’ representing a hydrogen atom or an alkyl, aryl,
(di)(alkyl)amino or aryl(alkyl)amino group; preferentially a phenylamino or phenyl
group;
- R’’’-S(O)2-X’- with R’’’ representing an alkyl or optionally substituted aryl
25 group, X’ as defined previously;
- (di)(alkyl)amino;
- aryl(alkyl)amino optionally substituted with one or more groups chosen
from i) nitro; ii) nitroso; iii) (O)2S(O-
)-, M+
and iv) alkoxy with M+
as defined previously;
30 - optionally substituted heteroaryl; preferentially a benzothiazolyl group;
- cycloalkyl; especially cyclohexyl;
- Ar-N=N- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl, (O)2S(O-
)-, M+
or
phenylamino groups;
35 - or alternatively two contiguous groups R7 with R8 or R8 with R9 or R9 with
R10 together form a fused benzo group A’; and R'7 with R'8 or R'8 with R'9 or R'9 with
17
5 R'10 together form a fused benzo group B’; with A’ and B’ optionally substituted with
one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O-
)-, M+
; iv) hydroxyl;
v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X’-; viii) R°-X’-C(X)-; ix) R°-X’-C(X)-
X’’-; x) Ar-N=N- and xi) optionally substituted aryl(alkyl)amino; with M+
, R°, X, X’, X’’
and Ar as defined previously;
10  W represents a sigma bond, an oxygen or sulfur atom, or a divalent radical i)
–NR- with R as defined previously, or ii) methylene -C(Ra)(Rb)- with Ra and Rb,
which may be identical or different, representing a hydrogen atom or an aryl group,
or alternatively Ra and Rb form, with the carbon atom that bears them, a spiro cycloalkyl; preferentially, W represents a sulfur atom or Ra and Rb together form a
15 cyclohexyl;
it being understood that formulae (II) and (II’) comprise at least one sulfonate radical (O)2S(O-
)-, M+
or one carboxylate radical (O)CO-
-, M+
on one of the rings A, A',
B, B' or C; preferentially sodium sulfonate.
20 Among the dyes of formula (II) that may be mentioned are: Acid Red 1, Acid Red 4,
Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32,
Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42,
Acid Red 44, Pigment red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red
138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid
25 Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3, Acid Violet 7, Acid Violet
14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid
Black 26, Acid Black 52, Food Black 1, Food Black 2, Food yellow 3 or sunset yellow.
30 Among the dyes of formula (II’) that may be mentioned are: Acid Red 111, Acid
Red 134, Acid Yellow 38;
b) the pyrazolone anionic azo dyes of formulae (III) and (III'):
R11
R12
R13
N
N
N
N
Y
R14
R20 R19
R15
R16
R18
R R17
'
16
R'
20
R'
19
E (III)
D
18
R11
R12
R13
N
N
N
N
Y
R14
N
N
N
N
Y
R14
Ra Rb
R11
R12
R13
R21 R21
(III')
D D
F F
5
in which formulae (III) and (III'):
 R11, R12 and R13, which may be identical or different, represent a hydrogen
or halogen atom, an alkyl group or -(O)2S(O-
), M+ with M+
as defined previously;
 R14 represents a hydrogen atom, an alkyl group or a group -C(O)O-, M+ with
M
+ 10 as defined previously;
 R15 represents a hydrogen atom;
 R16 represents an oxo group, in which case R’16 is absent, or alternatively
R15 with R16 together form a double bond;
- R17 and R18, which may be identical or different, represent a hydrogen
atom, a group chosen from i) (O)2S(O-
)-, M
+ with M+
15 as defined previously, and ii)
Ar-O-S(O)2- with Ar representing an optionally substituted aryl group; preferentially
a phenyl optionally substituted with one or more alkyl groups;
 R19 and R20 together form either a double bond, or a benzo group D’, which
is optionally substituted;
20  R’16, R’19 and R’20, which may be identical or different, represent a hydrogen
atom or an alkyl or hydroxyl group;
 R21 represents a hydrogen atom or an alkyl or alkoxy group;
 Ra and Ra, which may be identical or different, are as defined previously,
preferentially Ra represents a hydrogen atom and Rb represents an aryl group;
25  Y represents either a hydroxyl group or an oxo group;
 represents a single bond when Y is an oxo group; and represents a
double bond when Y represents a hydroxyl group;
it being understood that formulae (III) and (III’) comprise at least one sulfonate radical (O)2S(O-
)-, M+
or one carboxylate radical C(O)O-
-, M
+
on one of the rings D or
30 E; preferentially sodium sulfonate;
Among the dyes of formula (III) that may be mentioned are: Acid Red 195, Acid
Yellow 23, Acid Yellow 27, Acid Yellow 76, and as examples of dyes of formula
(III'), mention may be made of: Acid Yellow 17;
35
c) the anthraquinone dyes of formulae (IV) and (IV'):
19 O
O N
R26
R27
R22
R23
R24
R25
O
O
N
R26
R27
R22
R23
R24
R25
R28
O
O
R26
R27
R22
R23
R24
R25
Z
(IV)
Z
Z
(IV')
Z'
5
in which formulae (IV) and (IV'):
 R22, R23, R24, R25, R26 and R27, which may be identical or different, represent
a hydrogen or halogen atom, or a group chosen from:
- alkyl;
10 - hydroxyl, mercapto;
- alkoxy, alkylthio;
- optionally substituted aryloxy or arylthio, preferentially substituted with
one or more groups chosen from alkyl and (O)2S(O-
)-, M+ with M+
as defined previously;
15 - aryl(alkyl)amino optionally substituted with one or more groups chosen
from alkyl and (O)2S(O-
)-, M+ with M+
as defined previously;
- (di)(alkyl)amino;
- (di)(hydroxyalkyl)amino;
- (O)2S(O-
)-, M+ with M+
as defined previously;
20  Z’ represents a hydrogen atom or a group NR28R29 with R28 and R29, which
may be identical or different, representing a hydrogen atom or a group chosen
from:
- alkyl;
- polyhydroxyalkyl such as hydroxyethyl;
25 - aryl optionally substituted with one or more groups, particularly i) alkyl
such as methyl, n-dodecyl, n-butyl; ii) (O)2S(O-
)-, M+ with M+
as defined previously;
iii) R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X’’- with R°, X, X’ and X’’ as defined previously, preferentially R° represents an alkyl group;
- cycloalkyl; especially cyclohexyl;
30  Z, represents a group chosen from hydroxyl and NR’28R’29 with R’28 and R’29,
which may be identical or different, representing the same atoms or groups as R28
and R29 as defined previously;
it being understood that formulae (IV) and (IV’) comprise at least one sulfonate radical (O)2S(O-
)-, M+
or one carboxylate radical -C(O)O-
-, M+
; preferentially sodium
35 sulfonate;
20
5 Among the dyes of formula (IV) that may be mentioned are: Acid Blue 25, Acid
Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140,
Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT violet No. 2; and, as an example of a dye of formula (IV'), mention may be made of: Acid Black 48;
10
d) the nitro dyes of formulae (V) and (V’):
(R30
)
p
N N
Rc
Rd
O2N
J
SO3
-
R31
n
M'
R32
(V) (R30
)
q
M'
u
ALK SO3
- W
NO2
(V')
in which formulae (V) and (V'):
15  R30, R31 and R32, which may be identical or different, represent a hydrogen
or halogen atom, or a group chosen from:
- alkyl;
- alkoxy optionally substituted with one or more hydroxyl groups, alkylthio
optionally substituted with one or more hydroxyl groups;
20 - hydroxyl, mercapto;
- nitro, nitroso;
- polyhaloalkyl;
- R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X’’- with R°, X, X’ and X’’ as defined
previously;
- (O)2S(O-
)-, M+ with M+
25 as defined previously;
- (O)CO-
-, M+ with M+ as defined previously;
- (di)(alkyl)amino;
- (di)(hydroxyalkyl)amino;
- heterocycloalkyl such as piperidino, piperazino or morpholino;
30 in particular, R30, R31 and R32 represent a hydrogen atom;
 Rc and Rd, which may be identical or different, represent a hydrogen atom or
an alkyl group;
 W is as defined previously; W particularly represents a group –NH–;
 ALK represents a linear or branched divalent C1-C6 alkylene group; in par35 ticular, ALK represents a group -CH2-CH2-;
21
5  n is 1 or 2;
 p represents an integer between 1 and 5 inclusive;
 q represents an integer between 1 and 4 inclusive;
 u is 0 or 1;
 when n is 1, J represents a nitro or nitroso group; particularly nitro;
10  when n is 2, J represents an oxygen or sulfur atom, or a divalent radical –
S(O)m– with m representing an integer 1 or 2; preferentially, J represents a radical
–SO2–;
 M’ represents a hydrogen atom or a cationic counterion;
15 
when it is present, represents a benzo group optionally substituted with one
or more groups R30 as defined previously;
it being understood that formulae (V) and (V’) comprise at least one sulfonate radical (O)2S(O-
)-, M+
or one carboxylate radical -C(O)O-
-, M+
20 ; preferentially sodium
sulfonate;
As dyes of formula (V), mention may be made of: Acid Brown 13 and Acid Orange
3; as examples of dyes of formula (V'), mention may be made of: Acid Yellow 1,
25 the sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidino-5-
nitrobenzenesulfonic acid, 2(4'-N,N(2"-hydroxyethyl)amino-2'-
nitro)anilineethanesulfonic acid, 4--hydroxyethylamino-3-nitrobenzenesulfonic
acid; EXT D&C Yellow 7;
30 e) the triarylmethane dyes of formula (VI):
N
+
N
R36
R33
R35
R34
R37
R38
R39
R40
R41
R42 R43
R44
(VI)
G H
I
in which formula (VI):
 R33, R34, R35 and R36, which may be identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally
35 substituted arylalkyl; particularly an alkyl and benzyl group optionally substituted
with a group (O)mS(O-
)-, M+ with M+
and m as defined previously;
 R37, R38, R39, R40, R41, R42, R43 and R44, which may be identical or different,
represent a hydrogen atom or a group chosen from:
22
5 - alkyl;
- alkoxy, alkylthio;
- (di)(alkyl)amino;
- hydroxyl, mercapto;
- nitro, nitroso;
10 - R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X’’- with R° representing a hydrogen
atom or an alkyl or aryl group; X, X’ and X’’, which may be identical or different,
representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom
or an alkyl group;
- (O)2S(O-
)-, M+ with M+
representing a hydrogen atom or a cationic coun15 terion;
- (O)CO-
-, M+ with M+ as defined previously;
- or alternatively two contiguous groups R41 with R42 or R42 with R43 or R43
with R44 together form a fused benzo group: I’; with I’ optionally substituted with
one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O-
)-, M+
; iv) hydroxyl;
20 v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X’-; viii) R°-X’-C(X)- and ix) R°-X’-
C(X)-X’’-; with M+
, R°, X, X’ and X’’ as defined previously;
particularly, R37 to R40 represent a hydrogen atom, and R41 to R44, which may be
identical or different, represent a hydroxyl group or (O)2S(O-
)-, M+
; and when R43
with R44 together form a benzo group, it is preferentially substituted with a group
(O)2S(O25 )-;
it being understood that at least one of the rings G, H, I or I’ comprises at least one
sulfonate radical (O)2S(O-
)- or a carboxylate radical -C(O)O-
; preferentially sulfonate;
30 as examples of dyes of formula (VI), mention may be made of: Acid Blue 1; Acid
Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid Green 3; Acid Green 5 and
Acid Green 50;
f) the xanthene-based dyes of formula (VII):
R48
R46
R45 R47
R52
R51
R50
R49
L G L'
Q'
-
Q
M
+
(VII)
35
in which formula (VII):
 R45, R46, R47 and R48, which may be identical or different, represent a hydrogen or halogen atom;
23
5  R49, R50, R51 and R52, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- hydroxyl, mercapto;
10 - nitro, nitroso;
- (O)2S(O-
)-, M+ with M+
representing a hydrogen atom or a cationic counterion;
- (O)CO-
-, M+ with M+ as defined previously;
particularly, R53, R54, R55 and R48 represent a hydrogen or halogen atom;
15  G represents an oxygen or sulfur atom or a group NRe with Re as defined
previously; particularly G represents an oxygen atom;
 L represents an alkoxide O-
, M+
; a thioalkoxide S-
, M+
or a group NRf, with Rf
representing a hydrogen atom or an alkyl group and M+
as defined previously; M+
is particularly sodium or potassium;
 L' represents an oxygen or sulfur atom or an ammonium group: N+
20 RfRg, with
Rf and Rg, which may be identical or different, representing a hydrogen atom, an
alkyl group or optionally substituted aryl; L’ represents more particularly an oxygen
atom or a phenylamino group optionally substituted with one or more alkyl or
(O)mS(O-
)-, M+
groups with m and M+
as defined previously;
25  Q and Q’, which may be identical or different, represent an oxygen or sulfur
atom; particularly, Q and Q’ represent an oxygen atom;
 M
+
is as defined previously;
as examples of dyes of formula (VI), mention may be made of: Acid Yellow 73; Ac30 id Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9;
g) the indole-based dyes of formula (VIII):
N
G
N
Rh G
Ri
R53
R54
R55
R56
R57
R58
R59
R60
(VIII)
 R53, R54, R55, R56, R57, R58, R59 and R60, which may be identical or different,
35 represent a hydrogen atom or a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- hydroxyl, mercapto;
- nitro, nitroso;
40 - R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X’’- with R° representing a hydrogen
atom or an alkyl or aryl group; X, X’ and X’’, which may be identical or different,
24
5 representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom
or an alkyl group;
- (O)2S(O-
)-, M+ with M+
representing a hydrogen atom or a cationic counterion;
- (O)CO-
-, M+ with M+ as defined previously;
10  G represents an oxygen or sulfur atom or a group NRe with Re as defined
previously; particularly G represents an oxygen atom;
 Ri and Rh, which may be identical or different, represent a hydrogen atom or
an alkyl group;
it being understood that formula (VIII) comprises at least one sulfonate radical
(O)2S(O-
)-, M+
or one carboxylate radical -C(O)O-
, M+
15 ; preferentially sodium sulfonate;
As examples of dyes of formula (VIII), mention may be made of: Acid Blue 74;
h) the quinoline-based dyes of formula (IX):
R64
R63
R62
R61
N
O
HO
(IX)
20
 R61 represents a hydrogen or halogen atom or an alkyl group;
 R62, R63, and R64, which may be identical or different, represent a hydrogen
atom or a group (O)2S(O-
)-, M+ with M+
representing a hydrogen atom or a cationic
counterion;
25  or alternatively R61 with R62, or R61 with R64, together form a benzo group
optionally substituted with one or more groups (O)2S(O-
)-, M+ with M+
representing
a hydrogen atom or a cationic counterion;
it being understood that formula (IX) comprises at least one sulfonate radical
(O)2S(O-
)-, M+
preferentially sodium sulfonate.
30 As examples of dyes of formula (IX), mention may be made of: Acid Yellow 2, Acid
Yellow 3 and Acid Yellow 5.
More particularly, the dyes of formulae (II) to (VII) are chosen from:
(C.I. 45380) Acid Red 87 (VII)
(C.l. 10316) Sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid (V’)
(C.l. 10383) Acid Orange 3 (V)
(C.l. 13015) Acid Yellow 9 / Food Yellow 2 (II)
(C.l. 14780) Direct Red 45 / Food Red 13 (II)
(C.l. 13711) Acid Black 52 (II)
25
(C.l. 13065) Acid Yellow 36 (II)
(C.l. 14700) Sodium salt of 1-hydroxy-2-(2',4'-xylyl-5-sulfonatoazo)naphthalene4-sulfonic acid / Food Red 1 (II)
(C.l. 14720) Acid Red 14 / Food Red 3 / Mordant Blue 79 (II)
(C.l. 14805) Sodium salt of 4-hydroxy-3-[(2-methoxy-5-nitrophenyl)diaza]-6-
(phenylamino)naphthalene-2-sulfonic acid / Acid Brown 4 (II)
(C.l. 15510) Acid Orange 7 / Pigment Orange 17 / Solvent Orange 49 / Orange
4 (II)
(C.l. 15985) Food Yellow 3 / Pigment Yellow 104 (II)
(C.l. 16185) Acid Red 27 / Food Red 9 (II)
(C.l. 16230) Acid Orange 10 / Food Orange 4 (II)
(C.l. 16250) Acid Red 44 (II)
(C.l. 17200) Acid Red 33 / Food Red 12 (II)
(C.l. 15685) Acid Red 184 (II)
(C.l. 19125) Acid Violet 3 (II)
(C.I. 18055) Sodium salt of 1-hydroxy-2-(4’-acetamidophenylazo)-8-
acetamidonaphthalene-3,6-disulfonic acid / Acid Violet 7 / Food
Red 11 (II)
(C.l. 18130) Acid Red 135 (II)
(C.l. 19130) Acid Yellow 27(III)
(C.l. 19140) Acid Yellow 23 / Food Yellow 4 (III)
(C.l. 20170) 4'-(Sulfonato-2'',4''-dimethyl)bis(2,6-phenylazo)-1,3-
dihydroxybenzene / Acid Orange 24 (II)
(C.l. 20470) Sodium salt of 1-amino-2-(4'-nitrophenylazo)-7-phenylazo-8-
hydroxynaphthalene-3,6-disulfonic acid / Acid Black 1 (II)
(C.l. 23266) (4-((4-Methylphenyl)sulfonyloxy)phenylazo)-2,2'-dimethyl-4-((2-
hydroxy-5,8-disulfonato)naphthylazo)biphenyl / Acid Red 111 (II’)
(C.l. 27755) Food Black 2 (II)
(C.l. 25440) 1-(4'-Sulfonatophenylazo)-4-((2"-hydroxy-3"-acetylamino-6",8"-
disulfonato)naphthylazo)-6-sulfonatonaphthalene (tetrasodium salt)
/ Food Black 1 (II)
(C.I. 42090) Acid Blue 9 (VI)
(C.I. 60730) Acid Violet 43 (IV)
(C.I. 61570) Acid Green 25 (IV)
(C.I. 62045) Sodium salt of 1-amino-4-cyclohexylamino-9,10-anthraquinone-2-
sulfonic acid / Acid Blue 62 (IV)
(C.I. 62105) Acid Blue 78 (IV)
(C.l. 14710) Sodium salt of 4-hydroxy-3-((2-methoxyphenyl)azo)-1-
naphthalenesulfonic acid / Acid Red 4 (II)
2-Piperidino-5-nitrobenzenesulfonic acid (V’)
2-(4'-N,N-(2"-Hydroxyethyl)amino-2'-nitro)anilineethanesulfonic
acid (V’)
26
4--Hydroxyethylamino-3-nitrobenzenesulfonic acid (V’)
(C.I. 42640) Acid Violet 49 (VI)
(C.I. 42080) Acid Blue 7 (VI)
(C.I. 58005) Sodium salt of 1,2-dihydroxy-3-sulfoanthraquinone / Mordant Red
3 (IV)
(C.I. 62055) Sodium salt of 1-amino-9,10-dihydro-9,10-dioxo-4-(phenylamino)
2-anthracenesulfonic acid / Acid Blue 25 (IV)
(C.I. 14710) Sodium salt of 4-hydroxy-3-((2-methoxyphenyl)azo)-1-
naphthalenesulfonic acid / Acid Red 4 (II)
(C.I. 16255) Acid Red 18 (II)
(C.I. 19140) Yellow 5 (III)
5
Most of these dyes are described in particular in the Colour Index published by
The Society of Dyers and Colourists, P.O. Box 244, Perkin House, 82 Grattan
Road, Bradford, Yorkshire, BD12 JBN England.
10 The anionic dyes that are most particularly preferred are the dyes designated in
the Colour Index under the code:
C.I. 58005 (monosodium salt of 1,2-dihydroxy-9,10-anthraquinone-3-sulfonic acid),
C.I. 60730 (monosodium salt of 2-[(9,10-dihydro-4-hydroxy-9,10-dioxo-1-
anthracenyl)amino]-5-methylbenzenesulfonic acid),
15 C.I. 15510 (monosodium salt of 4-[(2-hydroxy-1-naphthyl)azo]benzenesulfonic acid),
C.I. 15985 (disodium salt of 6-hydroxy-5-[(4-sulfophenyl)azo]-2-
naphthalenesulfonic acid),
C.I. 17200 (disodium salt of 5-amino-4-hydroxy-3-(phenylazo)-2,7-
20 naphthalenedisulfonic acid),
C.I. 20470 (disodium salt of 1-amino-2-(4'-nitrophenylazo)-7-phenylazo-8-hydroxy3,6-naphthalenedisulfonic acid),
C.I. 42090 (disodium salt of N-ethyl-N-[4-[[4-[ethyl[3-
sulfophenyl)methyl]amino]phenyl](2-sulfophenyl)methylene]-2,5-cyclohexadien-1-
25 ylidene]-3-sulfobenzenemethanaminium hydroxide, inner salt),
C.I. 61570 (disodium salt of 2,2'-[(9,10-dihydro-9,10-dioxo-1,4-
anthracenediyl)diimino]bis[5-methyl]benzenesulfonic acid),
C.I. 19140 (Yellow 5, the trisodium salt of 5-hydroxy-1-(4-sulfophenyl)-4-(4-
sulfophenylazo)pyrazole-3-carboxylic acid),
30 C.I. 16255 (Acid Red 18, the trisodium salt of 7-hydroxy-8-[(4-sulfo-1-
naphthalenyl)azo]-1,3-naphthalenedisulfonic acid).
Preferably, the anionic dyes are chosen from the compounds of formulae (II) and/or
(III).
35 Use may also be made of compounds corresponding to the mesomeric or tautomeric forms of structures (II) to (IX).
27
5
The direct dye(s) (v) may be present in the composition according to the invention
in a total content ranging from 0.001% to 15% by weight, preferably ranging from
0.005% to 10% by weight, preferentially ranging from 0.01% to 5% by weight, especially from 0.05% to 3% by weight, or even from 0.1% to 2% by weight, relative
10 to the total weight of the composition.
In particular, the composition according to the invention preferably comprises the
anionic direct dyes in a total content ranging from 0.001% to 15% by weight, preferably ranging from 0.005% to 10% by weight, preferentially ranging from 0.01%
15 to 5% by weight, especially from 0.05% to 3% by weight, or even from 0.1% to
2% by weight, relative to the total weight of the composition.
Cationic polymers
The cosmetic composition may also comprise one or more cationic polymers,
20 preferably with a cationic charge density of greater than or equal to 4 milliequivalents/gram (meq/g).
The cationic charge density of a polymer corresponds to the number of moles of
cationic charges per unit mass of polymer under conditions in which it is totally
25 ionized. It may be determined by calculation if the structure of the polymer is
known, i.e. the structure of the monomers constituting the polymer and their molar
proportion or weight proportion. It may also be determined experimentally by the
Kjeldahl method.
For the purposes of the present invention, the term "cationic polymer" denotes any
30 non-silicone (not comprising any silicon atoms) polymer containing cationic groups
and/or groups that can be ionized into cationic groups and not containing any anionic groups and/or groups that can be ionized into anionic groups.
The cationic polymers that may be used preferably have a weight-average molar
mass (Mw) of between 500 and 5×106
approximately and preferably between 103
and 3×106
35 approximately.
Among the cationic polymers, mention may be made more particularly of:
(1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of the following formulae:
40
28
5
in which:
- R3, which may be identical or different, denote a hydrogen atom or a CH3 radical;
- A, which may be identical or different, represent a linear or branched divalent
alkyl group of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms, or a hydroxy10 alkyl group of 1 to 4 carbon atoms;
- R4, R5 and R6, which may be identical or different, represent an alkyl group containing from 1 to 18 carbon atoms or a benzyl radical, preferably an alkyl group
containing from 1 to 6 carbon atoms;
- R1 and R2, which may be identical or different, represent a hydrogen atom or an
15 alkyl group containing from 1 to 6 carbon atoms, preferably methyl or ethyl;
- X denotes an anion derived from a mineral or organic acid, such as a methosulfate anion or a halide such as chloride or bromide.
The copolymers of family (1) may also contain one or more units derived from
20 comonomers that may be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on
the nitrogen with lower (C1-C4) alkyls, acrylic or methacrylic acid esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.
Among these copolymers of family (1), mention may be made of:
25 - copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized
with dimethyl sulfate or with a dimethyl halide, such as that sold under the name
Hercofloc by the company Hercules,
- copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride, such as the products sold under the name Bina Quat P 100 by the company
30 Ciba Geigy,
- the copolymer of acrylamide and of methacryloyloxyethyltrimethylammonium
methosulfate, such as that sold under the name Reten by the company Hercules,
- quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or
methacrylate copolymers, such as the products sold under the name Gafquat by
35 the company ISP, for instance Gafquat 734 or Gafquat 755, or alternatively the
products known as Copolymer 845, 958 and 937. These polymers are described in
detail in French patents 2 077 143 and 2 393 573;
- dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers,
R3
C
C
O
A
N
CH2
O
R2
R1
R3
C
C
O
A
N+
O
R4 R6
R5
XCH2
R3
C
C
NH
A
N
CH2
O
R1
R2
R3
C
C
NH
A
N
+
CH2
O
R4
R5
R6
X
_
29
5 such as the product sold under the name Gaffix VC 713 by the company ISP,
- vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers, such as the
copolymers sold under the name Styleze CC 10 by ISP;
- quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers
such as the product sold under the name Gafquat HS 100 by the company ISP,
10 - preferably crosslinked polymers of methacryloyloxy(C1-C4)alkyltri(C1-
C4)alkylammonium salts, such as the polymers obtained by homopolymerization of
dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with
methyl chloride, the homopolymerization or copolymerization being followed by
15 crosslinking with an olefinically unsaturated compound, in particular methylenebisacrylamide. Use may be made more particularly of a crosslinked acrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by
weight) in the form of a dispersion comprising 50% by weight of said copolymer in
mineral oil. This dispersion is sold under the name Salcare® SC 92 by the compa20 ny Ciba. Use may also be made of a crosslinked methacryloyloxyethyltrimethylammonium chloride homopolymer comprising approximately 50% by weight of
the homopolymer in mineral oil or in a liquid ester. These dispersions are sold under the names Salcare® SC 95 and Salcare® SC 96 by the company Ciba.
25 (2) cationic polysaccharides, in particular cationic celluloses and galactomannan
gums. Among the cationic polysaccharides, mention may be made more particularly of cellulose ether derivatives comprising quaternary ammonium groups, cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and cationic galactomannan gums.
30 The cellulose ether derivatives comprising quaternary ammonium groups are in
particular described in FR 1 492 597, and mention may be made of the polymers
sold under the name Ucare Polymer JR (JR 400 LT, JR 125 and JR 30M) or LR
(LR 400 and LR 30M) by the company Amerchol. These polymers are also defined
in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose that
35 have reacted with an epoxide substituted with a trimethylammonium group.
Cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble
quaternary ammonium monomer are described in particular in patent US
4 131 576, and mention may be made of hydroxyalkyl celluloses, for instance hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses grafted, in particular, with a
40 methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium
or dimethyldiallylammonium salt. The commercial products corresponding to this
definition are more particularly the products sold under the names Celquat L 200
and Celquat H 100 by the company National Starch.
The cationic galactomannan gums are described more particularly in patents US
45 3 589 578 and US 4 031 307, and mention may be made of guar gums comprising
cationic trialkylammonium groups. Use is made, for example, of guar gums modified with a 2,3-epoxypropyltrimethylammonium salt (for example, a chloride). Such
30
5 products are in particular sold under the names Jaguar C13 S, Jaguar C 15, Jaguar C 17 and Jaguar C162 by the company Rhodia.
(3) polymers constituted of piperazinyl units and divalent alkylene or hydroxyalkylene radicals containing linear or branched chains, optionally interrupted with
10 oxygen, sulfur or nitrogen atoms or with aromatic or heterocyclic rings, and also
the oxidation and/or quaternization products of these polymers.
(4) water-soluble polyaminoamides prepared in particular by polycondensation of
an acidic compound with a polyamine; these polyaminoamides can be crosslinked
15 with an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a
bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bishaloacyldiamine, a bis-alkyl halide or alternatively with an oligomer resulting from
the reaction of a difunctional compound which is reactive with a bis-halohydrin, a
bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide, an epihalohydrin, a di20 epoxide or a bis-unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mol per amine group of the polyaminoamide;
these polyaminoamides can be alkylated or, if they comprise one or more tertiary
amine functions, they can be quaternized.
25 (5) polyaminoamide derivatives resulting from the condensation of polyalkylene
polyamines with polycarboxylic acids followed by alkylation with difunctional
agents. Mention may be made, for example, of adipic acid/dialkylaminohydroxyalkyldialkylenetriamine polymers in which the alkyl radical
comprises from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or pro30 pyl. Among these derivatives, mention may be made more particularly of the adipic
acid/dimethylaminohydroxypropyl/diethylenetriamine polymers sold under the
name Cartaretine F, F4 or F8 by the company Sandoz.
(6) polymers obtained by reacting a polyalkylene polyamine comprising two prima35 ry amine groups and at least one secondary amine group with a dicarboxylic acid
chosen from diglycolic acid and saturated aliphatic dicarboxylic acids containing
from 3 to 8 carbon atoms; the mole ratio between the polyalkylene polyamine and
the dicarboxylic acid preferably being between 0.8:1 and 1.4:1; the resulting polyaminoamide being reacted with epichlorohydrin in a mole ratio of epichlorohydrin
40 relative to the secondary amine group of the polyaminoamide preferably of between 0.5:1 and 1.8:1. Polymers of this type are sold in particular under the name
Hercosett 57 by the company Hercules Inc. or else under the name PD 170 or
Delsette 101 by the company Hercules in the case of the adipic acid/epoxypropyl/diethylenetriamine copolymer.
45
(7) cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium, such as the
homopolymers or copolymers containing, as main constituent of the chain, units
31
5 corresponding to formula (I) or (II):

in which
- k and t are equal to 0 or 1, the sum k + t being equal to 1;
10 - R12 denotes a hydrogen atom or a methyl radical;
- R10 and R11, independently of each other, denote a C1-C6 alkyl group, a C1-C5
hydroxyalkyl group, a C1-C4 amidoalkyl group; or alternatively R10 and R11 may
denote, together with the nitrogen atom to which they are attached, a heterocyclic
group such as piperidyl or morpholinyl; R10 and R11, independently of each other,
15 preferably denote a C1-C4 alkyl group;
- Y
-
is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate.
Mention may be made more particularly of the homopolymer of dimethyldiallylammonium salts (for example chloride) for example sold under the name Mer20 quat 100 by the company Nalco and the copolymers of diallyldimethylammonium
salts (for example chloride) and of acrylamide, sold in particular under the name
Merquat 550 or Merquat 7SPR.
(8) quaternary diammonium polymers comprising repeating units of formula:
25
in which:
- R13, R14, R15 and R16, which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals comprising from 1 to 20 carbon atoms or C1-C12 hydroxyalkyl aliphatic radicals,
30 or else R13, R14, R15 and R16, together or separately, form, with the nitrogen atoms
to which they are attached, heterocycles optionally comprising a second nonnitrogen heteroatom;
or else R13, R14, R15 and R16 represent a linear or branched C1-C6 alkyl radical
substituted with a nitrile, ester, acyl, amide or -CO-O-R17-D or -CO-NH-R17-D
35 group, where R17 is an alkylene and D is a quaternary ammonium group;
- A1 and B1 represent linear or branched, saturated or unsaturated, divalent
CR12
H2
C
N+
CH2
C(R12
)-CH2
-
(CH2
)k
-(CH2
)tR10
R11
(I) YCR12
H2
C
N
CH2
C(R12
)-CH2
-
(CH2
)k
-(CH2
)tR10
(II)
N+
R13
R14
A1 N+
R15
R16
B1
X- X-
(III)
32
5 polymethylene groups comprising from 2 to 20 carbon atoms, which may contain,
linked to or intercalated in the main chain, one or more aromatic rings or one or
more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino,
hydroxyl, quaternary ammonium, ureido, amide or ester groups, and
- X
-
denotes an anion derived from a mineral or organic acid;
10 it being understood that A1, R13 and R15 can form, with the two nitrogen atoms to
which they are attached, a piperazine ring;
in addition, if A1 denotes a linear or branched, saturated or unsaturated alkylene or
hydroxyalkylene radical, B1 may also denote a group (CH2)n-CO-D-OC-(CH2)pwith n and p, which may be identical or different, being integers ranging from 2 to
15 20, and D denoting:
a) a glycol residue of formula -O-Z-O-, in which Z denotes a linear or
branched hydrocarbon-based radical, or a group corresponding to one of the following formulae: -(CH2CH2O)x-CH2CH2- and -[CH2CH(CH3)O]y-CH2CH(CH3)-, in
which x and y denote an integer from 1 to 4, representing a defined and unique
20 degree of polymerization or any number from 1 to 4 representing an average degree of polymerization;
b) a bis-secondary diamine residue, such as a piperazine derivative;
c) a bis-primary diamine residue of formula -NH-Y-NH-, in which Y denotes
a linear or branched hydrocarbon-based radical, or else the divalent radical -CH2-
25 CH2-S-S-CH2-CH2-;
d) a ureylene group of formula -NH-CO-NH-.
Preferably, Xis an anion, such as chloride or bromide. These polymers have a
number-average molar mass (Mn) generally of between 1000 and 100 000.
30 Mention may be made more particularly of polymers that are constituted of repeating units corresponding to the formula:
in which R1, R2, R3 and R4, which may be identical or different, denote an alkyl or
35 hydroxyalkyl radical containing from 1 to 4 carbon atoms, n and p are integers
ranging from 2 to 20, and Xis an anion derived from a mineral or organic acid.
A particularly preferred compound of formula (IV) is the one for which R1, R2, R3
and R4 represent a methyl radical and n = 3, p = 6 and X = Cl, known as Hexadimethrine chloride according to the INCI (CTFA) nomenclature.
40
(9) polyquaternary ammonium polymers comprising units of formula (V):
N
+
R2
R1
(CH2
)
n N
+
R4
R3
(CH2
)
p
(IV)
X- X-
33
5
in which:
- R18, R19, R20 and R21, which may be identical or different, represent a hydrogen
atom or a methyl, ethyl, propyl, -hydroxyethyl, -hydroxypropyl or -
CH2CH2(OCH2CH2)pOH radical, in which p is equal to 0 or to an integer between 1
10 and 6, with the proviso that R18, R19, R20 and R21 do not simultaneously represent
a hydrogen atom,
- r and s, which may be identical or different, are integers between 1 and 6,
- q is equal to 0 or to an integer between 1 and 34,
- X
-
denotes an anion such as a halide,
15 - A denotes a divalent dihalide radical or preferably represents -CH2-CH2-O-CH2-
CH2-.
Examples that may be mentioned include the products Mirapol® A 15, Mirapol®
AD1, Mirapol® AZ1 and Mirapol® 175 sold by the company Miranol.
20 (10) quaternary polymers of vinylpyrrolidone and of vinylimidazole, for instance the
products sold under the names Luviquat® FC 905, FC 550 and FC 370 by the
company BASF.
(11) polyamines such as Polyquart® H sold by Cognis, referred to under the name
25 Polyethylene glycol (15) tallow polyamine in the CTFA dictionary.
(12) polymers comprising in their structure:
(a) one or more units corresponding to formula (A) below:
30
(b) optionally one or more units corresponding to formula (B) below:
In other words, these polymers may be chosen in particular from homopolymers or
35 copolymers comprising one or more units derived from vinylamine and optionally
one or more units derived from vinylformamide.
Preferably, these cationic polymers are chosen from polymers comprising, in their
structure, from 5 mol% to 100 mol% of units corresponding to the formula (A) and
from 0 to 95 mol% of units corresponding to the formula (B), preferably from 10
N+
R19
R18
(CH2
)
r NH CO (CH2
)
q CO NH (CH2
)
s
R21
R20
N+ A
XX- (V)
CH2 CH
NH2
(A)
CH2 CH
NH C
O
H
(B)
34
5 mol% to 100 mol% of units corresponding to the formula (A) and from 0 to 90
mol% of units corresponding to the formula (B).
These polymers may be obtained, for example, by partial hydrolysis of polyvinylformamide. This hydrolysis may take place in acidic or basic medium.
The weight-average molecular weight of said polymer, measured by light scatter10 ing, may range from 1000 to 3 000 000 g/mol, preferably from 10 000 to 1 000 000
and more particularly from 100 000 to 500 000 g/mol.
The polymers comprising units of formula (A) and optionally units of formula (B)
are sold in particular under the Lupamin name by the company BASF, for instance,
in a non-limiting way, the products provided under the names Lupamin 9095, Lu15 pamin 5095, Lupamin 1095, Lupamin 9030 (or Luviquat 9030) and Lupamin 9010.
Other cationic polymers that may be used in the context of the invention are cationic proteins or cationic protein hydrolysates, polyalkyleneimines, in particular polyethyleneimines, polymers comprising vinylpyridine or vinylpyridinium units, con20 densates of polyamines and of epichlorohydrin, quaternary polyureylenes and chitin derivatives.
Preferably, the cationic polymers are chosen from those of families (1), (2), (7) and
(10) mentioned above.
25
Among the cationic polymers mentioned above, the ones that may preferably be
used are cationic polysaccharides, in particular cationic celluloses and cationic
galactomannan gums, and in particular quaternary cellulose ether derivatives such
as the products sold under the name JR 400 by the company Amerchol, cationic
30 cyclopolymers, in particular dimethyldiallylammonium salt (for example chloride)
homopolymers or copolymers, sold under the names Merquat 100, Merquat 550
and Merquat S by the company Nalco, quaternary polymers of vinylpyrrolidone
and of vinylimidazole, optionally crosslinked homopolymers or copolymers of
methacryloyloxy(C1-C4)alkyltri(C1-C4)alkylammonium salts, and mixtures thereof.
35
The total content of cationic polymer(s) in the composition according to the invention may range from 0.05% to 5% by weight relative to the total weight of the composition, preferably from 0.1% to 3% by weight and preferentially from 0.2% to 2%
by weight relative to the total weight of the composition.
40
Amphoteric polymers
The cosmetic composition may also comprise one or more amphoteric polymers.
For the purposes of the present invention, the term "amphoteric polymer" denotes
any non-silicone (not comprising any silicon atoms) polymer containing cationic
45 groups and/or groups that can be ionized into cationic groups and also anionic
groups and/or groups that can be ionized into anionic groups.
35
5 The amphoteric polymers may preferably be chosen from amphoteric polymers
comprising the repetition of:
(i) one or more units derived from a (meth)acrylamide-type monomer,
(ii) one or more units derived from a (meth)acrylamidoalkyltrialkylammonium-type
monomer, and
10 (iii) one or more units derived from a (meth)acrylic acid-type acid monomer.
Preferably, the units derived from a (meth)acrylamide-type monomer are units of
structure (Ia) below:
15 in which R1 denotes H or CH3 and R2 is chosen from an amino, dimethylamino,
tert-butylamino, dodecylamino and -NH-CH2OH radical.
Preferably, said amphoteric polymer comprises the repetition of only one unit of
formula (Ia).
The unit derived from a monomer of (meth)acrylamide type of formula (Ia) in which
20 R1 denotes H and R2 is an amino radical (NH2) is particularly preferred. It corresponds to the acrylamide monomer per se.
Preferably, the units derived from a monomer of
(meth)acrylamidoalkyltrialkylammonium type are units of structure (IIa) below:
25
in which:
- R3 denotes H or CH3,
- R4 denotes a group (CH2)k, with k being an integer ranging from 1 to 6 and preferably from 2 to 4;
30 - R5, R6 and R7, which may be identical or different, denote a C1-C4 alkyl,
- Y
-
is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate.
Preferably, said amphoteric polymer comprises the repetition of only one unit of
formula (IIa).
35 Among these units derived from a (meth)acrylamidoalkyltrialkylammonium-type
CH2
O R2
R1
(Ia)
CH2
O NH
R3
R4
N
+
R7
R6
R5
Y
(IIa)
36
5 monomer of formula (IIa), the ones that are preferred are those derived from the
methacrylamidopropyltrimethylammonium chloride monomer, for which R3 denotes
a methyl radical, k is equal to 3, R5, R6 and R7 denote a methyl radical, and Ydenotes a chloride anion.
10 Preferably, the units derived from a monomer of (meth)acrylic acid type are units
of formula (IIIa):
in which R8 denotes H or CH3 and R9 denotes a hydroxyl radical or an –NH15 C(CH3)2-CH2-SO3H radical.
The preferred units of formula (IIIa) correspond to the acrylic acid, methacrylic acid
and 2-acrylamido-2-methylpropanesulfonic acid monomers.
Preferably, the unit derived from a monomer of (meth)acrylic acid type of formula
(IIIa) is that derived from acrylic acid, for which R8 denotes a hydrogen atom and
20 R9 denotes a hydroxyl radical.
The acidic monomer(s) of (meth)acrylic acid type may be non-neutralized or partially or totally neutralized with an organic or mineral base.
Preferably, said amphoteric polymer comprises the repetition of only one unit of
formula (IIIa).
25
According to a preferred embodiment of the invention, the amphoteric polymer(s)
of this type comprise at least 30 mol% of units derived from a monomer of
(meth)acrylamide type (i). Preferably, they comprise from 30 mol% to 70 mol% and
more preferably from 40 mol% to 60 mol% of units derived from a
30 (meth)acrylamide-type monomer.
The content of units derived from a monomer of
(meth)acrylamidoalkyltrialkylammonium type (ii) may advantageously be from 10
mol% to 60 mol% and preferentially from 20 mol% to 55 mol%.
The content of units derived from an acidic monomer of (meth)acrylic acid type (iii)
35 may advantageously be from 1 mol% to 20 mol% and preferentially from 5 mol%
to 15 mol%.
According to a particularly preferred embodiment of the invention, the amphoteric
polymer of this type comprises:
- from 30 mol% to 70 mol% and more preferably from 40 mol% to 60 mol% of units
40 derived from a monomer of (meth)acrylamide type (i),
- from 10 mol% to 60 mol% and preferentially from 20 mol% to 55 mol% of
units derived from a monomer of (meth)acrylamidoalkyltrialkylammonium type (ii),
and
CH2
O R9
R8
(IIIa)
37
5 - from 1 mol% to 20 mol% and preferentially from 5 mol% to 15 mol% of units derived from a monomer of (meth)acrylic acid type (iii).
Amphoteric polymers of this type may also comprise additional units, other than
the units derived from a (meth)acrylamide-type monomer, a
10 (meth)acrylamidoalkyltrialkylammonium-type monomer and a (meth)acrylic acidtype monomer as described above.
However, according to a preferred embodiment of the invention, said amphoteric
polymers are constituted solely of units derived from monomers of
(meth)acrylamide type (i), of (meth)acrylamidoalkyltrialkylammonium type (ii) and
15 of (meth)acrylic acid type (iii).
Mention may be made, as an example of particularly preferred amphoteric polymers, of acrylamide/methacrylamidopropyltrimethylammonium chloride/acrylic acid
terpolymers. Such polymers are listed in the CTFA dictionary (INCI) under the
name "Polyquaternium 53". Corresponding products are in particular sold under
20 the names Merquat 2003 and Merquat 2003 PR by Nalco.
As another type of amphoteric polymer that may be used, mention may also be
made of copolymers based on (meth)acrylic acid and on a dialkyldiallylammonium
salt, such as copolymers of (meth)acrylic acid and of dimethyldiallylammonium
25 chloride. An example that may be mentioned is Merquat 280 sold by Nalco.
The amphoteric polymer(s) may generally be present in the composition according
to the invention in a total amount of between 0.05% and 5% by weight, preferably
between 0.1% and 3% by weight, and more particularly between 0.2% and 2% by
30 weight, relative to the total weight of the composition.
According to a preferred embodiment of the invention, the composition according
to the invention comprises:
- one or more anionic surfactants (i) chosen from polyoxyalkylenated al35 kyl(amido)ether carboxylic acids and salts thereof, preferably of formula (I) as defined above;
- one or more anionic surfactants (ii) chosen from sodium, triethanolamine, magnesium or ammonium (C12-C14)alkyl sulfates and/or sodium, ammonium or magnesium (C12-C14)alkyl ether sulfates, which are oxyethylenated, for example with
40 1 to 10 mol of ethylene oxide;
- one or more nonionic surfactants in a total content of at least 1% by weight relative to the total weight of the composition, chosen, alone or as a mixture, from:
- saturated or unsaturated, linear or branched, oxyethylenated fatty alcohols
comprising at least one C8 to C40, especially C8-C20 and better still C10-C18 al45 kyl chain and from 1 to 100 mol of ethylene oxide, preferably from 2 to 50, more
particularly from 2 to 40 mol, or even from 3 to 20 mol of ethylene oxide and lauryl
alcohol containing 12 mol of ethylene oxide; and
38
5 - (C6-C24 alkyl)(poly)glycosides, and more particularly (C8-C18 alkyl)(poly)glycosides;
- one or more amphoteric surfactants, in a total content of at least 3% by weight
relative to the total weight of the composition, comprising one or more surfactants
chosen from (C8-C20)alkylbetaines, (C8-C20)alkylsulfobetaines, (C8-
10 C20)alkylamido(C3-C8)alkylbetaines and (C8-C20)alkylamido(C6-
C8)alkylsulfobetaines;
- one or more direct dyes, preferably chosen, alone or as mixtures, from anionic
direct dyes;
- optionally, one or more cationic polymers preferably with a cationic charge densi15 ty of greater than or equal to 4 meq/g, preferentially chosen from dialkyldiallylammonium halide homopolymers; and
- optionally, one or more amphoteric polymers preferably constituted solely of units
derived from monomers (i) of acrylamide type, (ii) of acrylamidoalkyltrialkylammonium type and (iii) of (meth)acrylic acid type.
20
The composition according to the invention may comprise water or a mixture of
water and one or more cosmetically acceptable solvents chosen from C1-C4 alcohols, such as ethanol, isopropanol, tert-butanol or n-butanol; polyols such as glycerol, propylene glycol and polyethylene glycols; and mixtures thereof.
25 Preferably, the composition according to the invention has a total water content of
between 20% and 95% by weight, preferably between 30% and 90%, preferentially
between 50% and 85% by weight and better still between 65% and 80% by weight
relative to the total weight of the composition.
30 The pH of the compositions according to the invention generally ranges from 3 to
9, preferably from 3 to 7, preferentially from 3.5 to 6 and better still from 4 to 5.5.
The composition according to the invention may also comprise one or more standard additives that are well known in the art, such as natural or synthetic thickeners
35 or viscosity regulators; C12-C30 fatty alcohols; ceramides; C12-C32 fatty esters such
as isopropyl myristate, myristyl myristate, cetyl palmitate and stearyl stearate;
mineral, plant or synthetic oils; vitamins or provitamins; nonionic or anionic polymers; pH stabilizers, preserving agents; dyes; fragrances; agents for preventing
hair loss, anti-seborrhoeic agents, antidandruff agents.
40 A person skilled in the art will take care to select the optional additives and the
amount thereof such that they do not harm the properties of the compositions of
the present invention.
These additives are generally present in the composition according to the invention in an amount ranging from 0 to 20% by weight relative to the total weight of
45 the composition.
The compositions in accordance with the invention may be used as shampoos for
39
5 washing and conditioning the hair; they are preferably applied in this case to wet
hair in amounts that are effective for washing it; the lather generated by massaging
or rubbing with the hands may then be removed, after an optional leave-on time,
by rinsing with water, the operation possibly being repeated one or more times.
10 Process and use according to the invention
Another subject of the present invention relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising the application
to said fibres of a composition as defined above, followed by an optional leave-on
time and/or rinsing and/or drying.
15 The composition may be applied to wet or dry hair, and preferably to wet or moist
hair.
According to one embodiment, the process consists in applying to keratin fibres an
effective amount of the composition according to the invention, optionally massaging the fibres, optionally leaving the composition to stand on the fibres, and rinsing.
20 The leave-on time of the composition on the keratin fibres may be between a few
seconds and 30 minutes and preferably between 30 seconds and 20 minutes. The
composition is generally rinsed out with water.
An optional step of drying the keratin fibres may be performed.
25 The present invention also relates to the use of the composition according to the
invention as described previously for dyeing keratin fibres, in particular human
keratin fibres such as the hair.
The examples that follow serve to illustrate the invention without, however, being
30 limiting in nature.
EXAMPLES
The cosmetic compositions according to the invention are prepared from the ingredients shown in the table below, the amounts of which are expressed as weight
35 percentages of active material (AM).
Compositions (% AM)
A B C D
Sodium Laureth Sulfate 1.75 7 10 7
Cocamidopropyl betaine 3.8 7 7 7
Laureth-5 carboxylic acid 6.3 6 1 6
Laureth-12 4 4 5.7 -
40
Laureth-4 6 1 1 -
Caprylyl/capryl glucoside - - - 3
Polyquaternium-6 0.3 0.3 0.3 0.3
Orange 4 0.2 - - -
Yellow 5 - 0.2 - -
Acid Red 18 - - 0.2 0.2
Preserving agents, fragrance
qs qs qs qs
pH agent qs pH 5 qs pH 5 qs pH 5 qs pH 5
Water qs 100% qs 100% qs 100% qs 100%
5
The compositions according to the invention may be used as shampoos.
1 g of composition was applied to 2.5 g locks of hair containing 90% white hairs,
and the locks were then rinsed and dried. It was found that the locks thus treated
10 were advantageously dyed, most particularly after several successive applications
of the composition, especially after at least five successive applications.
The hair has a very cosmetic feel: it is easy to disentangle and has a soft, smooth
feel.
41
5 WE CLAIM:
1. Cosmetic composition, preferably a hair composition, comprising:
(i) one or more anionic surfactants chosen from polyoxyalkylenated al10 kyl(amido)ether carboxylic acids and/or salts thereof;
(ii) one or more anionic surfactants other than the polyoxyalkylenated alkyl(amido)ether carboxylic acid anionic surfactants (i);
15 (iii) one or more nonionic surfactants chosen from:
(a) oxyethylenated alcohols comprising at least one saturated or unsaturated, linear or branched C8 to C40 alkyl chain, and comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50 and more particularly from 2 to 40 mol of ethylene oxide and comprising one or two fatty chains;
20 (b) nonionic surfactants of alkyl(poly)glycoside type, represented especially by the
following general formula: R1O-(R2O)t-(G)v
in which:
- R1 represents a linear or branched alkyl or alkenyl radical comprising 6 to 24
carbon atoms and especially 8 to 18 carbon atoms, or an alkylphenyl radical
25 whose linear or branched alkyl radical comprises 6 to 24 carbon atoms and especially 8 to 18 carbon atoms,
- R2 represents an alkylene radical comprising 2 to 4 carbon atoms,
- G represents a sugar unit comprising 5 to 6 carbon atoms,
- t denotes a value ranging from 0 to 10 and preferably 0 to 4,
30 - v denotes a value ranging from 1 to 15 and preferably 1 to 4; and/or
(c ) polyethoxylated fatty acid esters of sorbitan, preferably containing from 2 to 40
mol of ethylene oxide and comprising at least one saturated or unsaturated, linear
or branched C8 to C40 alkyl chain, preferably C10-C28 alkyl chain (fatty acid);
(d) fatty acid esters of sucrose, preferably comprising at least one saturated or un35 saturated, linear or branched C8 to C40 alkyl chain, preferably C10-C28 alkyl
chain (fatty acid), such as sucrose cocoate and sucrose palmitate; and/or
(e ) polyglycerolated fatty esters, the number of glycerol groups possibly ranging
from 2 to 30 and comprising at least one saturated or unsaturated, linear or
branched C8 to C40 alkyl chain, preferably C10-C28 alkyl chain (fatty acid), such
40 as polyglyceryl-5 laurate, polyglyceryl-4 laurate, polyglyceryl-10 laurate, polyglyceryl-6 dicaprate.
(iv) one or more amphoteric surfactants; and
45 (v) one or more direct dyes.
2. Composition according to the preceding claim, characterized in that the polyox-
42
5 yalkylenated alkyl(amido)ether carboxylic acids are chosen from those of formula
(1):
in which:
10 - R1 represents a linear or branched C6-C24 alkyl or alkenyl radical, a (C8-
C9)alkylphenyl radical, a radical R2CONH-CH2-CH2- with R2 denoting a linear or
branched C9-C21 alkyl or alkenyl radical; preferably R1 is a C8-C20, preferably
C8-C18, alkyl radical,
- n is an integer or decimal number ranging from 2 to 24 and preferably from 2 to
15 10,
- A denotes H, ammonium, Na, K, Li, Mg, Ca or a monoethanolamine or triethanolamine residue.
3. Composition according to one of the preceding claims, in which the polyoxy20 alkylenated alkyl(amido)ether carboxylic acids are chosen from those of formula
(1):
in which:
25 - R1 denotes a C12-C14 alkyl, cocoyl, oleyl, nonylphenyl or octylphenyl radical,
- A denotes a hydrogen or sodium atom, and
- n ranges from 2 to 20, preferably from 2 to 10;
preferentially, R1 denotes a C12 alkyl radical, A denotes a hydrogen or sodium
atom and n ranges from 2 to 10.
30
4. Composition according to one of the preceding claims, comprising said polyoxyalkylenated alkyl(amido)ether carboxylic acid(s) and/or salts thereof in a total
amount ranging from 0.05% to 30% by weight, preferably from 0.1% to 25% by
weight, better still from 0.5% to 20% by weight and preferentially from 1% to 10%
35 by weight, relative to the total weight of the composition.
5. Composition according to one of the preceding claims, in which the anionic surfactants (ii) are chosen, alone or as a mixture, from:
- C6-C24 and especially C12-C20 alkyl sulfates;
40 - C6-C24 and especially C12-C20 alkyl ether sulfates; preferably comprising from
2 to 20 ethylene oxide units;
- C6-C24 and especially C12-C20 alkylsulfosuccinates, especially laurylsulfosuccinates;
- C6-C24 and especially C12-C20 alkyl ether sulfosuccinates;
45 - (C6-C24)acylisethionates and preferably (C12-C18)acylisethionates;
- C6-C24 and especially C12-C20 acylsarcosinates; especially palmitoylsarcosinates;
R1
(OC2H4
)n
OCH2COOA (1) R1
(OC2H4
)n
OCH2COOA (1)
43
5 - C6-C24 and especially C12-C20 acylglutamates;
- C6-C24 and especially C12-C20 acylglycinates;
in particular in the form of alkali metal or alkaline-earth metal, ammonium or amino
alcohol salts;
preferentially chosen from C8-C14 and more particularly C12-C14 alkyl sulfates
10 and alkyl ether sulfates, and more particularly lauryl (ether) sulfates.
6. Composition according to one of the preceding claims, comprising the anionic
surfactant(s) (ii) in a total content ranging from 0.05% to 30% by weight, preferably
in a content ranging from 0.1% to 25%, better still from 0.5% to 20% by weight and
15 even better still from 1% to 15% by weight, relative to the total weight of the composition.
7. Composition according to any one of the preceding claims, in which the nonionic
surfactants are chosen, alone or as a mixture, from:
- saturated or unsaturated, linear or branched, oxyethylenated C8 to C40, especially
20 C8-C20 and better still C10-C18 fatty alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50, more particularly from 2 to 40 mol, or even
from 3 to 20 mol of ethylene oxide; especially lauryl alcohol containing 4 mol of
ethylene oxide (INCI name: Laureth-4) and lauryl alcohol containing 12 mol of ethylene oxide (INCI name: Laureth-12); and
25 - (C6-C24 alkyl)(poly)glycosides, and more particularly (C8-C18 alkyl)(poly)glycosides;
better still from oxyethylenated C8-C20 alcohols comprising from 2 to 50 and in particular from 3 to 20 mol of ethylene oxide.
30 8. Composition according to any one of the preceding claims, comprising the
nonionic surfactants in a total content ranging from 0.05% to 30% by weight, preferentially ranging from 0.1% to 25% by weight, in particular ranging from 0.5% to
20% by weight, especially from 1% to 15% by weight and better still from 2% to
10% by weight, relative to the total weight of the composition.
35
9. Composition according to any one of the preceding claims, in which the amphoteric surfactants are chosen from (C8-C20)alkylbetaines, (C8-C20)alkylsulfobetaines,
(C8-C20)alkylamido(C3-C8)alkylbetaines and (C8-C20)alkylamido(C6-
C8)alkylsulfobetaines, and also:
40 - the compounds having the respective structures (II) and (III) below:
Ra-CONHCH2CH2-N
+
(Rb)(Rc)-CH2COO-
, M+
, X-
(II)
in which:
- Ra represents a C10 to C30 alkyl or alkenyl group derived from an acid RaCOOH
45 preferably present in hydrolysed coconut oil, or a heptyl, nonyl or undecyl group;
- Rb represents a beta-hydroxyethyl group; and
- Rc represents a carboxymethyl group;
44
- M
+
5 represents a cationic counterion derived from an alkali metal or alkaline-earth
metal, such as sodium, an ammonium ion or an ion derived from an organic
amine; and
- X
-
represents an organic or mineral anionic counterion, such as that chosen from
halides, acetates, phosphates, nitrates, (C1-C4)alkyl sulfates, (C1-C4)alkyl- or (C1-
10 C4)alkylarylsulfonates, in particular methyl sulfate and ethyl sulfate; or alternatively
M
+
and Xare absent;
Ra'-CONHCH2CH2-N(B)(B') (III)
in which:
15 - B represents the group -CH2CH2OX';
- B' represents the group -(CH2)zY', with z = 1 or 2;
- X' represents the group -CH2COOH, -CH2-COOZ’, CH2CH2COOH or -CH2CH2-
COOZ’, or a hydrogen atom;
- Y' represents the group -COOH, -COOZ' or -CH2-CH(OH)SO3H or the group
20 CH2CH(OH)SO3-Z';
- Z' represents a cationic counterion resulting from an alkali metal or alkaline-earth
metal, such as sodium, an ammonium ion or an ion resulting from an organic
amine;
- Ra’ represents a C10 to C30 alkyl or alkenyl group of an acid Ra’-COOH which is
25 preferably present in coconut oil or in hydrolysed linseed oil, or an alkyl group, especially a C17 group, and its iso form, or an unsaturated C17 group;
- compounds of formula (IV):
Ra''-NHCH(Y'')-(CH2)nCONH(CH2)n'-N(Rd)(Re) (IV)
30 in which:
- Y'' represents the group -COOH, -COOZ'' or -CH2-CH(OH)SO3H or the group
CH2CH(OH)SO3-Z'';
- Rd and Re represent, independently of each other, a C1 to C4 alkyl or hydroxyalkyl
radical;
35 - Z’’ represents a cationic counterion derived from an alkali metal or alkaline-earth
metal, such as sodium, an ammonium ion or an ion derived from an organic
amine;
- Ra'' represents a C10 to C30 alkyl or alkenyl group of an acid Ra''-COOH which is
preferably present in coconut oil or in hydrolysed linseed oil;
40 - n and n' denote, independently of each other, an integer ranging from 1 to 3.
10. Composition according to any one of the preceding claims, comprising the amphoteric surfactants in a total content ranging from 0.1% to 25% by weight, preferentially in a total content ranging from 1% to 20% by weight, especially from 3% to
45 15% by weight and better still from 3.5% to 10% by weight, relative to the total
weight of the composition.
45
5 11. Composition according to any one of the preceding claims, in which the direct
dyes are chosen, alone or as a mixture, from synthetic or natural, anionic, cationic
or nonionic direct dyes; and in particular from the anionic dyes of formulae (II), (II'),
(III), (III'), (IV), (IV'), (V), (V'), (VI), (VII), (VIII) and (IX) below:
10 a) the diaryl anionic azo dyes of formula (II) or (II'):
N
N
R9
R7
R'
7
R'
9
R8
R'
8
R10
R'
10
(II)
A
B
R9
R7
R'
7
R8
R10
N
N
N
N
W
R9
R7
R'
7
R8
R10
A A
(II') C C
in which formulae (II) and (II'):
 R7, R8, R9, R10, R’7, R’8, R’9 and R’10, which may be identical or different,
15 represent a hydrogen atom or a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- hydroxyl, mercapto;
- nitro, nitroso;
20 - R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X’’- with R° representing a hydrogen
atom or an alkyl or aryl group; X, X’ and X’’, which may be identical or different,
representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom
or an alkyl group;
- (O)2S(O-
)-, M+ with M+
representing a hydrogen atom or a cationic coun25 terion;
- (O)CO-
-, M+ with M+ as defined previously;
- R’’-S(O)2-, with R’’ representing a hydrogen atom or an alkyl, aryl,
(di)(alkyl)amino or aryl(alkyl)amino group; preferentially a phenylamino or phenyl
group;
30 - R’’’-S(O)2-X’- with R’’’ representing an alkyl or optionally substituted aryl
group, X’ as defined previously;
- (di)(alkyl)amino;
- aryl(alkyl)amino optionally substituted with one or more groups chosen
from i) nitro; ii) nitroso; iii) (O)2S(O-
)-, M+
and iv) alkoxy with M+
as defined previ35 ously;
- optionally substituted heteroaryl; preferentially a benzothiazolyl group;
46
5 - cycloalkyl; especially cyclohexyl;
- Ar-N=N- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl, (O)2S(O-
)-, M+
or
phenylamino groups;
- or alternatively two contiguous groups R7 with R8 or R8 with R9 or R9 with
10 R10 together form a fused benzo group A’; and R'7 with R'8 or R'8 with R'9 or R'9 with
R'10 together form a fused benzo group B’; with A’ and B’ optionally substituted with
one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O-
)-, M+
; iv) hydroxyl;
v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X’-; viii) R°-X’-C(X)-; ix) R°-X’-C(X)-
X’’-; x) Ar-N=N- and xi) optionally substituted aryl(alkyl)amino; with M+
, R°, X, X’, X’’
15 and Ar as defined previously;
 W represents a sigma bond, an oxygen or sulfur atom, or a divalent radical i)
–NR- with R as defined previously, or ii) methylene -C(Ra)(Rb)- with Ra and Rb,
which may be identical or different, representing a hydrogen atom or an aryl group,
or alternatively Ra and Rb form, with the carbon atom that bears them, a spiro cy20 cloalkyl; preferentially, W represents a sulfur atom or Ra and Rb together form a
cyclohexyl;
it being understood that formulae (II) and (II’) comprise at least one sulfonate radical (O)2S(O-
)-, M+
or one carboxylate radical (O)CO-
-, M+
on one of the rings A, A',
B, B' or C; preferentially sodium sulfonate;
25
b) the pyrazolone anionic azo dyes of formulae (III) and (III'):
R11
R12
R13
N
N
N
N
Y
R14
R20 R19
R15
R16
R18
R R17
'
16
R'
20
R'
19
E (III)
D
R11
R12
R13
N
N
N
N
Y
R14
N
N
N
N
Y
R14
Ra Rb
R11
R12
R13
R21 R21
(III')
D D
F F
in which formulae (III) and (III'):
30  R11, R12 and R13, which may be identical or different, represent a hydrogen
or halogen atom, an alkyl group or -(O)2S(O-
), M+ with M+
as defined previously;
 R14 represents a hydrogen atom, an alkyl group or a group -C(O)O-, M+ with
M
+ as defined previously;
47
5  R15 represents a hydrogen atom;
 R16 represents an oxo group, in which case R’16 is absent, or alternatively
R15 with R16 together form a double bond;
- R17 and R18, which may be identical or different, represent a hydrogen
atom, a group chosen from i) (O)2S(O-
)-, M+ with M+
as defined previously, and ii)
10 Ar-O-S(O)2- with Ar representing an optionally substituted aryl group; preferentially
a phenyl optionally substituted with one or more alkyl groups;
 R19 and R20 together form either a double bond, or a benzo group D’, which
is optionally substituted;
 R’16, R’19 and R’20, which may be identical or different, represent a hydrogen
15 atom or an alkyl or hydroxyl group;
 R21 represents a hydrogen atom or an alkyl or alkoxy group;
 Ra and Rb, which may be identical or different, are as defined previously,
preferentially Ra represents a hydrogen atom and Rb represents an aryl group;
 Y represents either a hydroxyl group or an oxo group;
20  represents a single bond when Y is an oxo group; and represents a
double bond when Y represents a hydroxyl group;
it being understood that formulae (III) and (III’) comprise at least one sulfonate radical (O)2S(O-
)-, M+
or one carboxylate radical -C(O)O-
-, M+
on one of the rings D or
E; preferentially sodium sulfonate;
25
c) the anthraquinone dyes of formulae (IV) and (IV'):
O
O N
R26
R27
R22
R23
R24
R25
O
O
N
R26
R27
R22
R23
R24
R25
R28
O
O
R26
R27
R22
R23
R24
R25
Z
(IV)
Z
Z
(IV')
Z'
in which formulae (IV) and (IV'):
 R22, R23, R24, R25, R26 and R27, which may be identical or different, represent
30 a hydrogen or halogen atom, or a group chosen from:
- alkyl;
- hydroxyl, mercapto;
- alkoxy, alkylthio;
- optionally substituted aryloxy or arylthio, preferentially substituted with
one or more groups chosen from alkyl and (O)2S(O-
)-, M+ with M+
35 as defined previously;
48
5 - aryl(alkyl)amino optionally substituted with one or more groups chosen
from alkyl and (O)2S(O-
)-, M+ with M+
as defined previously;
- (di)(alkyl)amino;
- (di)(hydroxyalkyl)amino;
- (O)2S(O-
)-, M+ with M+
as defined previously;
10  Z’ represents a hydrogen atom or a group NR28R29 with R28 and R29, which
may be identical or different, representing a hydrogen atom or a group chosen
from:
- alkyl;
- polyhydroxyalkyl such as hydroxyethyl;
15 - aryl optionally substituted with one or more groups, particularly i) alkyl
such as methyl, n-dodecyl, n-butyl; ii) (O)2S(O-
)-, M+ with M+
as defined previously;
iii) R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X’’- with R°, X, X’ and X’’ as defined previously, preferentially R° represents an alkyl group;
- cycloalkyl; especially cyclohexyl;
20  Z, represents a group chosen from hydroxyl and NR’28R’29 with R’28 and R’29,
which may be identical or different, representing the same atoms or groups as R28
and R29 as defined previously;
it being understood that formulae (IV) and (IV’) comprise at least one sulfonate radical (O)2S(O-
)-, M+
or one carboxylate radical -C(O)O-
-, M+
; preferentially sodium
25 sulfonate;
d) the nitro dyes of formulae (V), (V’) and (V’’):
(R30
)
p
N N
Rc
Rd
O2N
J
SO3
-
R31
n
M'
R32
(V) (R30
)
q
M'
u
ALK SO3
- W
NO2
(V')
30 in which formulae (V) and (V'):
 R30, R31 and R32, which may be identical or different, represent a hydrogen
or halogen atom, or a group chosen from:
- alkyl;
- alkoxy optionally substituted with one or more hydroxyl groups, alkylthio
35 optionally substituted with one or more hydroxyl groups;
49
5 - hydroxyl, mercapto;
- nitro, nitroso;
- polyhaloalkyl;
- R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X’’- with R°, X, X’ and X’’ as defined
previously;
- (O)2S(O-
)-, M+ with M+
10 as defined previously;
- (O)CO-
-, M+ with M+ as defined previously;
- (di)(alkyl)amino;
- (di)(hydroxyalkyl)amino;
- heterocycloalkyl such as piperidino, piperazino or morpholino;
15 in particular, R30, R31 and R32 represent a hydrogen atom;
 Rc and Rd, which may be identical or different, represent a hydrogen atom or
an alkyl group;
 W is as defined previously; W particularly represents a group –NH–;
 ALK represents a linear or branched divalent C1-C6 alkylene group; in par20 ticular, ALK represents a group -CH2-CH2-;
 n is 1 or 2;
 p represents an integer between 1 and 5 inclusive;
 q represents an integer between 1 and 4 inclusive;
 u is 0 or 1;
25  when n is 1, J represents a nitro or nitroso group; particularly nitro;
 when n is 2, J represents an oxygen or sulfur atom, or a divalent radical –
S(O)m– with m representing an integer 1 or 2; preferentially, J represents a radical
–SO2–;
 M’ represents a hydrogen atom or a cationic counterion;
30

when it is present, represents a benzo group optionally substituted with one
or more groups R30 as defined previously;
35 it being understood that formulae (V) and (V’) comprise at least one sulfonate radical (O)2S(O-
)-, M+
or one carboxylate radical -C(O)O-
-, M+
; preferentially sodium
sulfonate;
e) the triarylmethane dyes of formula (VI):
50 N
+
N
R36
R33
R35
R34
R37
R38
R39
R40
R41
R42 R43
R44
(VI)
G H
I
5
in which formula (VI):
 R33, R34, R35 and R36, which may be identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally
substituted arylalkyl; particularly an alkyl and benzyl group optionally substituted
with a group (O)mS(O-
)-, M+ with M+
10 and m as defined previously;
 R37, R38, R39, R40, R41, R42, R43 and R44, which may be identical or different,
represent a hydrogen atom or group chosen from:
- alkyl;
- alkoxy, alkylthio;
15 - (di)(alkyl)amino;
- hydroxyl, mercapto;
- nitro, nitroso;
- R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X’’- with R° representing a hydrogen
atom or an alkyl or aryl group; X, X’ and X’’, which may be identical or different,
20 representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom
or an alkyl group;
- (O)2S(O-
)-, M+ with M+
representing a hydrogen atom or a cationic counterion;
- (O)CO-
-, M+ with M+ as defined previously;
25 - or alternatively two contiguous groups R41 with R42 or R42 with R43 or R43
with R44 together form a fused benzo group: I’; with I’ optionally substituted with
one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O-
)-, M+
; iv) hydroxyl;
v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X’-; viii) R°-X’-C(X)- and ix) R°-X’-
C(X)-X’’-; with M+
, R°, X, X’ and X’’ as defined previously;
30 particularly, R37 to R40 represent a hydrogen atom, and R41 to R44, which may be
identical or different, represent a hydroxyl group or (O)2S(O-
)-, M+
; and when R43
with R44 together form a benzo group, it is preferentially substituted with a group
(O)2S(O-
)-;
it being understood that at least one of the rings G, H, I or I’ comprises at least one
sulfonate radical (O)2S(O-
)- or a carboxylate radical -C(O)O35 ; preferentially sulfonate;
f) the xanthene-based dyes of formula (VII):
51
R48
R46
R45 R47
R52
R51
R50
R49
L G L'
Q'
-
Q
M
+
(VII)
5
in which formula (VII):
 R45, R46, R47 and R48, which may be identical or different, represent a hydrogen or halogen atom;
 R49, R50, R51 and R52, which may be identical or different, represent a hydro10 gen or halogen atom, or a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- hydroxyl, mercapto;
- nitro, nitroso;
- (O)2S(O-
)-, M+ with M+
15 representing a hydrogen atom or a cationic counterion;
- (O)CO-
-, M+ with M+ as defined previously;
particularly, R53, R54, R55 and R48 represent a hydrogen or halogen atom;
 G represents an oxygen or sulfur atom or a group NRe with Re as defined
20 previously; particularly G represents an oxygen atom;
 L represents an alkoxide O-
, M+
; a thioalkoxide S-
, M+
or a group NRf, with Rf
representing a hydrogen atom or an alkyl group and M+
as defined previously; M+
is particularly sodium or potassium;
 L' represents an oxygen or sulfur atom or an ammonium group: N+RfRg, with
25 Rf and Rg, which may be identical or different, representing a hydrogen atom, an
alkyl group or optionally substituted aryl; L’ represents more particularly an oxygen
atom or a phenylamino group optionally substituted with one or more alkyl or
(O)mS(O-
)-, M+
groups with m and M+
as defined previously;
 Q and Q’, which may be identical or different, represent an oxygen or sulfur
30 atom; particularly, Q and Q’ represent an oxygen atom;
 M
+
is as defined previously;
g) the indole-based dyes of formula (VIII):
52
N
G
N
Rh G
Ri
R53
R54
R55
R56
R57
R58
R59
R60
(VIII)
5
 R53, R54, R55, R56, R57, R58, R59 and R60, which may be identical or different,
represent a hydrogen atom or group chosen from:
- alkyl;
- alkoxy, alkylthio;
10 - hydroxyl, mercapto;
- nitro, nitroso;
- R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X’’- with R° representing a hydrogen
atom or an alkyl or aryl group; X, X’ and X’’, which may be identical or different,
representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom
15 or an alkyl group;
- (O)2S(O-
)-, M+ with M+
representing a hydrogen atom or a cationic counterion;
- (O)CO-
-, M+ with M+ as defined previously;
 G represents an oxygen or sulfur atom or a group NRe with Re as defined
20 previously; particularly G represents an oxygen atom;
 Ri and Rh, which may be identical or different, represent a hydrogen atom or
an alkyl group;
it being understood that formula (VIII) comprises at least one sulfonate radical
(O)2S(O-
)-, M+
or one carboxylate radical -C(O)O-
, M+
; preferentially sodium sul25 fonate;
h) the quinoline-based dyes of formula (IX):
R64
R63
R62
R61
N
O
HO
(IX)
 R61 represents a hydrogen or halogen atom or an alkyl group;
30  R62, R63, and R64, which may be identical or different, represent a hydrogen
atom or a group (O)2S(O-
)-, M+ with M+
representing a hydrogen atom or a cationic
counterion;
 or alternatively R61 with R62, or R61 with R64, together form a benzo group
optionally substituted with one or more groups (O)2S(O-
)-, M+ with M+
representing
35 a hydrogen atom or a cationic counterion;
53
5 it being understood that formula (IX) comprises at least one sulfonate radical
(O)2S(O-
)-, M+
preferentially sodium sulfonate.
12. Composition according to any one of the preceding claims, in which the direct
dyes are chosen from the following dyes:
10
(C.I. 45380) Acid Red 87 (VII)
(C.l. 10316) Sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid (V’)
(C.l. 10383) Acid Orange 3 (V)
(C.l. 13015) Acid Yellow 9 / Food Yellow 2 (II)
(C.l. 14780) Direct Red 45 / Food Red 13 (II)
(C.l. 13711) Acid Black 52 (II)
(C.l. 13065) Acid Yellow 36 (II)
(C.l. 14700) Sodium salt of 1-hydroxy-2-(2',4'-xylyl-5-
sulfonatoazo)naphthalene-4-sulfonic acid / Food Red 1 (II)
(C.l. 14720) Acid Red 14 / Food Red 3 / Mordant Blue 79 (II)
(C.l. 14805) Sodium salt of 4-hydroxy-3-[(2-methoxy-5-nitrophenyl)diaza]-6-
(phenylamino)naphthalene-2-sulfonic acid / Acid Brown 4 (II)
(C.l. 15510) Acid Orange 7 / Pigment Orange 17 / Solvent Orange 49 / Orange
4 (II)
(C.l. 15985) Food Yellow 3 / Pigment Yellow 104 (II)
(C.l. 16185) Acid Red 27 / Food Red 9 (II)
(C.l. 16230) Acid Orange 10 / Food Orange 4 (II)
(C.l. 16250) Acid Red 44 (II)
(C.l. 17200) Acid Red 33 / Food Red 12 (II)
(C.l. 15685) Acid Red 184 (II)
(C.l. 19125) Acid Violet 3 (II)
(C.I. 18055) Sodium salt of 1-hydroxy-2-(4’-acetamidophenylazo)-8-
acetamidonaphthalene-3,6-disulfonic acid / Acid Violet 7 / Food
Red 11 (II)
(C.l. 18130) Acid Red 135 (II)
(C.l. 19130) Acid Yellow 27(III)
(C.l. 19140) Acid Yellow 23 / Food Yellow 4 (III)
(C.l. 20170) 4'-(Sulfonato-2'',4''-dimethyl)bis(2,6-phenylazo)-1,3-
dihydroxybenzene / Acid Orange 24 (II)
(C.l. 20470) Sodium salt of 1-amino-2-(4'-nitrophenylazo)-7-phenylazo-8-
hydroxynaphthalene-3,6-disulfonic acid / Acid Black 1 (II)
(C.l. 23266) (4-((4-Methylphenyl)sulfonyloxy)phenylazo)-2,2'-dimethyl-4-((2-
hydroxy-5,8-disulfonato)naphthylazo)biphenyl / Acid Red 111 (II’)
(C.l. 27755) Food Black 2 (II)
(C.l. 25440) 1-(4'-Sulfonatophenylazo)-4-((2"-hydroxy-3"-acetylamino-6",8"-
disulfonato)naphthylazo)-6-sulfonatonaphthalene (tetrasodium
54
salt) / Food Black 1 (II)
(C.I. 42090) Acid Blue 9 (VI)
(C.I. 60730) Acid Violet 43 (IV)
(C.I. 61570) Acid Green 25 (IV)
(C.I. 62045) Sodium salt of 1-amino-4-cyclohexylamino-9,10-anthraquinone-2-
sulfonic acid / Acid Blue 62 (IV)
(C.I. 62105) Acid Blue 78 (IV)
(C.l. 14710) Sodium salt of 4-hydroxy-3-((2-methoxyphenyl)azo)-1-
naphthalenesulfonic acid / Acid Red 4 (II)
2-Piperidino-5-nitrobenzenesulfonic acid (V’)
2-(4'-N,N-(2"-Hydroxyethyl)amino-2'-nitro)anilineethanesulfonic
acid (V’)
4--Hydroxyethylamino-3-nitrobenzenesulfonic acid (V’)
(C.I. 42640) Acid Violet 49 (VI)
(C.I. 42080) Acid Blue 7 (VI)
(C.I. 58005) Sodium salt of 1,2-dihydroxy-3-sulfoanthraquinone / Mordant Red
3 (IV)
(C.I. 62055) Sodium salt of 1-amino-9,10-dihydro-9,10-dioxo-4-(phenylamino)
2-anthracenesulfonic acid / Acid Blue 25 (IV)
(C.I. 14710) Sodium salt of 4-hydroxy-3-((2-methoxyphenyl)azo)-1-
naphthalenesulfonic acid / Acid Red 4 (II)
(C.I. 16255) Acid Red 18 (II)
(C.I. 19140) Yellow 5 (III)
5
13. Composition according to any one of the preceding claims, comprising the
direct dyes in a total content ranging from 0.001% to 15% by weight, preferably
ranging from 0.005% to 10% by weight, preferentially ranging from 0.01% to 5%
by weight, especially from 0.05% to 3% by weight, or even from 0.1% to 2% by
10 weight, relative to the total weight of the composition.
14. Composition according to one of the preceding claims, also comprising one or
more cationic polymers, preferably with a cationic charge density of greater than or
equal to 4 milliequivalents/gram (meq/g); preferably in a total content ranging from
15 0.05% to 5% by weight, preferably from 0.1% to 3% by weight and preferentially
from 0.2% to 2% by weight, relative to the total weight of the composition.
15. Composition according to one of the preceding claims, also comprising one or
more amphoteric polymers, chosen especially from amphoteric polymers compris20 ing the repetition of:
(i) one or more units derived from a (meth)acrylamide-type monomer,
(ii) one or more units derived from a (meth)acrylamidoalkyltrialkylammonium-type
monomer, and
55
5 (iii) one or more units derived from a (meth)acrylic acid-type acid monomer;
preferably in a total content of between 0.05% and 5% by weight, preferably between 0.1% and 3% by weight and more particularly between 0.2% and 2% by
weight relative to the total weight of the composition.
10 16. Composition according to any one of the preceding claims, comprising water,
especially in a total water content of between 20% and 95% by weight, preferably
between 30% and 90%, preferentially between 50% and 85% by weight and better
still between 65% and 80% by weight relative to the total weight of the composition.
15
17. Process for dyeing keratin fibres, in particular human keratin fibres such as the
hair, comprising the application to said fibres of a composition as defined according to any one of Claims 1 to 16, followed by an optional leave-on time and/or rinsing and/or drying.
20
18. Use of the composition according to any one of Claims 1 to 16, for dyeing
keratin fibres, in particular human keratin fibres such as the hair.