DIRECT DYE COMPOSITION COMPRISING A CATIONIC
SURFACTANT, A BIOHETEROPOLYSACCHARIDE, AN AMPHOTERIC OR
NONIONIC SURFACTANT AND A DIRECT DYE
The present invention relates to a composition for the direct dyeing of keratin fibres, in particular of human keratin fibres.
It is known practice to dye keratin fibres, and in particular human hair, with dye compositions containing direct dyes, in particular nitrobenzene dyes, acidic azo dyes, cationic azo dyes, anthraquinone dyes or natural dyes.
These colorations may be carried out by direct application of the composition containing the direct dye(s) to the keratin fibres, or by application of an extemporaneously prepared mixture of a composition containing the direct dye(s) with a composition containing an oxidizing bleaching agent which is preferably aqueous hydrogen peroxide. In the latter case, this is referred to as lightening direct dyeing.
It is already known practice to prepare compositions for the direct dyeing of keratin fibres by combining, with the direct dyes, surfactants and/or thickeners in order to improve the physical properties and/or the colorations obtained.
Compositions comprising a direct dye and a xanthan gum for obtaining better thickening of the direct dye compositions are in particular known from FR 2 548 893, it being possible for these compositions to contain surfactants.
However, these compositions do not give entirely satisfactory cosmetic and/or dyeing properties, in particular as regards the intensity of the colorations and their selectivities representative of colour
differences between various parts of one or more hairs according to the degree of sensitization.
Thus, the aim of the present invention is to develop novel compositions for the direct dyeing of keratin fibres such as the hair, which make it possible to solve this technical problem. In particular, the invention seeks to obtain compositions which make it possible to obtain intense and relatively nonselective shades, the hair having, moreover, good cosmetic properties.
Thus, this aim is achieved with the present invention, the subject of which is a composition for dyeing keratin fibres, comprising at least one direct dye, at least one bioheteropolysaccharide, at least one cationic surfactant and at least one amphoteric or nonionic surfactant.
In the composition of the invention, the direct dyes may be chosen from all the direct dyes known in the art for dyeing keratin fibres, in particular the hair.
The direct dyes that can be used according to the invention are preferably chosen from neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, neutral, acidic or cationic quinone, and in particular anthraquinone, direct dyes, azine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.
Among the benzene-based direct dyes that can be used according to the invention, mention may be made, in a non-limiting manner, of the following compounds:
- 1,4-diamino-2-nitrobenzene
- l-amino-2-nitro-4-ß-hydroxyethylaminobenzene
- l-amino-2-nitro-4-bis (ß-hydroxyethyl) aminobenzene
- 1, 4-bis ß-hydroxyethylamino) -2-nitrobenzene
- l-(3-hydroxyethylamino-2-nitro-4-bis (ß-hydroxyethyl-
amino)benzene
- 1-ß-hydroxyethylamino-2-nitro-4-aminobenzene
- l-ß-hydroxyethylamino-2-nitro-4-(ethyl) (ß-hydroxy-
ethyl)aminobenzene
- l-amino-3-methyl-4-ß-hydroxyethylamino-6-nitrobenzene
- l-amino-2-nitro-4-ß-hydroxyethylamino-5-chlorobenzene
- 1,2-diamino-4-nitrobenzene
- 1 - amino-2 - ß-hydroxye thy lamino-5-nitrobenzene
- 1, 2-bis (ß-hydroxyethylamino) -4-nitrobenzene
- l-amino-2-tris(hydroxymethyl)methylamino-5-nitro-
benzene
- 1-hydroxy-2-amino-5-nitrobenzene
- 1-hydroxy-2-amino-4-nitrobenzene
- 1-hydroxy-3-nitro-4-aminobenzene
- l-hydroxy-2-amino-4,6-dinitrobenzene
- l-(3-hydroxyethyloxy-2-ß-hydroxyethylamino-5-nitro¬
benzene
- 1-me thoxy-2-ß-hydroxyethylamino-5-nitrobenzene
- l-(3-hydroxyethyloxy-3-me thylamino-4-nitrobenzene
- l-ß,y-dihydroxypropyloxy-3-methylamino-4-nitrobenzene
- l-p-hydroxyethylamino-4-ß,y-dihydroxypropyloxy-2-
nitrobenzene
- 1-ß, y-dihydroxypropylamino-4-trif luoromethy 1-2-nitro¬
benzene
- l-p-hydroxyethylamino-4-trifluoromethyl-2-
nitrobenzene
- l-ß-hydroxyethylamino-3-methy 1-2-nitrobenzene
- 1 - (3 -aminoethylamino- 5 -me thoxy- 2 -nitrobenzene
- 1-hydroxy-2-chloro-6-ethylamino-4-nitrobenzene
- 1-hydroxy-2-chloro-6-amino-4-nitrobenzene
- l-hydroxy-6-bis (ß-hydroxyethyl) amino-3-nitrobenzene
- l-ß-hydroxyethylamino-2-nitrobenzene
- l-hydroxy-4-ß-hydroxyethylamino-3-nitrobenzene .
Among the azo direct dyes that can be used according to the invention, mention may be made of the cationic azo dyes described in patent applications WO 95/15144,
WO-95/01772 and EP-714954, the content of which forms an integral part of the invention.
Among these compounds, mention may most particularly be made of the following dyes:
- 1,3-dimethyl-2-[[4-(dimethylamino)phenyl]azo]-1H-
imidazolium chloride,
- 1,3-dimethyl-2-[(4-aminophenyl)azo]-IH-imidazolium
chloride,
- l-methyl-4-[(methylphenylhydrazono)methyl]pyridinium
methyl sulphate.
Among the azo direct dyes, mention may also be made of the following dyes, described in the Colour Index International 3rd edition:
- Disperse Red 17
- Acid Yellow 9
- Acid Black 1
- Basic Red 22
- Basic Red 76
- Basic Yellow 57
- Basic Brown 16
- Acid Yellow 36
- Acid Orange 7
- Acid Red 33
- Acid Red 35
- Basic Brown 17
- Acid Yellow 23
- Acid Orange 24
- Disperse Black 9.
Mention may also be made of 1-(4'-aminodiphenylazo)-2-methyl-4bis(p-hydroxyethyl)aminobenzene and 4-hydroxy-3-(2-methoxyphenylazo)-1-naphthalenesulphonic acid.
Among the quinone direct dyes, mention may be made of the following dyes:
- Disperse Red 15
- Solvent Violet 13
- Acid Violet 43
- Disperse Violet 1
- Disperse Violet 4
- Disperse Blue I
- Disperse Violet 8
- Disperse Blue 3
- Disperse Red 11
- Acid Blue 62
- Disperse Blue 7
- Basic Blue 22
- Disperse Violet 15
- Basic Blue 99
and also the following compounds:
- l-N-methylmorpholiniumpropylamino-4-hydroxy-
anthraquinone
- l-aminopropylamino-4-methylaminoanthraquinone
- 1-aminopropylaminoanthraquinone
- 5-p-hydroxyethyl-l,4-diaminoanthraquinone
- 2-aminoethylaminoanthraquinone
- 1, 4-bis (ß,y-dihydroxypropylamino) anthraquinone .
Among the azine dyes, mention may be made of the following compounds:
- Basic Blue 17
- Basic Red 2.
Among the triarylmethane dyes that can be used according to the invention, mention may be made of the following compounds:
- Basic Green 1
- Acid Blue 9
- Basic Violet 3
- Basic Violet 14
- Basic Blue 7
- Acid Violet 49
- Basic Blue 26
- Acid Blue 7.
Among the indoamine dyes that can be used according to the invention, mention may be made of the following compounds:
- 2-ß-hydroxyethylamino-5- [bis (ß-4' -hydroxyethyl) -
amino]anilino-1,4-benzoquinone
- 2-ß-hydroxyethylamino-5- (2' -methoxy-4' -amino) anilino-
1,4-benzoquinone
- 3-N(2'-chloro-4'-hydroxy)phenylacetylamino-6-methoxy-
1,4-benzoquinoneimine
- 3-N(3'-chloro-4'-methylamino)phenylureido-6-methyl-
I,4-benzoquinoneimine
- 3-[4'-N- (ethyl,carbamylmethyl)amino]phenylureido-6-
methyl-1,4-benzoquinoneimine.
Among the natural direct dyes that can be used according to the invention mention may be made of lawsone, juglone, alizarine, purpurine, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin and apigenidin. Extracts or decoctions containing these natural dyes may also be used, and especially henna-based poultices or extracts.
The direct dyes may be fluorescent. By way of fluorescent dyes, mention may be made of the compounds having the following structures I or II:
(Formula Removed)
with R1, R2, R3; R'1, R2 and R'3 denoting a C1-C10, and preferably C1-C4 alkyl radical; X" denoting a counterion of an inorganic and/or organic acid.
The direct dye(s) preferably represent approximately from 0.001% to 20% by weight of the total weight of the
composition, and preferably approximately from 0.005% to 10% by weight.
For the purpose of the present invention, the term "bioheteropolysaccharides" is intended to mean substances synthesized by fermentation of sugars by microorganisms. The bioheteropolysaccharides in particular commonly have units chosen from mannose, glucose, glucuronic acid and galacturonic acid units in their chain, these units being optionally acylated.
Mention may in particular be made of the xanthan gums produced by the bacterium Xanthomonas campestri and the mutants and variants thereof.
These xanthan gums generally have a molecular weight of between 1 000 000 and 50 000 000.
Mention may also be made of the sclerotium gums produced by Sclerotium rolfsii, the gellan gums produced by Pseudomonas elodea or Sphingomonias, the pullulan gums produced by Aureobacidium pullulens, the curdlan gums produced by the Alcaligenes of Faecalis myxogenes type, the xanthan gums produced by numerous organisms, including Leuconostoc mesenteroides and Leuconostoc dextrantum, the grifolan gums produced by Grifola frondara, the lentinan gums produced by Lentinus edodes, the schizophyllan gums produced by Schizophyllum commine, the spirulinan gums produced by Spirulina sybsyla and the krestin gums produced by Coriates versicolor.
Xanthan and sclerotium gums are preferably used. Sclerotium gums are even more preferably used.
The bioheteropolysaccharide is generally included in the dye composition in amounts ranging from 0.01% to 10% by weight of the total weight of the composition, preferably between 0.1% and 4%.
The composition according to the invention comprises one or more cationic surfactants that are well known per se, such as optionally polyoxyalkylenated primary, secondary or tertiary fatty amine salts, quaternary ammonium salts, and mixtures thereof.
According to the invention, the cationic surfactants are nonpolymeric, i.e. are not obtained by polymerization of monomers other than alkylene oxides or by grafting of cationic groups onto existing natural pigments.
By way of fatty amines, mention may in particular be made of alkylamidoamines such as, for example, (C8-C50) alkylamido (C1-C6) dialkylamines, and in particular stearamidopropyldimethylamine (Mackine 301 sold by Maclntyre),
By way of quaternary ammonium salts, mention may in particular be made, for example, of:
those having the general formula (V) below:
(Formula Removed)

in which the symbols R1 to R4, which may be identical or different, represent a linear or branched aliphatic radical containing from 1 to 30 carbon atoms or an aromatic radical such as aryl or alkylaryl. The aliphatic radicals may comprise heteroatoms such as, especially, oxygen, nitrogen, sulphur and halogens. The aliphatic radicals are chosen, for example, from (C1-C30) alkyl, alkoxy, (C2-C6) polyoxyalkylene, alkylamide, (C12-C22) alkylamido (C2-C6) alkyl, (C12-C22) alkyl acetate and hydroxyalkyl radicals, containing from
about 1 to 30 carbon atoms; X is an anion chosen from the group of halides, phosphates, acetates, lactates, (C2-C6)alkyl sulphates and alkylsulphonates or alkylarylsulphonates;
quaternary ammonium salts of imidazoline, for instance those of formula (VI) below:
(Formula Removed)
in which R5 represents an alkenyl or alkyl radical containing from 8 to 30 carbon atoms, for example fatty acid derivatives of tallow or of coconut, R6 represents a hydrogen atom, a C1-C4 alkyl radical or an alkenyl or alkyl radical containing from 8 to 30 carbon atoms, RT represents a C1-C4 alkyl radical, R8 represents a hydrogen atom or a C1-C4 alkyl radical, and X" is an anion chosen from the group of halides, phosphates, acetates, lactates, alkyl sulphates, alkylsulphonates and alkylarylsulphonates. Preferably, R5 and R6 denote a mixture of alkenyl or alkyl radicals containing from 12 to 21 carbon atoms, for example fatty acid derivatives of tallow, R7 denotes methyl and R8 denotes hydrogen. Such a product is, for example, Quaternium-27 (CTFA 2002), Quaternium-87 (CTFA 2002) or Quaternium-83 (CTFA 2002), which are sold under the name "Varisoft®" W575PG by the company Goldschmidt,
diquaternary ammonium salts of formula (VII):
(Formula Removed)
in which R9 denotes an aliphatic radical containing from about 16 to 30 carbon atoms, R10, RH, R12, RIS and R14, which may be identical or different, are chosen from hydrogen and an alkyl radical containing from 1 to 4 carbon atoms, and X" is an anion chosen from the group of halides, acetates, phosphates, nitrates, ethyl sulphates and methyl sulphates. Such diquaternary ammonium salts in particular comprise propanetallow-diammonium dichloride;
quaternary ammonium salts comprising at least one ester function, such as those of formula (VIII) below:
(Formula Removed)
in which:
R15 is chosen from C1-C6 alkyl radicals and C1-C6
hydroxyalkyl or dihydroxyalkyl radicals;
R16 is chosen from:
- linear or branched, saturated or unsaturated C1-C22
hydrocarbon-based radicals R2o/
- a hydrogen atom,
R17 is chosen from:
- linear or branched, saturated or unsaturated Ci-Ce
hydrocarbon-based radicals R22,
- a hydrogen atom,
R17/ R19 and R21, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C7-C21 hydrocarbon-based radicals; r, n and p, which may be identical or different, are integers ranging from 2 to 6;

y is an integer ranging from 1 to 10;
x and z, which may be identical or different, are
integers ranging from 0 to 10;
X" is a simple or complex, organic or inorganic anion;
with the proviso that the sum x + y + z is from 1 to
15, that when x is 0, then R16 denotes R20 and that when
z is 0, then RIB denotes R22.
The alkyl radicals R15 may be linear or branched, and more particularly linear.
Preferably, R15 denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl radical, and more particularly a methyl or ethyl radical.
Advantageously, the sum x + y + z is from 1 to 10.
When R16 is a hydrocarbon-based radical R20, it may be long and contain from 12 to 22 carbon atoms, or short and contain from 1 to 3 carbon atoms.
When R18 is a hydrocarbon-based radical R22, it preferably contains 1 to 3 carbon atoms.
Advantageously, R17, R19 and R21, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C11-C21 hydrocarbon-based radicals, and more particularly from linear or branched, saturated or unsaturated C11-C21 alkyl and alkenyl radicals.
Preferably, x and z, which may be identical or different, are 0 or 1.
Advantageously, y is equal to 1.
Preferably, r, n and p, which may be identical or different, are equal to 2 or 3 and even more particularly equal to 2.

The anion X" is preferably a halide (chloride, bromide or iodide) or a C1-C4 alkyl sulphate, more particularly methyl sulphate. However, methanesulphonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate or lactate, or any other anion that is compatible with the ammonium containing an ester function may be used.
The anion X" is even more particularly chloride or methyl sulphate.
Use is made more particularly in the composition according to the invention of the ammonium salts of formula (IV) in which:
- R15 denotes a methyl or ethyl radical,
- x and y are equal to 1;
- z is equal to 0 or 1;
- r, n and p are equal to 2;
- R16 is chosen from:
- methyl, ethyl or C14~C22 hydrocarbon-based radicals,
- a hydrogen atom;
- R18 is chosen from:
- a hydrogen atom;
R17 R19 and R21, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C13-C17 hydrocarbon-based radicals, and preferably from linear or branched, saturated or unsaturated C13-C17 alkyl and alkenyl radicals .
The hydrocarbon-based radicals are advantageously
linear.
Examples of compounds of formula (VIII) that may be
mentioned include the salts (especially chloride or
methyl sulphate) of diacyloxyethyldiruethylaininonium, of diacyloxyethylhydroxyethylmethylammonium, of monoacyl-oxyethyldihydroxyethylmethylammonium, of triacyloxy-ethylmethylammonium, of monoacyloxyethylhydroxyethyl-diraethylaramonium, and mixtures thereof. The acyl radicals preferably contain 14 to 18 carbon atoms and are more particularly derived from a plant oil, for instance palm oil or sunflower oil. When the compound contains several acyl radicals, these radicals may be identical or different.
These products are obtained, for example, by direct esterification of optionally oxyalkylenated triethanol-amine, triisopropanolamine, alkyldiethanolamine or alkyldiisopropanolamine onto fatty acids or onto mixtures of fatty acids of plant or animal origin, or by transesterification of the methyl esters thereof. This esterification is followed by a quaternization using an alkylating agent such as an alkyl halide (preferably a methyl or ethyl halide), a dialkyl sulphate (preferably dimethyl or diethyl sulphate), methyl methanesulphonate, methyl para-toluene-sulphonate, glycol chlorohydrin or glycerol chlorohydrin.
Such compounds are sold, for example, under the names
® ®
Dehyquart by the company Cognis, Stepanquat by the
® company Stepan, Noxamium by the company Ceca, and
® Rewoquat WE 18 by the company Rewo-Goldschmidt.
The composition according to the invention may
preferably contain a mixture of quaternary ammonium
mono-, di- and triester salts with a weight majority of
diester salts.
Examples of mixtures of ammonium salts that may be used include the mixture containing 15% to 30% by weight of acyloxyethyldihydroxyethylmethylammonium methyl sulphate, 45% to 60% of diacyloxyethylhydroxyethyl-
methylammonium methyl sulphate and 15% to 30% of triacyloxyethylmethylammonium methyl sulphate, the acyl radicals containing from 14 to 18 carbon atoms and being derived from optionally partially hydrogenated palm oil.
It is also possible to use the ammonium salts comprising at least one ester function described in patents US-A-4 874 554 and US-A-4 137 180.
Among the quaternary ammonium salts mentioned above that are preferably used are those corresponding to formula (V) or of formula (VIII). Mention may especially be made firstly of tetraalkylammonium chlorides, for instance dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl radical contains from about 12 to 22 carbon atoms, in particular behenyltrimethylammonium, distearyldimethyl-ammonium, cetyltrimethylammonium or benzyldimethyl-stearylammonium chlorides, or alternatively, secondly, palmitylamidopropyltrimethylammonium chloride or stearamidopropyldimethyl(myristyl acetate)ammonium chloride corresponding to Quaternium-70 (CTFA 2002) sold under the name Ceraphyl® 70 by the company ISP.
The cationic surfactants that are particularly preferred in the composition of the invention are chosen from quaternary ammonium salts, and in particular from behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, Quaternium-83, Quaternium-87, behenylamidopropyl-2,3-dihydroxypropyl-dimethylammonium chloride, palmitylamidopropyl-trimethylammonium chloride and stearamidopropyl-dimethylamine.
The composition according to the invention preferably comprises the cationic surfactant(s) in an amount ranging from 0.01% to 10% by weight, preferably from
0.1% to 4% by weight, relative to the total weight of the composition.
Preferably, the cationic surfactants/bio-polysaccharide(s) weight ratio is greater than 1 and ideally between 1 and 10.
The amphoteric surfactants contained in the composition of the invention are surfactants that are known per se in the field of the direct dyeing of keratin fibres.
These amphoteric surfactants may in particular be aliphatic secondary or tertiary amine derivatives, in which the aliphatic radical is a linear or branched chain containing 8 to 22 carbon atoms and containing at least one water-soluble anionic group (for example, carboxylate, sulphonate, sulphate, phosphate or phosphonate); mention may also be made of (C8-C20)alkyl-betains, sulphobetains, (C8-C20) alkylamido (C1-C6) alkyl-betains or (C8-C20) alkylamido (C1-C6) alkylsulphobetains .
Among the amine derivatives, mention may be made of the products sold under the name Miranol®, as described in patents US-2 528 378 and US-2 781 354 and having the structures:
R2 -CONHCH2CH2 -N(R3)(R4)(CH2COO-) (2)
in which: R2 denotes an alkyl radical derived from an acid R2-COOH present in hydrolysed coprah oil, or a heptyl, nonyl or undecyl radical, R3 denotes a beta-hydroxyethyl group and R4 denotes a carboxymethyl group; and
R2.-CONHCH2CH2-N(B)(C) (3)
in which:
B represents -CH2CH2OX' , C represents -(CH2)Z-Y', with
z = 1 or 2,
X' denotes the group -CH2CH2-COOH or a hydrogen atom,
Y' denotes -COOH or the radical -CH2-CHOH-S03H,
R2 denotes an alkyl radical of an acid R9 -COOH present
in coprah oil or in hydrolysed linseed oil, a alkyl
radical, in particular a C7, C9, C11 or C13 alkyl
radical, a C17 alkyl radical in its iso form or a C17
radical which is unsaturated.
These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the name Disodium Cocoamphodiacetate, Disodium Lauroamphodiacetate, Disodium Caprylamphodiacetate, Disodium Capryloampho-diacetate, Disodium Cocoamphodipropionate, Disodium Lauroamphodipropionate, Disodium Caprylampho-dipropionate, Disodium Capryloamphodipropionate, Lauroamphodipropionic acid and Cocoamphodipropionic acid.
By way of example, mention may be made of the cocoamphodiacetate sold under the trade name Miranol® C2M concentrate by the company Rhodia.
The preferred amphoteric surfactants are alkylbetains, alkylamidoalkylbetains and coamphodiacetate.
More preferably, the amphoteric surfactant is an alkylamidoalkylbetain.
The composition according to the invention preferably comprises the amphoteric surfactant(s) in an amount ranging from 0.01% to 20% by weight, preferably from 5% to 15% by weight, relative to the total weight of the composition.
The composition of the invention may comprise other surfactants, for example nonionic surfactants. By way of example, mention may be made of the nonionic
surfactants described in the "Handbook of Surfactants" by M.R. Porter, published by Blackie & Son (Glasgow and London), 1991, pp 116-178. Thus, they may in particular be chosen from alcohols, alpha-diols, alkylphenols or polyethoxylated, polypropoxylated or polyglycerylated fatty acids having a fatty chain containing, for example, 8 to 18 carbon atoms, it being possible for the number of ethylene oxide or propylene oxide groups to range in particular from 2 to 50 and for the number of glycerol groups to range in particular from 2 to 30. Mention may also be made of copolymers of ethylene oxide and of propylene oxide, condensates of ethylene oxide and of propylene oxide on fatty alcohols; polyethoxylated fatty amides preferably having from 2 to 30 mol of ethylene oxide, polyglycerylated fatty amides comprising on average 1 to 5 glycerol groups, and in particular 1.5 to 4; oxyethylenated fatty acid esters of sorbitan having from 2 to 30 mol of ethylene oxide; fatty acid esters of sucrose, fatty acid esters of polyethylene glycol, alkylpolyglycosides, N-alkyl glucamine derivatives, amine oxides such as (C10-C14) alkylamine oxides or N-acylaminopropyl-morpholine oxides. Preferably, alkylpolyglycosides or oxyalkylenated fatty alcohols are used.
The composition of the present invention may also contain oxidation bases and couplers conventionally used for oxidation dyeing.
By way of example, mention may be made of para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases, and addition salts thereof.
The couplers are, for example, meta-phenylenediamine couplers, meta-aminophenol couplers, meta-diphenol couplers, naphthalene couplers, heterocyclic couplers and addition salts thereof.
When they are present, the bases and the couplers are each generally present in an amount of between approximately 0.001% and 10% by weight of the total weight of the dye composition, preferably between 0.005% and 6%.
The medium suitable for dyeing, also referred to as dye support, generally consists of water or of a mixture of water and at least one organic solvent in order to solubilize the compounds that would not be sufficiently soluble in water. By way of organic solvent, mention may, for example, be made of Ci~C4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers, such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monomethyl ether, and also aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.
For the dyeing of human keratin fibres, the dyeing medium is an appropriate cosmetic medium.
The solvents may be present in proportions preferably of between approximately 1% and 40% by weight relative to the total weight of the dye composition, and even more preferably between approximately 5% and 30% by weight.
The dyeing composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, thickeners other than the bioheterosaccharides used in the present invention, antioxidants, penetrating agents, sequestering agents, fragrances, buffers, dispersing agents, conditioning agents such as, for example, modified or nonmodified,
volatile or nonvolatile silicones, film-forming agents, ceramides, preserving agents or opacifiers.
These above adjuvants are generally present in an amount, for each of them, of between 0.01% and 20% by weight relative to the weight of the composition.
Of course, those skilled in the art will take care to select this or these optional additional compound(s) in such a way that the advantageous properties intrinsically associated with the oxidation dye composition in accordance with the invention are not, or are not substantially, impaired by the addition(s) envisaged.
The pH of the dye composition in accordance with the invention is generally between approximately 3 and 12, and preferably between approximately 5 and 11.
It may be adjusted to the desired value by means of acidifying or basifying agents normally used in the dyeing of keratin fibres, or else by means of conventional buffer systems.
Among the acidifying agents, mention may, by way of example, be made of inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid or lactic acid, and sulphonic acids.
Among the basifying agents, mention may, by way of example, be made of aqueous ammonia, alkali metal carbonates, alkanolamines such as mono-, di- and triethanolamines and derivatives thereof, sodium hydroxide or potassium hydroxide, and the compounds of formula (III) below:
(Formula Removed)
in which W is a propylene residue optionally substituted with a hydroxyl group or a Ci-C4 alkyl radical; R6, R7, RS and R9/ which may be identical or different, represent a hydrogen atom, a Ci-C4 alkyl radical or a Ci-C4 hydroxyalkyl radical.
The dye composition according to the invention may be in various forms, such as in the form of liquids, creams or gels, or in any other form suitable for dyeing keratin fibres, and in particular human hair.
A subject of the invention is also a direct dyeing process which comprises the application of a composition as defined above to keratin fibres. After a leave-on time, the keratin fibres are rinsed, allowing coloured fibres to appear. The leave-on time is generally between approximately 3 and 50 minutes, preferably approximately 5 and 30 minutes.
When the dye composition comprises an oxidation base and/or a coupler, the dye composition may then contain an oxidizing agent. The oxidizing agents conventionally used for the oxidation dyeing of keratin fibres are, for example, hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulphates, peracids and oxidase enzymes, among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases, and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred.
The oxidizing agent may be added to the composition of the invention just at the moment of use, or it may be used from an oxidizing composition containing it,
applied simultaneously with or sequentially to the composition of the invention. The oxidizing composition may also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.
The pH of the oxidizing composition containing the oxidizing agent is such that, after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibres preferably ranges between approximately 3 and 12, and even more preferably between 5 and 11. It may be adjusted to the desired value by means of acidifying or basifying agents normally used in the dyeing of keratin fibres and as defined above.
The composition which is finally applied to the keratin fibres may be in various forms, such as in the form of liquids, creams or gels, or in any other form suitable for dyeing keratin fibres, and in particular human hair.

EXAMPLES
The following compositions were prepared, the amounts being given in amounts by weight, unless otherwise indicated.
Example 1
(Table Removed)
This composition is then applied to locks of natural grey hair containing 90% of white hairs, at ambient temperature. After 30 minutes, the locks of hair are rinsed with running water and then dried.
The locks were dyed in a relatively nonselective intense auburn shade. The hair was soft.
Example 2
(Rable Removed)
This composition is then applied to locks of natural grey hair containing 90% of white hairs, at ambient temperature. After 30 minutes, the locks of hair are rinsed with running water and then dried.
The locks were tinted in a relatively nonselective light chestnut shade of good intensity. The hair was soft.
Example 3

(Rable Removed)
This composition is then applied to locks of natural grey hair containing 90% of white hairs, at ambient temperature. After 30 minutes, the locks of hair are rinsed with running water and then dried.
The locks were tinted in a relatively nonselective intense golden shade. The hair was soft.
For each of these examples, the same type of result is obtained when the 1% of sclerotium gum is replaced with 1% of xanthan gum.
A composition of the present invention containing dyeing keratin fibers such as herein described along with at least one direct dye, at least one bioheteropolysaccharide, at least one cationic surfactant and at least one amphoteric surfactant, which showed surprising and unexpected, effects. Therefore, the said composition is synergistic in nature.

WE CLAIM
1. Composition for dyeing keratin fibres, comprising
at least one direct dye, at least one
bioheteropolysaccharide, at least one cationic
surfactant and at least one amphoteric surfactant.
2. Composition according to Claim 1, in which the
direct dye is chosen from neutral, acidic or
cationic nitrobenzene direct dyes, neutral, acidic
or cationic azo direct dyes, quinone direct dyes,
azine direct dyes, triarylmethane direct dyes,
indoamine direct dyes and natural direct dyes.
3. Composition according to Claim 1 or 2, in which
the amount of direct dyes is between approximately
0.001% and 20% by weight of the total weight of
the composition, preferably between approximately
0.005% and 10% by weight.
4. Composition according to any one of the preceding
claims, in which the bioheteropolysaccharide is
chosen from xanthan gums, sclerotium gums, gellan
gums, pullulan gums, curdlan gums, grifolan gums,
lentinan gums, schizophyllan gums, spirulinan gums
and krestin gums.
5. Composition according to any one of the preceding
claims, in which the bioheteropolysaccharide is
xanthan gum.
6. Composition according to any one of the preceding
claims, in which the bioheteropolysaccharide is a
sclerotium gum.
7. Composition according to any one of the preceding
claims, in which the amount of
bioheteropolysaccharide is between 0.01% and 10%by weight of the total weight of the composition, preferably between 0.1% and 4%.
8. Composition according to any one of the preceding
claims, in which the cationic surfactant (s) is
(are) chosen from primary, secondary or tertiary
fatty amine salts, quaternary ammonium salts, and
mixtures thereof.
9. Composition according to Claim 7, in which the
cationic surfactant is chosen from primary,
secondary or tertiary fatty amine salts,
quaternary ammonium salts, and mixtures thereof.
10. Composition according to Claim 7, in which the
cationic surfactant is chosen from behenyl-
trimethylammonium chloride, cetyltrimethylammonium
chloride, quaternium-83, quaternium-87, behenyl-
amidopropyl-2,3-dihydroxypropyldimethylammonium
chloride, palmitylamidopropyltrimethylammonium
chloride and stearamidopropyldimethylamine.
11. Composition according to any one of the preceding
claims, in which the amount of cationic surfactant
is between 0.01% and 10% by weight, preferably
from 0.1% to 4% by weight, relative to the total
weight of the composition.
12 . Composition according to any one of the preceding claims, in which the amphoteric surfactant is chosen from alkylbetains, alkylamidoalkylbetains and coamphodiacetate.
13. Composition according to any one of the preceding claims, in which the nonionic or amphoteric surfactant(s) is (are) present in an amount ranging from 0.01% to 20% by weight, preferably from 5% to 15% by weight, relative to the total weight of the composition.
14. , Composition according to any one" of the preceding
claims, in which the cationic surfactants/bio-heteropolysaccharides weight ratio is greater than 1.Composition according to any one of the preceding
claims, comprising at least one oxidation base
and/or at least one coupler.
15. Composition according to any one of the preceding
claims, comprising at least one oxidizing agent.
16. Process for dyeing keratin fibres in which the
composition as defined in any one of Claims 1 to
15 is applied to the fibres for a period of time
sufficient to develop the desired coloration.
18. Composition for dyeing keratin fibres and process for dyeing keratin fibres,
substantially as herein described, particularly with reference to, and as illustrated in
the foregoing examples.