WO2016084971A1

WO2016084971A1 - Silicone oil-rich composition

Info

Publication number: WO2016084971A1
Application number: PCT/JP2015/083515
Authority: WO
Inventors: Kenta Kitsuka; Daisuke Misu; Shoji Maruyama; Hidetoshi Yamada
Original assignee: L'oreal
Priority date: 2014-11-26
Filing date: 2015-11-20
Publication date: 2016-06-02
Also published as: JP2016098220A

Abstract

The present invention relates to a composition, in particular a cosmetic composition, which is preferably used for keratin fibers such as hair, comprising: (a) at least one silicone oil; (b) at least one dye; (c) at least one thickener; and (d) water, wherein the amount of the (a) silicone oil is 25% by weight or more relative to the total weight of the composition. The composition according to the present invention can provide improved color uptake.

Description

DESCRIPTION

SILICONE OIL-RICH COMPOSITION TECHNICAL FIELD

The present invention relates to a composition comprising a relatively large amount of silicone oil, which is preferably used for keratin fibers such as hair. BACKGROUND ART

In addition to higher performance of products for bleaching or coloring hair, consumers of such products are more and more sensitive to the usage quality of the products. From the viewpoint of usage quality, the following, for example, can be regarded as major drawbacks: malodor from ammonia, which is typically contained as an alkaline agent in conventional hair bleaching or coloring products; difficulty in self-handling conventional hair bleaching or coloring products in the form of a liquid, gel or cream; risk of the product dripping off during application to the hair; and the like. In order to reduce the problems occurring with the pungent odor of ammonia, total or partial replacement of this alkaline agent with another one, such as monoemanolamine, has been proposed. However, the consequence of this modification often results in a decrease of the bleaching or coloring efficiency of the products. Recently, as an alternative to hair dyeing or bleaching products based on ammonia as an alkaline agent, compositions comprising a large amount of fatty materials have been proposed. Such compositions may comprise more than 20% by weight of fatty compounds, relative to the total weight of the composition, in combination with an alkaline agent, with or without an oxidative dye. Such compositions can provide high bleaching or coloring ability with a relatively small amount of alkaline agent and advantageously without ammonia.

Also, hair color treatment products using a direct dye are widely used there days, but the products have an issue of less color uptake as compared to permanent or semi-permanent hair color using an oxidative dye.

DISCLOSURE OF INVENTION

However, there is still a need to further improve the color uptake of the above compositions including a large amount of fatty materials.

An objective of the present invention is to provide a composition, in particular a cosmetic composition, which is preferably used for keratin fibers such as hair, with improved color uptake.

The above objective of the present invention can be achieved by a composition, in particular a cosmetic composition, which is preferably used for keratin fibers such as hair, comprising: (a) at least one silicone oil;

(b) at least one dye;

(c) at least one thickener; and

(d) water,

wherein

the amount of the (a) silicone oil is 25% by weight or more relative to the total weight of the composition.

The (a) silicone oil may be selected from the group consisting of polydialkylsiloxanes,

polyalkylarylsiloxanes, polydiarylsiloxanes, and organomodified polysiloxanes comprising at least one functional moiety chosen from poly(oxyalkylene) moieties, amine moieties, alkoxy moieties, hydroxylated moieties, acyloxyalkyl moieties, carboxylic acid moieties,

hydroxyacylamino moieties, acrylic moieties, polyamine moieties, and oxazoline moieties. The amount of the (a) silicone oil may range from 25 to 90% by weight, preferably from 30 to 80% by weight, and more preferably from 35 to 70% by weight, relative to the total weight of the composition.

The (b) dye may be selected from synthetic direct dyes and oxidative dyes.

The synthetic direct dyes may be selected from the group consisting of: cationic direct dyes, nonionic direct dyes, and anionic direct dyes.

The oxidative dyes may be selected from oxidation bases and couplers.

The oxidation bases may be selected from ortho- and para-phenylenediarnines, double bases, ortho- and para-aminophenols, heterocyclic bases, and acid addition salts thereof.

The couplers may be selected from meta-aminophenols, meta-phenylenediamines, meta-diphenols, naphthols, heterocyclic couplers, and acid addition salts thereof.

The amount of the (b) dye may range from 0.001 to 10% by weight, preferably from 0.01 to 5% by weight, and more preferably from 0.1 to 3% by weight, relative to the total weight of the composition.

The (c) thickener may be selected from polysaccharides.

The amount of the (c) thickener may range from 0.001 to 15% by weight, preferably from 0.01 to 10% by weight, and more preferably from 0.1 to 5% by weight, relative to the total weight of the composition.

The composition according to the present invention may further comprise (e) at least one surfactant, preferably at least one nonionic surfactant.

The amount of the (e) surfactant may range from 0.1 to 30% by weight, preferably from 0.5 to 25% by weight, and more preferably from 1 to 20% by weight, relative to the total weight of the composition.

It is preferable that the composition according to the present invention be intended for dyeing keratin fibers, preferably hair.

Furthermore, the present invention also relates to a process for keratin fibers, preferably hair, comprising the steps of applying the composition according to the present invention to the keratin fibers.

BEST MODE FOR CARRYING OUT THE INVENTION

After diligent research, the inventors have discovered that it is possible to provide a composition, in particular a cosmetic composition, which is preferably used for keratin fibers such as hair, with improved color uptake, if the composition includes a combination of selected specific ingredients under specific conditions.

Thus, the present invention is a composition, in particular a cosmetic composition, which is preferably used for keratin fibers such as hair, comprising:

(a) at least one silicone oil;

(b) at least one dye;

(c) at least one thickener; and

(d) water,

wherein

The composition according to the present invention can provide improved color uptake. Thus, the keratin fibers treated with the composition according to the present invention can be effectively colored.

In addition, if the (b) dye is selected from oxidative dyes, the composition according to the present invention can provide enhanced coloring ability with a relatively small amount of alkaline agent even without ammonia.

Furthermore, due to the presence of the thickener, the composition according to the present invention can have an appropriate viscosity. Thus, it is easy for the composition according to the present invention to be applied onto keratin fibers such as hair with hand or fingers, and the risk of the composition according to the present invention dripping off during the application to the keratin fibers can be reduced.

Hereinafter, the composition according to the present invention will be explained in a more detailed manner.

[Silicone Oil] The composition according to the present invention comprises at least one (a) silicone oil. Here, "oil" means a fatty compound or substance which is in the form of a liquid at room temperature (25°C) under atmospheric pressure (760 mmHg). As the silicone oils, those generally used in cosmetics may be used alone or in combination thereof.

The (a) silicone oil may be selected from the group consisting of polydialkylsiloxanes such as polydimethylsiloxanes (PDMS), polyalkylarylsiloxanes such as phenyltrimethicone,

polydiarylsiloxanes, and organo-modified polysiloxanes comprising at least one functional moiety chosen from poly(oxyalkylene) moieties, amine moieties, alkoxy moieties, hydroxylated moieties, acyloxyalkyl moieties, carboxylic acid moieties, hydroxyacylamino moieties, acrylic moieties, polyamine moieties, and oxazoline moieties.

Silicone oils suitable for use according to the present invention include, but are not limited to, volatile and non- volatile, cyclic, linear, and branched silicones, optionally modified with organic moieties.

Silicone oils that may be used according to the present invention may be soluble or insoluble in the composition and may be, for instance, polyorganosiloxanes that are not soluble in the composition of the present invention. .

Silicones or organopolysiloxanes are defined, for instance, by Walter NOLL in "Chemistry and Technology of Silicones" ( 1968), Academic Press. They may be volatile or non- volatile. When they are volatile, the silicone oils may be chosen from those having a boiling point ranging from 60°C to 260°C, for example:

(i) cyclic polydialkylsiloxanes comprising from 3 to 7, for instance, from 4 to 5 silicon atoms. Non-limiting examples of such siloxanes include octamethylcyclotetrasiloxane marketed, for instance, under the trade name VOLATILE SILICONE® 7207 by UNION CARBIDE and SILBIONE® 70045 V2 by RHODIA, decamethylcyclopentasiloxane marketed under the trade name VOLATILE SILICONE® 7158 by UNION CARBIDE, and SILBIONE® 70045 V5 by RHODIA, as well as mixtures thereof. Cyclomethicones may also be used, for example, those marketed under the references DC 244, DC 245, DC 344, DC 345, and DC 246 by DOW

CORNING. Cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type may also be used, such as SILICONE VOLATILE® FZ 3109 marketed by UNION CARBIDE, of formula

wherein: Si— 0—; and

CH₃

Si— ·

C₈H_l7

Combinations of cyclic polydialkylsiloxanes with silicon derived organic compounds may also be used, such as an octamethylcyclotetrasiloxane and tetralrimethylsilylpentaerythritol (50/50) mixture, and an octamethylcyclotetrasiloxane and oxy-l, -(hexa-2,2,2',2',3,3'-trimethylsilyloxy) bis-neopentane mixture; and

(ii) linear volatile polydialkylsiloxanes comprising from 2 to 9 silicon atoms. A

non-limiting example of such a compound is decamethyltetrasiloxane marketed, for instance, under the trade name " SH-200" by TORAY SILICONE. Silicones belonging to this class are also described, for example, in Cosmetics and Toiletries, Vol. 91, Jan. 76, P. 27-32--TODD & BYERS "Volatile Silicone Fluids for Cosmetics" .

In at least one embodiment, the silicones may be chosen from non-volatile silicones, such as polydialkylsiloxanes, polyalkylarylsiloxanes, polydiarylsiloxanes, and polyorganosiloxanes modified with the hereabove organofunctional moieties.

According to another embodiment, the silicones are chosen from polydialkylsiloxanes, for example, polydimethylsiloxanes with trimethylsilyl end groups known under the trade name dimethicones.

Non-limiting examples of commercial products corresponding to such polydialkylsiloxanes include:

SILBIONE® fluids of the series 47 and 70 047 and MIRASIL® fluids marketed by RHODIA, for example 70 047 fluid V 500 000;

fluids of the MIRASIL® series marketed by RHODIA;

fluids of the series 200 marketed by DOW CORNING such as DC200, with a viscosity of 60,000 mm²/s;

VISCASIL® fluids of GENERAL ELECTRIC and some fluids of the SF series (e.g., SF 96 and SF 18) of GENERAL ELECTRIC; and

the fluid marketed under the reference DC 1664 by DOW CORNING.

Polydimethylsiloxanes with dimethylsilanol end groups may also be used, for example, those sold under the trade name dimethiconol (CTFA), such as fluids of the 48 series marketed by RHODIA.

Products marketed under the trade names "ABIL Wax® 9800 and 9801 " by GOLDSCHMIDT belonging to this class of polydialkylsiloxanes, that are polydialkyl (CpC₂o) siloxanes, may also be used. Polyalkylarylsiloxanes may be chosen from polydimethyl/methylphenylsiloxanes, linear and/or branched polydimethyl/diphenyl siloxanes. Non-limiting examples of such polyalkylarylsiloxanes include the products marketed under the following trade names:

SILBIONE® fluids of the 70 641 series from RHODIA; RHODORSIL® fluids of the 70 633 and 763 series from RHODIA;

phenyltrimethicone fluid marketed under the reference DOW CORNING 556 COSMETIC GRADE FLUID by DOW CORNING;

PK series silicones from BAYER, for example, the PK20 product;

PN, PH series silicones from BAYER, for example, the PN1000 and PHI 000 products; and some SF series fluids from GENERAL ELECTRIC, such as SF 1023, SF 1154, SF 1250, and SF 1265.

Organomodified silicones which may be used according to the present invention include, but are not limited to, silicones such as those previously defined and comprising within their structure at least one organofunctional moiety linked by means of a hydrocarbon group. Organomodified silicones may include, for example, polyorganosiloxanes comprising:

polyethyleneoxy and/or polypropyleneoxy moieties optionally comprising C₆-C₂₄ alkyl moieties, such as products called dimethicone copolyols marketed by DOW CORNING under the trade name DC 1248 and under the trade name DC Q2-5220 and SILWET® L 722, L 7500, L 77, and L 711 fluids marketed by UNION CARBIDE and (Ci₂)alkyl-methicone copolyol marketed by DOW CORNING under the trade name Q2 5200;

optionally substituted amine moieties, for example, the products marketed under the trade name GP 4 Silicone Fluid and GP 7100 by GENESEE and the products marketed under the trade names Q2 8220 and DOW CORNING 929 and 939 by DOW CORNING. Substituted amine moieties may be chosen, for example, from amino C1-C4 alkyl moieties. Aminosilicones may have additional Q-C4 alkoxy functional groups, such as those corresponding to the WACKER BELSIL ADM LOG 1 product;

alkoxylated moieties, such as the product marketed under the trade name "SILICONE

COPOLYMER F-755" by SWS SILICONES and ABIL WAX® 2428, 2434, and 2440 by GOLDSCHMIDT;

hydroxylated moieties, such as hydroxyalkyl function-containing polyorganosiloxanes described, for instance, in French Patent Application No. FR-A-85 163 34;

acyloxyalkyl moieties, for example, the polyorganosiloxanes described in U.S. Pat. No.

4,957,732;

anionic moieties of the carboxylic acid type, for example, the products described in European Patent No. 0 186 507, marketed by CHISSO CORPORATION, and carboxylic alkyl anionic moieties, such as those present in the X-22-3701E product marketed by SHIN-ETSU;

2-hydroxyalkyl sulfonate; and 2-hydroxyalkyl thiosulfate such as the products marketed by

GOLDSCHMIDT under the trade names «ABIL® S201» and «ABIL® S255»;

hydroxyacylamino moieties, such as the polyorganosiloxanes described in European Patent Application No. 0 342 834. A non-limiting example of a corresponding commercial product is the Q2-8413 product marketed by DOW CORNING;

acrylic moieties, such as the products marketed under the names VS80 and VS70 by 3M;

polyamine moieties, and

oxazoline moieties C¾-C¾-N ;

o=c 1

!

c% silicones that may be used according to the present invention may comprise 1 or 2 oxazoline groups; for example, poly(2 -methyl oxazoline-b-dimethyl siloxane-b-2 -methyl oxazoline) and poly(2-ethyl-2-oxazoline-dimethyl siloxane). The products marketed by KAO under the references OX-40, OS-51, OS-96, and OS-88 may also be used.

It is preferable that the silicone oil be selected from volatile or non- volatile silicone oils, such as volatile or non- volatile polydimethylsiloxanes (PDMS) containing a linear or cyclic silicone chain, that are liquid or pasty at ambient temperature, in particular cyclopolydimethylsiloxanes

(cyclomethicones) such as cyclohexasiloxane; polydimethylsiloxanes containing alkyl, alkoxy, or phenyl groups that are pendent or at the end of the silicone chain, which groups have from 2 to 24 carbon atoms; phenyl silicones such as phenyltrimethicones, phenyldimethicones,

phenylfrimethylsiloxydiphenylsiloxanes, diphenyldimethicones,

diphenylmethyldiphenyltrisiloxanes, 2-phenylethyltrimethyl siloxysilicates, and

polymethylphenylsiloxanes; and organomodified silicones such as amodimethicone.

The amount in the composition according to the present invention of the (a) silicone oil is 25% by weight or more relative to the total weight of the composition, and it may range from 25 to 90% by weight, preferably from 30 to 80% by weight, and more preferably from 35 to 70% by weight, relative to the total weight of the composition.

In a preferred embodiment, the amount of the (a) silicone oil may range from 30 to 90% by weight, preferably from 30 to 80% by weight, and more preferably from 30 to 70% by weight, relative to the total weight of the composition. In a more preferred embodiment, the amount of the (a) silicone oil may range from 35 to 90% by weight, preferably from 35 to 80% by weight, and more preferably from 35 to 70% by weight, relative to the total weight of the composition.

In a more preferred embodiment, the amount of the (a) silicone oil may range from 40 to 90% by weight, preferably from 40 to 80% by weight, and more preferably from 40 to 70% by weight, relative to the total weight of the composition.

In a furthermore preferred embodiment, the amount of the (a) silicone oil may range from 50 to 90% by weight, preferably from 50 to 80% by weight, and more preferably from 50 to 70% by weight, relative to the total weight of the composition. [Dye]

The composition according to the present invention comprises at least one (b) dye. A single type of dye may be used, but two or more different types of dyes may be used in combination.

The (b) dye may be selected from the group consisting of direct dyes and oxidative dyes.

The direct dye means a colored substance which does not require the use of an oxidizing agent in order to develop its color.

The direct dyes may be selected from natural direct dyes.

The expression "natural dye" is understood to mean any dye or dye precursor that is naturally occurring and is produced either by extraction (and optionally purification) from a plant matrix optionally in the presence of natural compounds such as ash or ammonia, or by chemical synthesis.

As natural dyes, mention may be made of quinone dyes (such as lawsone and juglone), alizarin, purpurin, laccaic acid, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigoids (such as indigo), sorghum, isatin, betanin, curcuminoids (such as curcumin), spinulosin, various types of chlorophyll and chlorophyllin, hematoxylin, hematein, brazilein, brazilin, safflower dyes (such as carmamin), flavonoids (such as rutin, quercetin, catechin, epicatechin, morin, apigenidin, and sandalwood), anthocyans (such as apigeninidin and apigenidin), carotenoids, tannins, orceins, santalins, and cochineal carmine.

It is also possible to use extracts or decoctions containing natural direct dye(s), in particular henna-based extracts, curcuma longa extract, sorghum leaf-sheath extract, haematoxylon campechianum extract, green tea extract, pine bark extract, cocoa extract, and logwood extract.

It is preferable that the natural dye be chosen from the group consisting of curcuminoids, santalins, chlorophyllin, haematoxylin, haematein, brazilein, brazilin, sorghum, laccaic acid, lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigoids, isatin, spinulosin, apigenidin, orcein, betanin, flavonoids, anthocyans, and extracts or decoctions containing these compounds.

Alternatively, the natural dyes may be preferably chosen, for example, from hydroxylated quinones, indigoids, hydroxyflavones, santalins A and B, isatin and its derivatives, and brasilin and its hydroxylated derivative.

The hydroxylated quinones are preferably benzoquinones, naphthoquinones, and mono- or polyhydroxylated anthraquinones which are optionally substituted with groups such as alkyl, alkoxy, alkenyl, chloro, phenyl, hydroxyalkyl, and carboxyl. The naphthoquinones are preferably lawsone, juglone, flaviolin, naphthazarin,

lapachol, plumbagin, chloroplumbagin, droserone, shikonin,

2- hydroxy-3 -methyl- 1 ,4-naphthoquinone, 3 ,5-dihydroxy- 1 ,4-naphthoquinone,

2,5-dihydroxy- 1 ,4-naphthoquinone, 2-methoxy-5-hydroxy- 1 ,4-naphthoquinone, and

3 - methoxy-5 -hydroxy- 1 ,4-naphthoquinone.

The benzoquinones are preferably spinulosin, atromentin, aurentioglyocladin,

2,5-dihydroxy-6-methylbenzoquinone, 2-hydroxy-3-methyl-6-methoxybenzoquinone, 2, 5-dihydroxy-3,6-diphenylbenzoquinone, 2,3-dimethyl-5-hydroxy-6-methoxybenzoquinone, and 2,5-dihydroxy-6-isopropylbenzoquinone.

The anthraquinones are preferably alizarin, quinizarin, purpurin, carminic acid, chrysophanol, kermesic acid, rhein, aloe emodin, pseudopurpurin, quinizarincarboxylic acid, frangula emodin, 2-methylquinizarin, 1-hydroxyanthraquinone, and 2-hydroxyanthraquinone. The indigoids are preferably indigo, indirubin, isoindigo, and Tyrian purple.

The hydroxyfiavones are preferably quercetin and morin.

The direct dyes may be selected from synthetic direct dyes.

The expression "synthetic direct dye" is understood to mean any dye or dye precursor that is produced by chemical synthesis.

The synthetic direct dye may be hydrophilic or hydrophobic. The synthetic direct dye may be a hydrophilic direct dye selected from the group consisting of acidic (anionic) direct dyes, basic (cationic) direct dyes and neutral (noninic) direct dyes and a hydrophobic direct dye, which cover all possible types of direct dyes, such as so-called nitro dyes, HC dyes, azo, methine, carbonyl, azine, nitro(hetero)aryl types or tri(hetero)arylmethane direct dyes, poφhyrins and

phthalocyanines, alone or as mixtures. Acidic direct dyes have an anionic moiety in their chemical structure. Basic direct dyes have a cationic moiety in their chemical structure.

Neutral direct dyes are nonionic.

More particularly, the azo dyes comprise an -N=N- functional group, the two nitrogen atoms of which are not simultaneously involved in a ring. However, it is not ruled out for one of the two nitrogen atoms of the -N=N- sequence to be involved in a ring.

The dyes of the family of the methines are more particularly compounds comprising at least one sequence chosen from >C=C< and -N=C<, the two atoms of which are not simultaneously involved in a ring. However, it is specified that one of the nitrogen or carbon atoms of the sequences can be involved in a ring. More particularly, the dyes of this family result from compounds of the following types: true methine (comprising one or more above-mentioned -C=C- sequences); azomethine (comprising at least one or more -C=N- sequences) with, for example, the azacarbocyanines and their isomers, the diazacarbocyanines and their isomers, the tetraazacarbocyanines; mono- and diarylmethane; indoarnines (or diphenylamines); indophenols; and indoanilines. As regards the dyes of the family of the carbonyls, mention may be made, for example, of synthetic dyes chosen from acridone, benzoquinone, anthraquinone, naphthoquinone,

benzanthrone, anthranthrone, pyranthrone, pyrazolanthrone, pyrimidinoanthrone, flavanthrone, indanthrone, flavone, (iso)violanthrone, isoindolinone, benzimidazolone, isoquinolinone, anthrapyridone, pyrazoloquinazolone, perinone, quinacridone, quinophthalone, naphthalimide, anthrapyrimidine, diketopyrrolopyrrole, or coumarin dyes.

As regards the dyes of the family of the cyclic azines, mention may in particular be made of azine, xanthene, thioxanthene, fluorindine, acridine, (di)oxazine, (di)thiazine, or pyronine dyes.

The nitro(hetero)aromatic dyes are more particularly nitrobenzene or nitropyridine direct dyes.

As regards the dyes of porphyrin or phthalocyanine type, use may be made of cationic or noncationic compounds optionally comprising one or more metals or metal ions, such as, for example, alkali and alkaline earth metals, zinc, and silicon.

Mention may be made, as examples of synthetic direct dyes which are particularly suitable, of nitrobenzene dyes, azo, azomethine, or methine direct dyes, azacarbocyanines, such as

tetraazacarbocyanines (tetraazapentamethines), quinone, and in particular anthraquinone, naphthoquinone, or benzoquinone direct dyes, or azine, xanthene, triarylmethane, indoarnine, phthalocyanine, and porphyrin direct dyes, alone or as mixtures. More preferably still, these synthetic direct dyes are chosen from nitrobenzene dyes, azo, azomethine, or methine direct dyes, and tetraazacarbocyanines (tetraazapentamethines); alone or as mixtures.

Mention may be made, among the azo, azomethine, methine, or tetraazapentamethine direct dyes which can be used according to the invention, of the cationic dyes described in Patent

Applications WO 95/15144, WO 95/01772, and EP 714 954; FR 2 189 006, FR 2 285 851, FR-2 140 205, EP 1 378 544, and EP 1 674 073.

Thus, mention may be made of the cationic direct dyes corresponding to the following formulae:

in which:

D represents a nitrogen atom or the -CH group,

Ri and R₂, which are identical or different, represent a hydrogen atom; a Q-C₄ alkyl radical which can be substituted by a -CN, -OH, or -NH₂ radical or can form, with a carbon atom of the benzene ring, an optionally oxygen-comprising or nitrogen-comprising heterocycle which can be substituted by one or more Q-C4 alkyl radicals; or a 4'-aminophenyl radical,

R₃ and R'₃, which are identical or different, represent a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine, and fluorine, a cyano radical, a CrC₄ alkyl radical, a C1-C₄ alkoxy radical, or an acetyloxy radical, X^" represents an anion, preferably chosen from chloride, methyl sulphate, and acetate,

in which:

R.5 represents a hydrogen atom, a Q-C₄ alkoxy radical, or a halogen atom, such as bromine, chlorine, iodine, or fluorine,

¾ represents a hydrogen atom or a Ci-C₄ alkyl radical or forms, with a carbon atom in the benzene ring, a heterocycle which optionally comprises oxygen and/or is optionally substituted by one or more Q-Q alkyl groups,

R₇ represents a hydrogen atom or a halogen atom, such as bromine, chlorine, iodine, or fluorine, Di and D₂, which are identical or different, represent a nitrogen atom or the -CH group, m = 0 or 1,

X^" represents a cosmetically acceptable anion preferably chosen from chloride, methyl sulphate, and acetate,

E represents a group chosen from the following structures:

in which R' represents a C₁-C₄ alkyl radical;

when m = 0 and when Ό_\ represents a nitrogen atom, then E can also denote a group with the following structure:

in which R' represents a Q-C4 alkyl radical. The fo

X^" represents an anion preferably chosen from chloride, iodide, methyl sulphate, ethyl sulphate, or acetate.

As examples of the cationic direct dyes, mention may be made of 4-mtro-o-phenylenediamine, 2-nitro-p-phenylenediamine, N,N'-bis-(2-hydroxyethyl)-2-nitro-p-phenylenediamine,

4-nitrophenylaminoethylurea, and 2-amino-6-chloro-4-nitrophenol,

2,6-diammo-3-((pyridine-3-yl)-azo)pyridine.

According to an embodiment, it is preferable that the direct dye be selected from acidic direct dyes. The anionic direct dyes are commonly known as "acidic direct dyes" for their affinity with alkaline substances (see, for example, "Industrial Dyes, Chemistry, Properties, Application", Klaus Hunger Ed. Wiley- VCH Verlag GmbH & Co KGaA, Weinheim 2003). Anionic or acid dyes are known in the literature (see, for example, " Ullman s ' Encyclopedia of Industrial Chemistry", Azo Dyes, 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a03 245, point 3.2; ibid, Textile Auxiliaries, 2002 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a26 227 and "Ashford's Dictionary of Industrial Chemicals", Second Edition, p. 14-p. 39, 2001).

The term "anionic direct dyes" means any direct dye comprising in its structure at least one sulfonate group S0₃ ^" and/or at least one carboxylate group C(0)0^~ and/or at least one phosphonate group Ρ(=0)ΟΌ^" and optionally one or more anionic groups G^" with G^", which may be identical or different, representing an anionic group chosen from alkoxide O^", thioalkoxide S^", phosphonate, carboxylate and thiocarboxylate: C(Q)Q'^" with Q and Q', which may be identical or different, representing an oxygen or sulfur atom; preferably, G^" represents a carboxylate, i.e. Q and Q' represent an oxygen atom.

The preferred anionic dyes of formula of the invention are chosen from acidic nitro direct dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic indoamine dyes, acidic anthraquinone dyes, anionic styryl dyes, and indigoids and acidic natural dyes; each of these dyes containing at least one sulfonate, phosphonate or carboxylate group bearing a cationic counterion X*, where X^"1" represents an organic or mineral cationic counter ion preferably chosen from alkali and alkaline-earth metals, such as Na⁺ and K⁺.

Preferred acid dyes may be chosen from the dyes below. The diaryl anionic azo dyes of formula (II) or (IT):

in which formulae (II) and (ΙΓ):

R₇, Rg, R9, Rio, R'₇, R'8, R' and R'io, which may be identical or different, represent a hydrogen atom or a group chosen from:

alkyl;

alkoxy, alkylthio;

hydroxyl, mercapto;

nitro;

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; (0)₂S(0^~)-, X^1" as defined previously;

(O)CO^"-, XT^1" as defined previously;

(0)P(0₂ ^")-, 2X* as defined previously;

R"-S(0)₂-, with R" representing a hydrogen atom or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group; preferably a phenylamino or phenyl group;

R'"-S(0)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) (0)₂S(0^")-, X* and iv) alkoxy with X⁺;

optionally substituted heteroaryl; preferably a benzothiazolyl group;

cycloalkyl; especially cyclohexyl,

Ar-N=N- with Ar representing an optionally substituted aryl group, preferably a phenyl optionally substituted with one or more alkyl, (0)₂S(0^")-, X^4" or phenylamino groups; or alternatively two contiguous groups R with Rs or ¾ with R9 or R9 with Rio together form a fused benzo group A'; and R'₇ with R's or R'₈ with R'9 or R'9 with R'i₀ 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) (0)₂S(0^")-, X*^"; 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 X*, R°, X, X', X" and Ar as defined previously;

W represents a sigma bond σ, an oxygen or sulfur atom, or a divalent radical i) -NR- with R as defined previously, or ii) methylene -C(R_a)(R_b)- with R_a and R , which may be identical or different, representing a hydrogen atom or an aryl group, or alternatively R_a and Rb form, together with the carbon atom that bears them, a spiro cycloalkyl; preferably W represents a sulfur atom or Ra and R_b together form a cyclohexyl;

it being understood that formulae (II) and (ΙΓ) comprise at least one sulfonate (0)₂S(0^")-, X⁺ or phosphonate (0)P(0₂ ^") 2X ^" or carboxylate (O)C(O^')-, X^4" radical on one of the rings A, A', B, B' or C with * as defined previously.

As examples of dyes of formula (II), mention may be made of Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Food Red 17, Orange 4, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, 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, Pigment Red 57;

and as examples of dyes of formula (Π'), mention may be made of Acid Red 111, Acid Red 134, Acid yellow 38;

The ant raquinone dyes of formulae (III) and (ΙΙΓ):

in which formulae (III) and (III'):

R22, R23, R2 , R25, R26 and R27, which may be identical or different, represent a hydrogen or halogen atom or a group chosen from:

alkyl;

hydroxyl, mercapto;

- alkoxy, alkylthio;

aryloxy or arylthio optionally substituted, preferably substituted with one or more groups chosen from alkyl and (0)₂S(0^")-, X^1" with X^4" as defined previously; aryl(alkyl)amino optionally substituted with one or more groups chosen from alkyl and

(0)₂S(0^")-, *^" with X^4" as defined previously;

(di)(alkyl)amino;

(di)(hydroxyalkyl)amino;

- (0)₂S(0^")-, X^4" with X^1" as defined previously;

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;

- aryl optionally substituted with one or more groups, particularly i) alkyl such as methyl,

Λ-dodecyl, «-butyl; ii) (0)₂S(0>, X^4" with X⁺ 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, preferably

R° represents an alkyl group;

cycloakyl; especially cyclohexyl;

Z represents a group chosen from hydroxyl and NR'₂gR'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 (III) and (ΙΙΓ) comprise at least one sulfonate group (0)₂S(0^")-, X^1" with X^4" as defined previously. As examples of dyes of formula (III), mention may be made of 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 2,

and as examples of dyes of formula (III'), mention may be made of Acid Black 48; The quinoline-based dyes of formula (IV):

in which formula (TV):

¾i represents a hydrogen or halogen atom or an alkyl group;

R 2, R 3 and ¾4, which may be identical or different, represent a hydrogen atom or a group (0)₂S(0^~)-, X with X^4" as defined previously;

or alternatively ¾ι with ¾₂, or ¾i with ¾4, together form a benzo group optionally substituted with one or more groups (0)₂S(0^")-, X^4" with X^4" as defined previously;

G represents an oxygen or sulfur atom or a group Ν¾ with Re representing a hydrogen atom or an alkyl group; particularly G represents an oxygen atom;

it being understood that formula (IV) comprises at least one sulfonate group (0)₂S(0^~)-, X^4" with X^4' as defined previously. As examples of dyes of formula (IV), mention may be made of Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

As examples of the nonionic direct dyes, mention may be made of HC Red 13, HC Red 7, HC Blue 2, HC Yellow 4, HC Yellow 2, HC Red 3, 4-amino-3-nitrophenol,

l-hydroxyethylamino-5-nitroanisole, 3-nitro-p-(hydroxyethylarnino)phenol,

3-methylan ino-4-nitrophenoxyethanol, 2-nitro-5-(glyceryl)methylaniline, HC Violet 1, HC Orange 2, HC Yellow 9, HC Red 10, HC Red 11, 2-hydroxyethylpicramic acid, HC Blue 12, 3 -nitro-4-(N-(P-hydroxyethyl)amino)-toluene,

2-(N-(P-memoxyethyl)am o)-5-(N,N-bi^ HC Yellow 10, HC

Violet 2, 4-hydroxypropylamino-3-nitrophenol, and HC Blue 14.

As examples of the hydrophobic direct dyes mention may be made of Solvent Black 3, Solvent Blue 104, Solvent Blue 134, Solvent Blue 14, Disperse Blue 14, Solvent Red 2, Solvent Brown 5, Solvent Green 5, Solvent Orange 2, Solvent Orange 1 , Disperse Orange 24, Solvent Orange 63, Solvent Red 49, Solvent Red 1, Solvent Red 26, Solvent Red 27, Solvent Red 18, Solvent Red 23, Solvent Red 4, Disperse Orange 7, Disperse Blue 72, Disperse Violet 26, Disperse Yellow 16, Disperse Yellow 82, Disperse Yellow 54, Solvent Yellow 29, Solvent Yellow 163, Solvent Yellow 3, Solvent Yellow 56, Solvent Yellow 18, Solvent Yellow 98, Solvent Yellow 12, Solvent Yellow 14, Disperse Red 13, Disperse Green 9, Disperse Blue 148, Disperse Violet 63, Disperse Blue 60, and Solvent Orange 15.

The synthetic direct dye may be selected from fluorescent dyes. Two or more types of the fluorescent dye may be used in combination.

The use of some fluorescent dyes may make it possible to obtain, on dark hair, colors which are more visible than with conventional hydrophilic or hydrophobic direct dyes. Furthermore, these fluorescent dyes, when applied to dark hair, may also make it possible to lighten the hair without damaging it.

As used herein, the term "fluorescent dyes" is understood to mean fluorescent compounds and optical brighteners. In at least one embodiment, the fluorescent dye is soluble in the medium of the composition. Fluorescent dyes are fluorescent compounds which absorb visible radiation, for example, wavelengths ranging from 400 to 800 nm, and which are capable of re-emitting light in the visible region at a higher wavelength.

According to one embodiment, the fluorescent dyes useful for the present invention re-emit orange-colored fluorescent light. They exhibit, for instance, a maximum re-emission wavelength ranging from 500 to 700 nm.

Non-limiting examples of fluorescent dyes include compounds known in the art, for example, those described in Ullmann's Encyclopedia of Industrial Chemistry, Release 2004, 7th edition, "Fluorescent Dyes" chapter. The optical brighteners of the present disclosure, also known under the name of "brighteners", or "fluorescent brighteners", or "fluorescent brightening agents" or "FWA", or "fluorescent whitening agents", or "whitenefs", or "fluorescent whiteners", are colorless transparent compounds as they do not absorb radiation in visible light but only in ultraviolet light (wavelengths ranging from 200 to 400 nanometers) and convert the energy absorbed into fluorescent light of higher wavelength emitted in the visible part of the spectrum, generally in the blue and/or green, that is to say in wavelengths ranging from 400 to 550 nanometers. Optical brighteners are known in the art, for example, they are described in Ullmann's

Encyclopedia of Industrial Chemistry (2002), "Optical Brighteners" and Kirk-Othmer

Encyclopedia of Chemical Technology (1995): "Fluorescent Whitening Agents".

The fluorescent dyes which can be used in the composition of the present disclosure include compounds known from the art, for example, those described in French Patent No. 2 830 189.

Soluble fluorescent compounds that may especially be mentioned include those belonging to the following families: naphthalimides, coumarins, xanthenes, and in particular

xanthenodiquinolizines and azaxanthenes; naphtholactams; azlactones; oxazines; thiazines;

dioxazines; azo compounds; azomethines; methines; pyrazines; stilbenes; ketopyrroles; and pyrenes.

If present, the fluorescent dyes are preferred, more particularly, those re-emitting orange-colored fluorescent light.

The oxidative dyes may be selected from oxidation bases and couplers.

The oxidation base can be selected from those conventionally known in oxidation dyeing, preferably from the group consisting of ortho- and para-phenylenediamines, double bases, ortho- and para-arninophenols, heterocyclic bases, and the acid addition salts thereof.

There may be mentioned in particular:

- (T) the para-phenylenediamines of the following formula (I) and their addition salts with an acid:

Rj represents a hydrogen atom, a Q-Q alkyl radical, a monohydroxy(C₁-C₄ alkyl) radical, a polyhydroxy-(C₂-C₄ alkyl) radical, a (C₁-C₄)alkoxy(Ci-C₄)alkyl radical, a Q-C₄ alkylradical substituted with a nitrogen-containing group, a phenyl radical, or a 4'-aminophenyl radical;

R₂ represents a hydrogen atom, a d-0₄ alkyl radical, a monohydroxy(C₁-C₄ alkyl) radical, a polyhydroxy(C2-C₄ alkyl) radical, a (C₁-C₄)alkoxy(Ci-C₄)alkyl radical, or a Q-C₄ alkyl radical substituted with a nitrogen-containing group;

Ri and R₂ may also form with the nitrogen atom carrying them a 5- or 6-membered

nitrogen-containing heterocycle optionally substituted with one or more alkyl, hydroxyl, or ureido groups;

R₃ represents a hydrogen atom, a halogen atom such as a chlorine atom, a Q-C4 alkyl radical, a sulpho radical, a carboxyl radical, a monohydroxy(C_!-C₄ alkyl) radical, a hydroxy(C₁-C₄ alkoxy) radical, an acetylamino(CrC₄ alkoxy) radical, a mesylamino(Ci-C₄ alkoxy) radical, or a carbamoylarnino(Ci-C4 alkoxy) radical; and

R4 represents a hydrogen or halogen atom or a Q-C4 alkyl radical.

Among the nitrogen-containing groups of formula (I) above, there may be mentioned in particular the amino, mono(Ci-C₄)alkylamino, (Ci-C₄)dial¾ylamino, (C₁-C4)trialkylarnino,

monohydroxy(C₁-C₄)alkylamino, di(monohydroxy(C₁-C4)alkyl)amino, imidazolinium, and ammonium radicals.

Among the para-phenylenediamines of formula (I) above, there may be mentioned more particularly para-phenylenediamine, para-tolylenediarnine, 2-chloro-paraphenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediarnine,

2,6-diemyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine,

N,N-dimethylpara-phenylenediamine, N,N-diethyl-para-phenylenediarnine,

N,N-dipropyl-paraphenylenediamine, 4-arnino-N,N-diethyl-3-methylaniline,

N,N-bis(P-hydroxyethyl)-paraphenylenediamine,

4-N,N-bis( -hydroxyethyl)amino-2-methylaniline,

4-N,N-bis( -hydroxyethyl)amino-2-chloroaniline, 2-P-hydroxyethyl-para-phenylenediamine, 2-fluoro-paraphenylenediamine, 2-isopropyl-para-phenylenediamine,

N-( -hydroxypropyl)-paraphenylenediamine, 2-hydroxymethyl-para-phenylenediamine,

N,N-dimethyl-3-methylpara-phenylenediamine,

N,N-(ethyl- -hydroxyethyl)-para-phenylenediamine,

N-(P,y-dmydroxypropyl)-para-phenylenediamine, N-(4'-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2- -hydroxyethyloxy-para-phenylenediamine,

2-β-acetylamino-ethyloxy-para-phenylenediamine, N-( -memoxyethyl)-para-phenylenediamine, 2-methyl- 1 -Ν-β-hydroxyethyl-para-phenylenediamine, N-(4-aminophenyl)-3 -hydroxy-pyrrolidine, 2-[{2-[(4-Ammophenyl)amino]ethyl}(2-hydroxyethyl)amino]-ethanol, and their addition salts with an acid.

Among the para-phenylenediarnines of formula (I) above, there are most particularly preferred para-phenylenediamine, para-tolylenediamine, 2-isopropyl-paraphenylenediamine,

2- -hydroxyemyl-para-phenylenediarnine, 2-P-hydroxyethyloxy-para-phenylenediarnine,

2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,

2,3-dimethyl-para-phenylenediamine, N,N-bis(P-hydroxyemyl)-para-phenylenediamine,

2-chloro-para-phenylenediamine, and their addition salts with an acid.

- (II) According to the invention, "double bases" are understood to mean compounds containing at least two aromatic rings on which amino and/or hydroxyl groups are carried. Among the double bases which can be used as oxidation bases in the dyeing compositions in accordance with the invention, there may be mentioned in particular compounds corresponding to the following formula II), and their addition salts with an acid:

in which:

- Zi and Z₂, which are identical or different, represent a hydroxyl or - H₂ radical which may be substituted with a C₁-C₄ alkyl radical or with a linking arm Y;

- the linking arm Y represents a linear or branched alkylene chain comprising from 1 to 14 carbon atoms, which may be interrupted by or which may end with one or more nitrogen-containing groups and/or one or more heteroatoms such as oxygen, sulphur, or nitrogen atoms, and optionally substituted with one or more hydroxyl or Ci-C₆ alkoxy radicals;

- R5 and R represent a hydrogen or halogen atom, a Ci-C₄ alkyl radical, a monohydroxy(C₁-C₄ alkyl) radical, a polyhydroxy(C₂-C₄ alkyl) radical, an amino(C₁-C₄ alkyl) radical, or a linking arm Y;

- R₇, R₈, R₉, R₁₀, R\ and Ri₂, which are identical or different, represent a hydrogen atom, a linking arm Y, or a C₁-C₄ alkyl radical; it being understood that the compounds of formula (II) contain only one linking arm Y per molecule.

Among the nitrogen-containing groups of formula (II) above, there may be mentioned in particular the amino, mono(C₁-C4)alkylamino, (Ci-C₄)dialkylamino, (Ci-C4)trialkylamino, monohydroxy(Ci-C₄)alkylamino, imidazolinium, and ammonium radicals.

Among the double bases of formulae (II) above, there may be mentioned more particularly N,N'-bis(P-hydroxyethyl)-N,N'-bis(4'-arninophenyl)-l,3-diaminopropanol,

N,N ' -bis(P-hydroxyethyl)-N,N' -bis(4 ' -aminophenyl)ethylenediamine,

N,N ' -bis(4-ammophenyl)-tetramethylenediamine,

N,N'-bis( -hydroxyethyl)-N,N'-bis(4-ammophenyl)tetramethylenediamine,

N,N'-bis(4-memylammophenyl)tetramemylenediamine,

Ν,Ν' -bis(ethyl)-N,N' -bis(4 ' -amino-3 ' -methylphenyl)ethylene-diamine,

l,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and their addition salts with an acid.

Among these double bases of formula (II),

N,N ' -bis(P-hydroxyethyl)-N,N' -bis(4 ' -aminophenyl)- 1 ,3 -diaminopropanol,

1 ,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, or one of their addition salts with an acid are particularly preferred.

- (Ill) The para-aminophenols corresponding to the following formula (III), and their addition with an acid:

in which:

- R₁₃ represents a hydrogen atom, or a halogen atom such as fluorine, a Q-Q alkyl,

monohydroxy(Ci-C₄ alkyl), (Ci-C4)alkoxy(C₁-C4)-alkyl, amino(C₁-C₄ alkyl), or

hydroxy(C₁-C₄)alkylamino-(Ci-C4 alkyl) radical,

- represents a hydrogen atom, or a halogen atom such as fluorine, a Q-C4 alkyl,

monohydroxy(Ci-C4 alkyl), polyhydroxy(C₂-C4 alkyl), amino(Ci-C₄ alkyl), cyano(C!-C4 alkyl), or (Ci-C₄)alkoxy(C₁-C₄)alkyl radical.

Among the para-aminophenols of formula (III) above, there may be mentioned more particularly para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol,

4-amino-3 -hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-ammo-2-aminomethylphenol,

4-amino-2-( -hydroxyethylaminomethyl)phenol, and their addition salts with an acid.

- (IV) The ortho-aminophenols which can be used as oxidation bases in the context of the present invention are chosen in particular from 2-aminophenol, 2-amino-l-hydroxy-5-methylbenzene, 2-amino-l-hydroxy-6-methylbenzene, 5-acetamido-2-aminophenol, and their addition salts with an acid.

- (V) Among the heterocyclic bases which can be used as oxidation bases in the dyeing compositions in accordance with the invention, there may be mentioned more particularly pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, and their addition salts with an acid.

Among the pyridine derivatives, there may be mentioned more particularly the compounds described for example in Patents GB 1 ,026,978 and GB 1 , 153, 196, such as 2,5-diaminopyridine, 2-(4-me{hoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine,

2-(P-memoxyethyl)ammo-3-amino-6-methoxypyridine, 3,4-diaminopyridine, and their addition salts with an acid.

Among the pyrimidine derivatives, there may be mentioned more particularly the compounds described, for example, in Patents DE 2 359 399; JP 88-169571; and JP 91-10659, or patent application WO 96/15765, such as 2,4,5,6-tetraarninopyrirnidine,

4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrirnidine,

2,4-dmydroxy-5,6-diaminopyrirnidine, 2,5,6-triarnino-pyrimidine, and the pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which there may be mentioned pyrazolo[l,5-a]-pyriniidme-3,7-diarnine;

2,5-dimethyl-pyrazolo[l ,5-a]-pyrimidine-3,7-diamine; pyrazolo[l ,5-a]pyrimidme-3,5-diamine; 2,7-dimethylpyrazolo[l ,5-a]pyrimidine-3,5-diamine; 3-aminopyrazolo[l ,5-a]pyrimidin-7-ol;

3-amino-pyrazolo[l ,5-a]pyrimidin-5-ol; 2-(3-amino-pyrazolo-[l ,5-a]pyrimidin-7-ylamino)ethanol, 2-(7-aminopyrazolo[l ,5-a]pyrimidin-3-ylamino)ethanol,

2- [(3-amino-pyrazolo[l,5-a]pyrimidin-7-yl)-(2-hydroxy-ethyl)amm^

2- [(7-aminopyrazolo [ 1 ,5 -a] -pyrimidin-3 -yl)-(2-hydroxyethyl)amino]ethanol,

5,6-dimethylpyrazolo-[l,5-a]pyrimidine-3,7-diarnine,

2,6-dimethylpyrazolo-[l,5-a]pyrirrddine-3,7-diamine,

2,5,N7,N7-tetramethyl-pyrazolo[l,5-a]pyrimidine-3,7-diamine,

3- amino-5-memyl-7-irmdazolylpropyl-a their addition salts and their tautomeric forms, when a tautomeric equilibrium exists, and their addition salts with an acid.

Among the pyrazole derivatives, there may be mentioned more particularly the compounds described in Patents DE 3 843 892 and DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749, and DE 195 43 988 such as 4,5-diamino-l-methylpyrazole,

3,4-diaminopyrazole, 4,5-diamino-l-(4'-chlorobenzyl)-pyrazole,

4,5-diamino-l,3-dimethylpyrazole, 4,5-diarnino-3-methyl-l-phenylpyrazole,

4,5-diamino-l-methyl-3-phenylpyrazole, 4-amino-l,3-dimethyl-5-hydrazino-pyrazole,

1- ben2yl-4,5-diamino-3-methyl-pyrazole, 4,5-diamino-3-tert-butyl-l-methylpyrazole,

4,5 -diamino- 1 -tertbutyl-3 -methylpyrazole, 4, 5 -diamino- 1 -(P~hydroxyethyl)-3 -methylpyrazole, 4,5-diamino- 1 -(β-hydro yethyl) yrazole, 4,5-diamino- 1 -ethyl-3-methylpyrazole,

4,5^diamino-l-ethyl-3-(4'-methoxyphenyl)pyrazole,

4,5-diamino- l-ethyl-3-hydroxy-methylpyrazole, 4,5-diamino-3-hydroxymethyl-l -methylpyrazole, 4,5-diamino-3-hydroxymethyl-l -isopropyl-pyrazole, 4,5-diamino-3-methyl- 1 -isopropyl-pyrazole,

4- amino-5-(2 ' -aminoethyl)amino- 1 ,3 -dimethylpyrazole, 3 ,4,5-triaminopyrazole,

1 -methyl-3,4,5-triamino-pyrazole, 3,5-diamino- 1 -memyl-4-methylaminopyrazole,

3,5-diammo-4-( -hydroxy-emyl)amino-l -methylpyrazole, and their addition salts with an acid.

Among the heterocyclic bases which can be used as oxidation bases, there may be mentioned more particularly diaminopyrazolopyrazolones and especially

2,3-diamino-6,7-dihydro-lH5H-[pyrazolol,2,a]pyrazol-l-one and the addition salts of these diaminopyrazolopyrazolones with an acid.

The couplers may be an oxidation coupler which can be selected from those conventionally known in oxidation dyeing, preferably from the group consisting of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthols, heterocyclic couplers, and the acid addition salts thereof.

The heterocyclic couplers may be selected from the group consisting of indole derivatives, indoline derivatives, sesamol and its derivatives, pyridine derivatives, pyrazolotriazole derivatives, pyrazolones, indazoles, benzimidazoles, benzothiazoles, benzoxazoles, 1,3-benzodioxoles, quinolines, and their addition salts with an acid.

These couplers are more particularly chosen from 2,4-diarrrino-l-^-hydroxye1liyloxy)benzene,

2- methyl-5-aminophenol, 5-N-(p-hydroxyethyl)amino-2-methylphenol, 3 -aminophenol,

2-chloro-3-amino-6-methylphenol, 1,3-dihydroxybenzene, l,3-dihydroxy-2-methylbenzene, 4-chloro- 1 ,3 -dihydroxybenzene, 2-amino-4-(P-hydroxyethylamino)- 1 -methoxybenzene, 1 ,3-diaminobenzene, 2-methyl-5-hydroxyethylaminophenol, 4-amino-2-hydroxytoluene,

1 ,3-bis(2,4-diaminophenoxy)-propane, sesamol,

l-amino-2-methoxy-4,5-methylene-dioxybenzene, a-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxy-indoline, 2,6-dihydroxy-4-methylpyridine,

l-H-3-methylpyrazol-5-one, l-phenyl-3-methylpyrazol-5-one, 2-amino-3-hydroxypyridine, 3,6-dimethyl-pyrazolo[3,2-c]-l,2,4-triazole, 2,6-dimethylpyrazolo[l,5-b]-l,2,4-triazole, and their addition salts with an acid. In general, the addition acid salts of the oxidation bases and couplers are chosen in particular from hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates, and acetates.

The composition used for the present invention contains the (b) dye(s) in an amount of 0.001% by weight or more, and may contain, for example, 0.001 to 10% by weight, preferably 0.01 to 5% by weight, and more preferably 0.1 to 3% by weight, relative to the total weight of the composition.

[Thickener] The composition according to the present invention comprises at least one (c) thickener. A single type of thickener may be used, but two or more different types of thickener may be used in combination.

The (c) thickener may be selected from hydrophilic polymers, preferably water-soluble polymers.

It is preferable that the (c) thickener be selected from the group consisting of:

(i) associative thickeners;

(ϋ) crosslinked acrylic acid homopolymers;

(iii) crosslinked copolymers of (meth)acrylic acid and of (Q-Ce^kyl acrylate;

(iv) nonionic homopolymers and copolymers comprising ethylenically unsaturated

monomers of ester and/or amide type;

(v) ammonium acrylate homopolymers and copolymers of ammonium acrylate and of

acrylamide;

(vi) polysaccharides; and

(vii) C₁₂-C₃₀ fatty alcohols.

(i) As used herein, the expression "associative thickener" means an amphiphilic thickener comprising both hydrophilic units and hydrophobic units, for example, at least one C₈-C₃₀ fatty chain and at least one hydrophilic unit.

Representative associative thickeners that may be used are associative polymers chosen from: (aa) nonionic amphiphilic polymers comprising at least one fatty chain and at least one

hydrophilic unit;

(bb) anionic amphiphilic polymers comprising at least one hydrophilic unit and at least one fatty-chain unit; (cc) cationic amphiphilic polymers comprising at least one hydrophilic unit and at least one fatty-chain unit; and

(dd) amphoteric amphiphilic polymers comprising at least one hydrophilic unit and at least one fatty-chain unit,

wherein the fatty chain contains from 10 to 30 carbon atoms.

The (aa) nonionic amphiphilic polymers comprising at least one fatty chain and at least one hydrophilic unit may, for example, be chosen from:

(1) celluloses modified with groups comprising at least one fatty chain; examples that may be mentioned include:

hydroxyethylcelluloses modified with groups comprising at least one fatty chain chosen from alkyl, arylalkyl, and alkylaryl groups, and in which the alkyl groups are, for example, C_8-c22, such as the product Natrosol Plus Grade 330 CS(C_1-6 alkyls) sold by the company Aqualon, and the product Bermocoll EHM 100 sold by the company Berol Nobel, and

celluloses modified with polyalkylene glycol alkylphenyl ether groups, such as the product Amercell Polymer HM-1500 (polyethylene glycol (15) nonylphenyl ether) sold by the company Amerchol.

(2) hydroxypropyl guars modified with groups comprising at least one fatty chain, such as the product Esaflor HM 22 (C₂₂ alkyl chain) sold by the company Lamberti, and the products Miracare XC95-3 (C₁₄ alkyl chain) and RE205-1 (C₂₀ alkyl chain) sold by the company Rhodia Chimie.

(3) polyether urethanes comprising at least one fatty chain, such as 0-C30 alkyl or alkenyl groups, for instance the products Elfacos T 210 and Elfacos T 212 sold by the company Akzo or the products Aculyn 44 and Aculyn 46 sold by the company Rohm & Haas.

(4) copolymers of vinylpyrrolidone and of hydrophobic fatty-chain monomers;

examples that may be mentioned include:

the products Antaron V216 and Ganex V216 (vinylpyrrolidone/hexadecene copolymer) sold by the company I.S.P., and

the products Antaron V220 and Ganex V220 (vinylpyrrolidone/eicosene copolymer) sold by the company I.S.P.

(5) copolymers of Q-Q alkyl acrylates or methacrylates and of amphiphilic monomers comprising at least one fatty chain, such as the oxyethylenated methyl

methacrylate/stearyl acrylate copolymer sold by the company Goldschmidt under the name Antil 208.

(6) copolymers of hydrophilic acrylates or methacrylates and of hydrophobic monomers comprising at least one fatty chain, such as a polyethylene glycol methacrylate/lauryl methacrylate copolymer.

The (bb) anionic amphiphilic polymers comprising at least one hydrophilic unit and at least one fatty-chain unit, may, for example, be chosen from those comprising at least one fatty-chain allyl ether unit and at least one hydrophilic unit comprising an ethylenic unsaturated anionic monomelic unit, for example, a vinylcarboxylic acid unit and further, for example, be chosen from units derived from acrylic acids, methacrylic acids, and mixtures thereof, wherein the fatty-chain allyl ether unit corresponds to the monomer of formula (I) below: CH₂=C(R CH₂OB_nR (I) in which Ri is chosen from H and C¾, B is an ethyleneoxy radical, n is chosen from zero and integers ranging from 1 to 100, R is chosen from hydrocarbon-based radicals chosen from alkyl, arylalkyl, aryl, alkylaryl, and cycloalkyl radicals, containing from 10 to 30 carbon atoms, and further, for example, from 10 to 24 carbon atoms and even further, for example, from 12 to 18 carbon atoms. In one embodiment, a unit of formula (I) is, for example, a unit in which Ri can be H, n can be equal to 10, and R can be a stearyl (Ci₈) radical.

Anionic amphiphilic polymers of this type are described and prepared, according to an emulsion polymerization process, in patent EP-0 216 479 B2.

In one embodiment, anionic amphiphilic polymers are, for example, polymers formed from 20% to 60% by weight of acrylic acid and or of methacrylic acid, from 5% to 60% by weight of lower alkyl (meth)acrylates, from 2% to 50% by weight of fatty-chain allyl ether of formula (I), and from 0% to 1% by weight of a crosslinking agent which is a well-known copolymerizable unsaturated polyethylenic monomer, for example, diallyl phthalate, allyl(meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate, and methylenebisacrylamide.

Examples of such polymers are crosslinked terpolymers of methacrylic acid, of ethyl acrylate, and of polyethylene glycol (10 EO) stearyl ether (Steareth-10), such as those sold by the company Ciba under the names Salcare SC 80 and Salcare SC 90, which are aqueous 30% emulsions of a crosslinked terpolymer of methacrylic acid, of ethyl acrylate, and of steareth-10 allyl ether (40/50/10).

The anionic amphiphilic polymers may further be chosen, for example, from those comprising at least one hydrophilic unit of unsaturated olefinic carboxylic acid type, and at least one hydrophobic unit of a type such as a ( 0-C30) alkyl ester of an unsaturated carboxylic acid. The hydrophilic unit of unsaturated olefinic carboxylic acid type corresponds to, for example, the monomer of formula (II) below:

* L I f

0

(Π) in which R¹ is chosen from H, C¾, and C₂H₅, i.e., acrylic acid, methacrylic acid, and ethacrylic acid units. The hydrophobic unit of a type such as a (C₁0-C30) alkyl ester of an unsaturated carboxylic acid corresponds to, for example, the monomer of formula (III) below: HLC= C C— OR²

in which R¹ is chosen from H, CH₃, and C2H5 (i.e., acrylate, methacrylate, and ethacrylate units) and is, for example, chosen from, for example, H (acrylate units) and C¾ (methacrylate units), and R² is chosen from Cio-C₃₀ alkyl radicals, for example, C₁₂-C₂₂ alkyl radicals.

Examples of (Ci₀-C3o)alkyl esters of unsaturated carboxylic acids include lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.

Anionic amphiphilic polymers of this type are disclosed and prepared, for example, according to U.S. Pat. Nos. 3,915,921 and 4,509,949.

Representative anionic amphiphilic polymers that can be used may further be chosen from polymers formed from a mixture of monomers comprising:

(7) acrylic acid, an ester of formula (IV) below:

1 2

in which R is chosen from H and CH₃, R is chosen from 0-C30 alkyl radicals, such as alkyl radicals containing from 12 to 22 carbon atoms, and a crosslinking agent; such as polymers derived from 95% to 60% by weight of the acrylic acid (hydrophilic unit), 4% to 40% by weight of Ci₀-C3o alkyl acrylate (hydrophobic unit), and 0% to 6% by weight of crosslinking polymerizable monomer, or polymers derived from 98% to 96% by weight of the acrylic acid (hydrophilic unit), 1% to 4% by weight of C10-C30 alkyl acrylate (hydrophobic unit), and 0.1 % to 0.6% by weight of crosslinking polymerizable monomer; or

(8) acrylic acid and lauryl methacrylate, such as the polymers formed from 66% by weight of acrylic acid and 34% by weight of lauryl methacrylate.

The crosslinking agent can be a monomer comprising a group

with at least one other polymerizable group whose unsaturated bonds are not conjugated.

Mention may be made, for example, of polyallyl ethers such as polyallylsucrose and

polyallylpentaerythritol. Among said polymers above, mention may be made, for example, of the products sold by the company Goodrich under the trade names Pemulen TR1, Pemulen TR2, and Carbopol 1382, and further, for example, Pemulen TR1, and the product sold by the company S.E.P.C. under the name Coatex SX.

Among anionic amphiphilic fatty-chain polymers, mention may also be made, for example, of the ethoxylated copolymer of methacrylic acid/methyl acrylate/alkyl

dimethyl-meta-isopropenylbenzylisocyanate sold under the name Viscophobe DB 1000 by the company Amerchol.

The (cc) cationic amphiphilic polymers used are, for example, chosen from quaternized cellulose derivatives and polyacrylates comprising amino side groups. The quaternized cellulose derivatives are, for example, chosen from

quaternized celluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl, and alkylaryl groups comprising at least 8 carbon atoms, and mixtures thereof, and quaternized hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl, and alkylaryl groups comprising at least 8 carbon atoms, and mixtures thereof.

Quaternized and non-quaternized polyacrylates comprising amino side groups have, for example, hydrophobic groups, such as Steareth 20 (polyoxy-ethylenated(20) stearyl alcohol) and

(C₁₀-C₃o)alkyl PEG-20 itaconate. The alkyl radicals borne by the above quaternized celluloses and hydroxyethylcelluloses, for example, contain from 8 to 30 carbon atoms.

The aryl radicals, for example, are chosen from phenyl, benzyl, naphthyl, and anthryl groups. Examples of quaternized alkylhydroxyethyl-celluloses comprising C8-C30 fatty chains are the products Quatrisoft LM 200, Quatrisoft LM-X 529-18-A, Quatnsoft LM-X 529- 18B (C₁₂ alkyl), and Quatrisoft LM-X 529-8 (C₁₈ alkyl) sold by the company Amerchol, and the products Crodacel QM, Crodacel QL (Q₂ alkyl), and Crodacel QS (Cig alkyl) sold by the company Croda. Examples of polyacrylates comprising amino side chains are the polymers 8781-124B or

9492-103 and Structure Plus from the company National Starch.

Among the (dd) amphoteric amphiphilic polymers comprising at least one hydrophilic unit and at least one fatty-chain unit, mention may be made, for example, of copolymers of

memacrylamidopropyltrimemylanimonium chloride/acrylic acid/Ci₀-C₃o alkyl methacrylate, wherein the alkyl radical is, for example, a stearyl radical.

The associative thickeners in the compositions can have, for example, in solution or in dispersion at a concentration of 1% active material in water, a viscosity, measured using a Rheomat RM 180 rheometer at 25°C, of greater than 0.1 ps and further, for example, of greater than 0.2 cp, at a shear rate of 200 s^"1.

(ii) Among the crosslinked acrylic acid homopolymers that may be mentioned are those crosslinked with an allylic alcohol ether of the sugar series, such as the products sold under the names Carbopol 980, 981 , 954, 2984, and 5984 by the company Goodrich or the products sold under the names Synthalen M and Synthalen K by the company 3 VSA.

(iii) The crosslinked copolymers of (meth)acrylic acid and of Ci-C₆ alkyl acrylate can be chosen from crosslinked copolymers of methacrylic acid and of ethyl acrylate as an aqueous dispersion comprising 38% active material sold, for example, under the name Viscoatex 538C by the company Coatex, and crosslinked copolymers of acrylic acid and of ethyl acrylate as an aqueous dispersion comprising 28% active material sold under the name Aculyn 33 by the company Rohm & Haas. Crosslinked copolymers of methacrylic acid and of ethyl acrylate include an aqueous dispersion comprising 30% active material sold under the name CARBOPOL AQUA SF-1 by the company NOVEON.

(iv) Among the nonionic homopolymers or copolymers comprising ethylenically unsaturated monomers of ester and or amide type, mention may be made of the products sold under the names: Cyanamer P250 by the company Cytec (polyacrylamide); PMMA MBX-8C by the company US Cosmetics (methyl methacrylate/ethylene glycol dimethacrylate copolymer);

Acryloid B66 by the company Rohm & Haas (butyl methacrylate/methyl methacrylate copolymer); and BPA 500 by the company Kobo (polymethyl methacrylate).

(v) Ammonium acrylate homopolymers that may be mentioned include the product sold under the name Microsap PAS 5193 by the company Hoechst.

Copolymers of ammonium acrylate and of acrylamide include the product sold under the name Bozepol C Nouveau or the product PAS 5193 sold by the company Hoechst (which are described and prepared in documents FR-2 416 723, U.S. Pat. No. 2,798,053, and U.S. Pat. No. 2,923,692).

It is preferable that the (c) thickener is selected from polysaccharides.

(vi) The polysaccharides are, for example, chosen from glucans, modified and unmodified starches (such as those derived, for example, from cereals, for instance wheat, corn, or rice, from vegetables, for instance yellow peas, and tubers, for instance potatoes or cassava), amylose, amylopectin, glycogen, dextrans, celluloses, and derivatives thereof (e.g., methylcelluloses, hydroxyalkylcelluloses, ethyl hydroxyethylcelluloses, and carboxymethylcelluloses), mannans, xylans, lignins, arabans, galactans, galacturonans, chitin, chitosans, glucuronoxylans,

arabinoxylans, xyloglucans, glucomannans, pectic acids, and pectins, alginic acid and alginates, arabinogalactans, carrageenans, agars, glycosaminoglucans, gum arables, gum tragacanths, ghatti gums, karaya gums, carob gums, galactomannans, such as guar gums, and nonionic derivatives thereof (e.g., hydroxypropyl guar), and xanthan gums, and mixtures thereof.

For example, the polysaccharides that may be used are chosen from those described, for example, in "Encyclopedia of Chemical Technology", Kirk-Othmer, Third Edition, 1982, volume 3, pp. 896-900, and volume 15, pp. 439-458, in "Polymers in Nature" by E. A. MacGregor and C. T. Greenwood, published by John Wiley & Sons, Chapter 6, pp. 240-328, 1980, and in "Industrial Gums-Polysaccharides and their Derivatives", edited by Roy L. Whistler, Second Edition, published by Academic Press Inc., the content of these three publications being entirely incorporated by reference.

For example, starches, guar gums, celluloses, and derivatives thereof can be used.

Among the starches that may be used, mention may be made, for example, of macromolecules in the form of polymers comprising base units which are anhydroglucose units. The number of these units and their assembly make it possible to distinguish between amylose (linear polymer) and amylopectin (branched polymer). The relative proportions of amylose and amylopectin, as well as their degree of polymerization, can vary according to the botanical origin of the starches. The molecules of starches used may have cereals or tubers as their botanical origin. Thus, the starches can be, for example, chosen from maize, rice, cassava, tapioca, barley, potato, wheat, sorghum, and pea starches.

Starches generally exist in the form of a white powder, insoluble in cold water, whose elementary particle size ranges from 3 to 100 microns.

The starches may be optionally Ci-C₆ hydroxyalkylated or Q- s acylated (such as acetylated). The starches may have also undergone heat treatments. Distarch phosphates or compounds rich in distarch phosphate, such as the product provided under the references PREJEL VA-70-T AGGL (gelatinized hydroxypropylated cassava distarch phosphate) or PREJEL TKl (gelatinized cassava distarch phosphate) or PREJEL 200 (gelatinized acetylated cassava distarch phosphate) by the company AVEBE, may also be used. The guar gums can be modified or unmodified.

The unmodified guar gums are, for example, the products sold under the name Vidogum GH 175 by the company Unipectine and under the names Meypro-Guar 50 and Jaguar C by the company Meyhall.

The modified nonionic guar gums are, for example, modified with Ci-C₆ hydroxyalkyl groups.

Among the hydroxyalkyl groups that may be mentioned, for example, are hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxybutyl groups.

These guar gums are well known in the prior art and can be prepared, for example, by reacting the corresponding alkene oxides such as propylene oxides, with the guar gum so as to obtain a guar gum modified with hydroxypropyl groups. The degree of hydroxyalkylation, which corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functions present on the guar gum, may, for example, range from 0.4 to 1.2.

Such nonionic guar gums optionally modified with hydroxyalkyl groups are sold, for example, under the trade names Jaguar HP8, Jaguar HP60, Jaguar HP 120, Jaguar DC 293, and Jaguar HP 105 by the company Rhodia Chimie (Meyhall) or under the name Galactasol 4H₄FD2 by the company Aqualon.

Among the celluloses and cellulose derivatives, such as cellulose modified with hydroxylalkyl groups, that are used are, for example, hydroxypropylmethyl cellulose, hydroxyethylcellulose, and hydroxypropylcelluloses, as well as hydrophobicized hydroxypropylmethylcellulose. Mention may be made of the products sold under the names Klucel E F, Klucel H, Klucel L H F, Klucel M F, and Klucel G by the company Aqualon. (vii) The fatty alcohols are, for example, chosen from myristyl alcohol, cetyl alcohol, stearyl alcohol, and behenyl alcohol.

The (c) thickener may represent an amount ranging, for example, from 0.001 % to 15% by weight, and further, for example, from 0.01% to 10% by weight, and even further, for example, from 0.1% to 5% by weight, relative to the total weight of the composition.

[Water]

The composition according to the present invention comprises (d) water.

The amount of (d) water is not limited, and may be from 30 to 75% by weight, preferably from 35 to 70%) by weight, and more preferably 40 to 60% by weight, relative to the total weight of the composition. [Surfactant]

The composition according to the present invention may comprise at least one (e) surfactant.

Any surfactant may be used for the present invention. The (e) surfactant used in the present invention may be selected from the group consisting of anionic surfactants, amphoteric surfactants, cationic surfactants, and nonionic surfactants. Two or more surfactants may be used in combination. Thus, a single type of surfactant or a combination of different types of surfactants may be used. The (e) surfactant may preferably be selected from the group consisting of nonionic surfactants. (Anionic Surfactants)

According to the present invention, the type of anionic surfactant is not limited. It is preferable that the anionic surfactant be selected from the group consisting of (C₆-C₃₀)alkyl sulfates, (C₆-C3o)alkyl ether sulfates, (C₆-C₃o)alkylamido ether sulfates, alkylaryl polyether sulfates, and monoglyceride sulfates; (C₆-C₃o)alkylsulfonates, (C6-C3o)alkylamide sulfonates, (C₆-C3₀)alkylaryl sulfonates, a-olefm sulfonates, and paraffin sulfonates; (C -C₃o)alkyl phosphates; (C₆-C₃₀)alkyl sulfosuccinates, (C₆-C3o)alkyl ether sulfosuccinates, and (C₆-C3o)alkylamide sulfosuccinates; (C₆-C₃₀)alkyl sulfoacetates; (C₆-C₂₄)acyl sarcosinates; (C₆-C₂₄)acyl glutamates;

(C -C3o)alkylpolyglycoside carboxylic ethers; (C₆-C3₀)alkylpolyglycoside sulfosuccinates;

(C₆-C3o)alkyl sulfosuccinamates; (C₆-C₂₄)acyl isethionates; N-(C₆-C₂4)acyl taurates; C₆-C3₀ fatty acid salts; coconut oil acid salts or hydrogenated coconut oil acid salts; (C₈-C₂o)acyl lactylates; (C₆-C₃₀)alkyl-D-galactoside uronic acid salts; polyoxyalkylenated (C₆-C3₀)alkyl ether carboxylic acid salts; polyoxyalkylenated (C6-C3o)alkylaryl ether carboxylic acid salts; and

polyoxyalkylenated (C₆-C3₀)alkylamido ether carboxylic acid salts.

It is more preferable that the anionic surfactant be selected from salts of (C₆-C3o)alkyl sulfate or polyoxyalkylenated (C₆-C3₀)alkyl ether carboxylic acid salts.

In at least one embodiment, the anionic surfactants are in the form of salts such as salts of alkali metals, for instance sodium; salts of alkaline-earth metals, for instance magnesium; ammonium salts; amine salts; and amino alcohol salts. Depending on the conditions, they may also be in acid form.

(Amphoteric Surfactants)

According to the present invention, the type of amphoteric surfactant is not limited. The amphoteric or zwitterionic surfactants can be, for example (non-limiting list), amine derivatives such as aliphatic secondary or tertiary amine, and optionally quaternized amine derivatives, in which the aliphatic radical is a linear or branched chain comprising 8 to 22 carbon atoms and containing at least one water-solubilizing anionic group (for example, carboxylate, sulphonate, sulphate, phosphate, or phosphonate). The amphoteric surfactant may preferably be selected from the group consisting of betaines and amidoaminecarboxylated derivatives.

The betaine-type amphoteric surfactant is preferably selected from the group consisting of alkylbetaines, alkylamidoalkylbetaines, sulfobetaines, phosphobetaines, and

alkylamidoalkylsulfobetaines, in particular, (C₈-C₂4)alkylbetaines,

(C₈-C₂₄)alkylamido(Ci-C₈)alkylbetaines, sulphobetaines, and

(C₈-C2₄)alkylamido(Ci-C₈)alkylsulphobetaines. In one embodiment, the amphoteric surfactants of betaine type are chosen from (C -C₂4)alkylbetaines,

(C₈-C₂₄)alkylamido(C₁-C₈)alkylsulphobetaines, sulphobetaines, and phosphobetaines.

Non-limiting examples that may be mentioned include the compounds classified in the CTFA dictionary, 9th edition, 2002, under the names cocobetaine, laurylbetaine, cetylbetaine, coco/ oleamidopropylbetaine, cocamidopropylbetaine, palmitamidopropylbetaine,

stearamidopropylbetaine, cocamidoethylbetaine, cocamidopropylhydroxysultaine,

oleamidopropylhydroxysultaine, cocohydroxysultaine, laurylhydroxysultaine, and cocosultaine, alone or as mixtures.

The betaine-type amphoteric surfactant is preferably an alkylbetaine and an

alkylamidoalkylbetaine, in particular cocobetaine and cocamidopropylbetaine.

Among the amidoaminecarboxylated derivatives, mention may be made of the products sold under the name Miranol, as described in U.S. Pat. Nos. 2,528,378 and 2,781 ,354 and classified in the CTFA dictionary, 3rd edition, 1982 (the disclosures of which are incorporated herein by reference), under the names Amphocarboxyglycinates and Amphocarboxypropionates, with the respective structures:

R₁-CONHCH₂CH₂-N⁺(R₂)(R₃)(CH₂COO^") in which:

Ri denotes an alkyl radical of an acid R_t-COOH present in hydrolysed coconut oil, a heptyl, nonyl, or undecyl radical,

R₂ denotes a beta-hydroxyethyl group, and

R₃ denotes a carboxymethyl group; and R -CONHCH₂CH₂-N(B)(C) in which:

B represents -CH₂CH₂OX',

C represents -(CH₂)_Z-Y', with z=l or 2,

X' denotes a -CH₂CH₂-COOH group, -CH₂-COOZ' , -CH₂CH₂-COOH, -CH₂CH₂-COOZ' , or a hydrogen atom,

Y^* denotes -COOH, -COOZ', -CH₂-CHOH-S0₃Z', or a -CH₂-CHOH-S0₃H radical,

Z' represents an ion of an alkaline or alkaline earth metal such as sodium, an ammonium ion, or an ion issued from an organic amine, and

Ri' denotes an alkyl radical of an acid Ri'-COOH present in coconut oil or in hydrolysed linseed oil, an alkyl radical, such as a C₇, C₉, Cu, or Q₃ alkyl radical, a C₁₇ alkyl radical and its iso form, or an unsaturated C₁₇ radical.

It is preferable that the amphoteric surfactant be selected from (C -C₂₄)-alkyl amphomonoacetates, (C₈-C₂4)alkyl amphodiacetates, (C8-C₂₄)alkyl amphomonopropionates, and (C₈-C₂4)alkyl amphodipropionates

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 Lauroamphopropionate, Disodium Caprylamphodipropionate, Disodium

Caprylamphodipropionate, 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 Chimie. (Cationic Surfactants)

According to the present invention, the type of cationic surfactant is not limited. The cationic surfactant may be selected from the group consisting of optionally polyoxyalkylenated, primary, secondary, or tertiary fatty amine salts, quaternary ammonium salts, and mixtures thereof.

Examples of quaternary ammonium salts that may be mentioned include, but are not limited to: those of general formula (I) below:

N

/ \

¾ R₄

(I)

wherein

Ri, R₂, R₃, and R4, which may be identical or different, are chosen from linear and branched aliphatic radicals comprising from 1 to 30 carbon atoms and optionally comprising heteroatoms such as oxygen, nitrogen, sulfur, and halogens. The aliphatic radicals may be chosen, for example, from alkyl, alkoxy, C₂-C₆ polyoxyalkylene, alkylamide,

(Ci₂-C₂2)alkylamido(C₂-C₆)alkyl, (Ci2-C₂₂)alkylacetate, and hydroxyalkyl radicals; and aromatic radicals such as aryl and alkylaryl; and X^" is chosen from halides, phosphates, acetates, lactates, (C₂-C₆) alkyl sulfates, and alkyl- or alkylaryl-sulfonates;

quaternary ammonium salts of imidazoline, for instance those of formula (II) below:

(Π)

wherein:

R₅ is chosen from alkenyl and alkyl radicals comprising from 8 to 30 carbon atoms, for example fatty acid derivatives of tallow or of coconut;

R<5 is chosen from hydrogen, C1-C4 alkyl radicals, and alkenyl and alkyl radicals comprising from

8 to 30 carbon atoms;

R₇ is chosen from Q-C₄ alkyl radicals;

R₈ is chosen from hydrogen and Q-C₄ alkyl radicals; and

X^" is chosen from halides, phosphates, acetates, lactates, alkyl sulfates, alkyl sulfonates, and alkylaryl sulfonates. In one embodiment, R₅ and R<5 are, for example, a mixture of radicals chosen from alkenyl and alkyl radicals comprising from 12 to 21 carbon atoms, such as fatty acid derivatives of tallow, R₇ is methyl, and R_$ is hydrogen. Examples of such products include, but are not limited to, Quaternium-27 (CTFA 1997) and Quaternium-83 (CTFA 1997), which are sold under the names "Rewoquat®" W75, W90, W75PG, and W75HPG by the company Witco; diquaternary ammonium salts of formula (III):

(III)

wherein:

R₉ is chosen from aliphatic radicals comprising from 16 to 30 carbon atoms;

R₁₀ is chosen from hydrogen or alkyl radicals comprising from 1 to 4 carbon atoms or a group

Rn, R₁₂, R₁₃, R₁₄, Rj6a, Rna, and R_18a, which may be identical or different, are chosen from hydrogen and alkyl radicals comprising from 1 to 4 carbon atoms; and

X^" is chosen from halides, acetates, phosphates, nitrates, ethyl sulfates, and methyl sulfates.

An example of one such diquaternary ammonium salt is FINQUAT CT-P of

FINETEX(Quaternium-89) or FINQUAT CT of FINETEX (Quaternium-75); and

quaternary ammonium salts comprising at least one ester function, such as those of formula (IV) below:

R 24 - X

(IV)

wherein:

R₂₂ is chosen from Ci-C₆ alkyl radicals, and Ci-C₆ hydroxyalkyl and dihydroxyalkyl radicals; R₂₃ is chosen from:

the radical below:

linear and branched, saturated and unsaturated Q.C^ hydrocarbon-based radicals R₂₇, and hydrogen,

R₂₅ is chosen from:

the radical below:

linear and branched, saturated and unsaturated Ci-C hydrocarbon-based radicals R₂₉, and hydrogen,

R24, R26, and R₂₈, which may be identical or different, are chosen from linear and branched, saturated and unsaturated, C₇-C₂i, hydrocarbon-based radicals;

r, s, and t, which may be identical or different, are chosen from integers ranging from 2 to 6; each of rl and tl, which may be identical or different, is 0 or 1, and r2+rl=2r and tl+2t=2t;

y is chosen from integers ranging from 1 to 10;

x and z, which may be identical or different, are chosen from integers ranging from 0 to 10;

X^" is chosen from simple and complex, organic and inorganic anions; with the proviso that the sum x+y+z ranges from 1 to 15, that when x is 0, R₂₃ denotes R₂₇, and that when z is 0, R₂₅ denotes R₂₉. R₂₂ may be chosen from linear and branched alkyl radicals. In one embodiment, R₂₂ is chosen from linear alkyl radicals. In another embodiment, R₂₂ is chosen from methyl, ethyl, hydroxyethyl, and dihydroxypropyl radicals, for example methyl and ethyl radicals. In one embodiment, the sum x+y+z ranges from 1 to 10. When R₂₃ is a hydrocarbon-based radical R₂₇, it may be long and comprise from 12 to 22 carbon atoms, or short and comprise from 1 to 3 carbon atoms. When R₂₅ is a hydrocarbon-based radical R₂₉, it may comprise, for example, from 1 to 3 carbon atoms. By way of a non-limiting example, in one embodiment, R₂₄, R₂₆, and R₂₈, which may be identical or different, are chosen from linear and branched, saturated and

unsaturated, Cu-C₂] hydrocarbon-based radicals, for example from linear and branched, saturated and unsaturated Cn-C₂i alkyl and alkenyl radicals. In another embodiment, x and z, which may be identical or different, are 0 or 1. In one embodiment, y is equal to 1. In another embodiment, r, s, and t, which may be identical or different, are equal to 2 or 3, for example equal to 2. The anion X^" may be chosen from, for example, halides, such as chloride, bromide, and iodide; and Ci-C₄ alkyl sulfates, such as methyl sulfate. However, methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate and lactate, and any other anion that is compatible with the ammonium comprising an ester function, are other non-limiting examples of anions that may be used according to the invention. In one embodiment, the anion X^" is chosen from chloride and methyl sulfate. In another embodiment, the ammonium salts of formula (IV) may be used, wherein:

R₂₂ is chosen from methyl and ethyl radicals,

x and y are equal to 1 ;

z is equal to 0 or 1 ;

r, s, and t are equal to 2;

R₂₃ is chosen from:

the radical below:

methyl, ethyl, and C₁₄-C₂₂ hydrocarbon-based radicals, and hydrogen;

R₂5 is chosen from:

the radical below:

O

R ^l2. 8

and hydrogen;

24, 26, and R₂₈, which may be identical or different, are chosen from linear and branched, saturated and unsaturated, Ci₃-Ci₇ hydrocarbon-based radicals, for example from linear and branched, saturated and unsaturated, C13-C17 alkyl and alkenyl radicals.

In one embodiment, the hydrocarbon-based radicals are linear. Non-limiting examples of compounds of formula (IV) that may be mentioned include salts, for example chloride and methyl sulfate, of diacyloxyethyl-dimethylammonium, of

diacyloxyethyl-hydroxyethyl-methylammonium, of

monoacyloxyethyl-dihydroxyethyl-methylammonium, of triacyloxyethyl-methylammonium, of monoacyloxyethyl-hydroxyethyl-dimemyl-ammonium, and mixtures thereof. In one embodiment, the acyl radicals may comprise from 14 to 18 carbon atoms, and may be derived, for example, from a plant oil, for instance palm oil and sunflower oil. When the compound comprises several acyl radicals, these radicals may be identical or different.

These products may be obtained, for example, by direct esterification of optionally oxyalkylenated triethanolamine, 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 may be followed by a quaternization using an alkylating agent chosen from alkyl halides, for example methyl and ethyl halides; dialkyl sulfates, for example dimethyl and diethyl sulfates; methyl methanesulfonate; methyl

para-toluenesulfonate; glycol chlorohydrin; and 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.

Other non-limiting examples of ammonium salts that may be used in the compositions according to the invention include the ammonium salts comprising at least one ester function described in U.S. Pat. Nos. 4,874,554 and 4,137,180. Among the quaternary ammonium salts mentioned above that may be used in the compositions according to the invention include, but are not limited to, those corresponding to formula (I), for example tetraalkylammonium chlorides, for instance dialkyldimethylammonium and

alkyltrimethylammonium chlorides in which the alkyl radical comprises from about 12 to 22 carbon atoms, such as behenyltrimethylammonium, distearyldimethylammonium,

cetyllrimethylammonium, and benayldimemylstearylammonium chloride;

palmitylamidopropyltrimemylammonium chloride; and stearamidopropyldimethyl(myristyl acetate)ammonium chloride, sold under the name "Ceraphyl® 70" by the company Van Dyk.

According to one embodiment, the cationic surfactant that may be used in the compositions of the invention is chosen from quaternary ammonium salts, for example from

behenyltrimemylammonium chloride, cetyltrimethylammonium chloride, Quaternium-83, Quaternium-87, Quaternium-22, behenylamidopropyl-2,3 -dmydroxypropyldimethylammonium chloride, palmitylarnidopropyltrimethylammonium chloride, and

stearamidopropyldimethylamine. (Nonionic Surfactants)

The nonionic surfactants are compounds well known in themselves (see, e.g., in this regard, "Handbook of Surfactants" by M. R. Porter, Blackie & Son publishers (Glasgow and London), 1991, pp. 116-178). Thus, they can, for example, be chosen from alcohols, alpha-diols, alkylphenols and esters of fatty acids, these compounds being ethoxylated, propoxylated or glycerolated and having at least one fatty chain comprising, for example, from 8 to 30 carbon atoms, it being possible for the number of ethylene oxide or propylene oxide groups to range from 2 to 50, and for the number of glycerol groups to range from 1 to 30. Maltose derivatives may also be mentioned. Non-limiting mention may also be made of copolymers of ethylene oxide and/or of propylene oxide; condensates of ethylene oxide and/or of propylene oxide with fatty alcohols; polyethoxylated fatty amides comprising, for example, from 2 to 30 mol of ethylene oxide; polyglycerolated fatty amides comprising, for example, from 1.5 to 5 glycerol groups, such as from 1.5 to 4; ethoxyla^'ted fatty acid esters of sorbitan comprising from 2 to 30 mol of ethylene oxide; ethoxylated oils of plant origin; fatty acid esters of sucrose; fatty acid esters of polyethylene glycol; polyethoxylated fatty acid mono or diesters of glycerol (C₆-C24)alkylpolyglycosides; N-(C₆-C₂₄)alkylglucamine derivatives; amine oxides such as (Ci₀-Ci₄)alkylamine oxides or N-(Cio-C₁4)acylaminopropylmorpholine oxides; and mixtures thereof. The nonionic surfactants may preferably be chosen from monooxyalkylenated,

polyoxyalkylenated, monoglycerolated or polyglycerolated nonionic surfactants. The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or a combination thereof, and are preferably oxyethylene units. Examples of monooxyalkylenated or polyoxyalkylenated nonionic surfactants that may be mentioned include:

monooxyalkylenated or polyoxyalkylenated (C₈-C2₄)aIkylphenols,

saturated or unsaturated, linear or branched, monooxyalkylenated or polyoxyalkylenated C₈-C₃o alcohols,

saturated or unsaturated, linear or branched, monooxyalkylenated or polyoxyalkylenated C₈-C₃₀ amides,

esters of saturated or unsaturated, linear or branched, C₈-C₃₀ acids and of polyalkylene glycols, monooxyalkylenated or polyoxyalkylenated esters of saturated or unsaturated, linear or branched, C₈-C₃o acids and of sorbitol,

saturated or unsaturated, monooxyalkylenated or polyoxyalkylenated plant oils,

condensates of ethylene oxide and/or of propylene oxide, inter alia, alone or as mixtures.

The surfactants preferably contain a number of moles of ethylene oxide and/or of propylene oxide of between 1 and 100 and most preferably between 2 and 50. Advantageously, the nonionic surfactants do not comprise any oxypropylene units.

According to one of the embodiments of the present invention, the polyoxyalkylenated nonionic surfactants are chosen from polyoxyethylenated fatty alcohol (polyethylene glycol ether of fatty alcohol), polyoxyethylenated fatty ester (polyethylene glycol ester of fatty acid), and mixture of polyoxyethylenated fatty alcohol and polyoxyethylenated fatty ester. Examples of polyoxyethylenated fatty alcohol (or C₈-C3₀ alcohols) that may be mentioned include the adducts of ethylene oxide with lauryl alcohol, especially those containing from 2 to 50 oxyethylene units and more particularly those containing from 2 to 20 oxyethylene units

(Laureth-2 to Laureth-20, as the CTFA names); the adducts of ethylene oxide with behenyl alcohol, especially those containing from 2 to 50 oxyethylene units and more particularly those containing from 2 to 20 oxyethylene units (Beheneth-2 to Beheneth-20, as the CTFA names); the adducts of ethylene oxide with cetearyl alcohol (mixture of cetyl alcohol and stearyl alcohol), especially those containing from 2 to 30 oxyethylene units (Ceteareth-2 to Ceteareth-30, as the CTFA names); the adducts of ethylene oxide with cetyl alcohol, especially those containing from 2 to 30 oxyethylene units (Ceteth-2 to Ceteth-30, as the CTFA names); the adducts of ethylene oxide with stearyl alcohol, especially those containing from 2 to 50 oxyethylene units and more particularly those containing from 2 to 20 oxyethylene units (Steareth-2 to Steareth-20, as the CTFA names); the adducts of ethylene oxide with isostearyl alcohol, especially those containing from 2 to 50 oxyethylene units (Isosteareth-2 to Isosteareth-50, as the CTFA names); and mixtures thereof.

Examples of polyoxyethylenated fatty esters that may be mentioned include the adducts of ethylene oxide with esters of lauric acid, palmitic acid, stearic acid or behenic acid, and mixtures thereof, especially those containing from 9 to 100 oxyethylene units, such as PEG-9 to PEG-50 laurate (as the CTFA names: PEG-9 laurate to PEG-50 laurate); PEG-9 to PEG-50 palmitate (as the CTFA names: PEG-9 palmitate to PEG-50 palmitate); PEG-9 to PEG-50 stearate (as the CTFA names: PEG-9 stearate to PEG-50 stearate); PEG-9 to PEG-50 palmitostearate; PEG-9 to PEG-50 behenate (as the CTFA names: PEG-9 behenate to PEG-50 behenate); polyethylene glycol 100 EO monostearate (CTFA name: PEG- 100 stearate); and mixtures thereof.

According to one preferred embodiment of the invention, the composition according to the present invention comprises at least one polyoxyethylenated fatty alcohol. According to a more preferred embodiment, the composition according to the invention contains at least one fatty alcohol comprising from 2 to 9 ethyleneoxide units and at least one fatty alcohol comprising from 10 to 30 ethyleneoxide units.

As examples of monoglycerolated or polyglycerolated nonionic surfactants, monoglycerolated or polyglycerolated C₈-C₄₀ alcohols are preferably used.

In particular, the monoglycerolated or polyglycerolated C₈-C₄₀ alcohols correspond to the following formula: RO-[CH₂-CH(CH₂OH)-0]_m-H or RO-[CH(CH₂OH)-CH₂0]_m-H in which R represents a linear or branched C₈-C₄₀ and preferably Q-C30 alkyl or alkenyl radical, and m represents a number ranging from 1 to 30 and preferably from 1.5 to 10. As examples of compounds that are suitable in the context of the present invention, mention may be made of lauryl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcohol containing 1.5 mol of glycerol, oleyl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol containing 2 mol of glycerol (INCI name:

Polyglyceryl-2 Oleyl Ether), cetearyl alcohol containing 2 mol of glycerol, cetearyl alcohol containing 6 mol of glycerol, oleocetyl alcohol containing 6 mol of glycerol, and octadecanol containing 6 mol of glycerol.

The alcohol may represent a mixture of alcohols in the same way that the value of m represents a statistical value, which means that, in a commercial product, several species of polyglycerolated fatty alcohol may coexist in the form of a mixture.

Among the monoglycerolated or polyglycerolated alcohols, it is preferable to use the C₈/Cio alcohol containing 1 mol of glycerol, the Ci₀/C₁₂ alcohol containing 1 mol of glycerol and the Ci₂ alcohol containing 1.5 mol of glycerol.

The monoglycerolated or polyglycerolated C₈-C₄₀ fatty esters may correspond to the following formula:

R'0-[CH2-CH(CH₂OR'")-0]_m-R" or RO-[CH(CH₂OR'' CH₂0]_ra-R" in which each of R', R" and R'" independently represents a hydrogen atom, or a linear or branched C₈-C₄₀ and preferably C₈-C₃₀ alkyl-CO- or alkenyl-CO-radical, with the proviso that at least one of R', R" and R'" is not a hydrogen atom, and m represents a number ranging from 1 to 30 and preferably from 1.5 to 10.

Examples of polyoxyethylenated fatty esters that may be mentioned include the adducts of ethylene oxide with esters of lauric acid, palmitic acid, stearic acid or behenic acid, and mixtures thereof, especially those containing from 9 to 100 oxyethylene units, such as PEG-9 to PEG-50 laurate (as the CTFA names: PEG-9 laurate to PEG-50 laurate); PEG-9 to PEG-50 palmitate (as the CTFA names: PEG-9 palmitate to PEG-50 palmitate); PEG-9 to PEG-50 stearate (as the CTFA names: PEG-9 stearate to PEG-50 stearate); PEG-9 to PEG-50 pahnitostearate; PEG-9 to PEG-50 behenate (as the CTFA names: PEG-9 behenate to PEG-50 behenate); polyethylene glycol 100 EO monostearate (CTFA name: PEG- 100 stearate); and mixtures thereof. Preferably, the nonionic surfactant may be a nonionic surfactant with an HLB from 8 to 18. The HLB is the ratio between the hydrophilic part and the lipophilic part in the molecule. This term HLB is well known to those skilled in the art and is described in "The HLB system. A time-saving guide to emulsifier selection" (published by ICI Americas Inc., 1984). According to one embodiment of the present invention, the amount of the surfactant(s) may range from 0.1 to 30% by weight, preferably from 0.5 to 25% by weight, and more preferably from 1 to 20% by weight, relative to the total weight of the composition according to the present invention.

[Other Ingredients] The composition according to the present invention may also comprise an effective amount of other ingredients, which are preferably common in cosmetic products, such as various common adjuvants, antiageing agents, whitening agents, anti-greasy skin agents, sequestering agents such as EDTA and etidronic acid, UV-screening agents, preserving agents such as chlorphenesin, vitamins, or provitamins, for instance, panthenol, opacifiers, fragrances, plant extracts, cationic polymers, and so on.

The composition according to the present invention may further comprise at least one organic solvent. Thus, the organic solvent is preferably water miscible. As the organic solvent, there may be mentioned, for example, C C₄ alkanols, such as ethanol and isopropanol; aromatic alcohols such as benzyl alcohol and phenoxyethanol; analogous products; and mixtures thereof.

The organic water-soluble solvents may be present in an amount ranging from less than 10% by weight, preferably from 5% by weight or less, and more preferably from 1% by weight or less, relative to the total weight of the composition.

[Preparation and Properties]

The composition according to the present invention can be prepared by mixing the above essential and optional ingredients in accordance with a conventional process.

The pH of the composition according to the present invention may be controlled. The pH may be, for example, from 3 to 7, preferably from 4 to 7, and more preferably from 5 to 7, if the (b) dye is selected from acidic direct dyes. The pH may be, for example, from 7 to 11, preferably from 7 to 10, and more preferably from 7 to 9, if the (b) dye is selected from basic direct dyes and oxidative dyes.

The pH may be adjusted to the desired value using at least one acidifying agent and/or at least one basifying agent.

The acidifying agents can be, for example, mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, carboxylic acids, for instance tartaric acid, citric acid, and lactic acid, or sulphonic acids.

The basifying agent can be, for example, ammonium hydroxide, alkali metal hydroxide, alkali earth metal hydroxide, alkali metal carbonates, alkanolamines such as mono-, di-, and

triethanolamines, and also their derivatives, preferably sodium or potassium hydroxide and compounds of the formula below:

R1 R3

N-R-N

R2 R4

wherein

R denotes an alkylene such as propylene optionally substituted by a hydroxyl or a Q-Q alkyl radical, and Ri, R₂, R₃, and R₄ independently denote a hydrogen atom, an alkyl radical, or a Q-Q hydroxyalkyl radical, which may be exemplified by 1,3-propanediamine, and derivatives thereof. Arginine, urea, and monoethanolamine may be preferable. The acidifying or basifying agent may be present in an amount ranging from less than 10% by weight, preferably from 51% by weight or less, and more preferably from 3-0.5% by weight or less, relative to the total weight of the composition.

It is preferable that the composition according to the present invention be in the form of an emulsion, more preferably a fine emulsion, and even more preferably a nano- or micro-emulsion.

The composition according to the present invention may be in the form of an O/W emulsion, preferably an O/W nano- or micro-emulsion. If the dye is selected from direct dyes, the composition according to the present invention may be a so-called one-part composition or a ready-to-use composition. For the purposes of the present invention, the expression "ready-to-use composition" is defined herein as a composition to be applied immediately to keratin fibers such as hair. The so-called one-part composition or the ready-to-use composition may be in a form of hair color treatment composition.

As compared to a so-called two-part composition, a so-called one-part composition does not need to mix ingredients in the composition prior to use. Therefore, it is easy for a consumer to use the composition according to the present invention for dyeing keratin fibers. Furthermore, stable coloring of keratin fibers is possible for the composition according to the present invention, because it is not possible to fail to mix ingredients in a precise mixing ratio which is required for two-part compositions for dyeing keratin fibers.

[Process] The composition according to the present invention may be intended for dyeing a keratin substance, in particular keratin fibers. Thus, the compostion according to the present invention can be used as a cosmetic composition, in particular for keratin fibers.

The composition according to the present invention can be used for a non-therapeutic process, such as a cosmetic process, for dyeing keratin fibers such as eyelashes, eyebrows, and hair, comprising the step of applying the composition according to the present invention onto the keratin fibers.

The keratin fibers to which the composition according to the present invention has been applied can be left for an appropriate time which is required to treat the keratin fibers. The time length for the treatment is not limited, but it may be from 1 minute to 1 hours, preferably 1 minute to 30 minutes, and more preferably 1 minute to 15 minutes. For example, the time for dyeing the keratin fibers may be from 1 to 20 minutes, preferably 5 to 15 minutes. The keratin fibers may be treated at a room temperature. Alternatively, the keratin fibers can be heated at 25C to 65°C, preferably 30°C to 60 °C, more preferably35 °C to 55°C, more preferably 40 °C to 50 °C, during the step of applying the composition according to the present invention to the keratin fibers, and/or the step of leaving the keratin fibers to which the composition according to the present invention has been applied.

The keratin fibers may be rinsed after the step of applying the composition according to the keratin fibers onto the keratin fibers and/or after the step of leaving the keratin fibers to which the composition according to the present invention has been applied. If the (b) dye is selected from oxidative dyes, the composition according to the present invention is preferably mixed with an oxidizing composition including at least one oxidizing agent.

As the oxidizing agent, a single type of oxidizing agent or a combination of different types of oxidizing agents may be used.

The oxidizing agent may be selected from hydrogen peroxide, peroxygenated salts, and compounds capable of producing hydrogen peroxide by hydrolysis. For example, the oxidizing agent can be selected from aqueous hydrogen peroxide solution, urea peroxide, alkali metal bromates, and ferricyanides, and persalts such as perborates and persulphates.

It is preferable that the oxidizing agent be hydrogen peroxide.

The oxidizing agent's concentration may range from 0.1 to 45% by weight, preferably from 0.5 to 40% by weight, and more preferably 1 to 35% by weight, relative to the total weight of the oxidizing composition.

In one embodiment, when the oxidizing agent is hydrogen peroxide, the oxidizing composition may comprise at least one hydrogen peroxide stabilizer, which may be selected, for example, from alkali metal and alkaline-earth metal pyrophosphates, alkali metal and alkaline-earth metal stannates, phenacetin, and salts of acids and of oxyquinoline, for example, oxyquinoline sulphate. In another embodiment, at least one stannate optionally in combination with at least one pyrophosphate is used.

It is also possible to use salicylic acid and salts thereof, pyridinedicarboxylic acid and its salts, and paracetamol.

Moreover, the concentration of the hydrogen peroxide stabilizer may range from 0.0001 to 5% by weight such as from 0.01 to 2% by weight, relative to the total weight of the oxidizing

composition.

In the composition comprising hydrogen peroxide, the concentration ratio of the hydrogen peroxide to the stabilizer may range from 0.05: 1 to 1,000:1, such as from 0.1 :1 to 500:1, and further such as from 1 : 1 to 300: 1.

The oxidizing composition may further comprise any of the optional components described above for the composition according to the present invention.

In a preferred embodiment, the composition according to the invention is mixed prior to application on keratin fibers, with an oxidizing composition.

EXAMPLES

The present invention will be described in more detail by way of examples, which however should not be construed as limiting the scope of the present invention.

[Basic Dye and HC Dye]

[Examples 1-3 and Comparative Examples 1-3]

The following compositions according to Examples 1-3 and Comparative Examples 1-3, shown in Table 1 , were prepared by mixing the components shown in Table 1. The numerical values for the amounts of the components shown in Table 1 are all based on "% by weight" as active raw materials.

Table 1

[Evaluation] Each of the compositions according to Examples 1-3 and Comparative Examples 1-3 was applied onto a swatch of white goat hair in a weight ratio of 5 : 1 (the composition:the hair swatch). The applied hair swatch was left for 5 minutes at 27°C. It was then washed out with shampoo and dried. The color of the dyed hair swatch was then measured by Minolta CM-3600d. Based on the color (this was already measured before the application of the composition) of the undyed hair swatch and the measured color of the dyed hair swatch, ΔΕ (between the color of the undyed original hair and the color of the dyed hair under the L a b system) was calculated. For the evaluation of hair coloring ability, the following criteria was used. Hair Coloring Criteria

The evaluation results are shown in Table 1. It is clear from the experimental data in Table 1 that the presence of silicone oil in an amount of more than 25% by weight can provide better hair coloring ability.

[Examples 4-5 and Comparative Examples 4-7] The following compositions according to Examples 4-5 and Comparative Examples 4-7, shown in Table 2, were prepared by mixing the components shown in Table 2. The numerical values for the amounts of the components shown in Table 2 are all based on "% by weight" as active raw materials.

Table 2

[Evaluation] Each of the compositions according to Examples 4-5 and Comparative Examples 4-7 was applied onto a swatch of white goat hair in a weight ratio of 5: 1 (the composition:the hair swatch). The applied hair swatch was left for 5 minutes at 27°C. It was then washed out with shampoo and dried. The color of the dyed hair swatch was then measured by Minolta CM-3600d. Based on the color (this was already measured before the application of the composition) of the undyed hair swatch and the measured color of the dyed hair swatch, ΔΕ (between the color of the undyed original hair and the color of the dyed hair under the L a b system) was calculated. For the evaluation of hair coloring ability, the following criteria was used. Hair Coloring Criteria

The evaluation results are shown in Table 2. It is clear from the experimental data in Table 2 that silicone oils can provide better hair coloring ability than non-silicone oils.

[Acidic Dye] [Examples 6-7 and Comparative Example 8]

The following compositions according to Examples 6-7 and Comparative Example 8, shown in Table 3, were prepared by mixing the components shown in Table 3. The numerical values for the amounts of the components shown in Table 3 are all based on "% by weight" as active raw materials.

Table 3

[Evaluation]

Each of the compositions according to Examples 6-7 and Comparative Example 8 was applied onto a swatch of white goat hair in a weight ratio of 5 : 1 (the composition:the hair swatch). The applied hair swatch was left for 5 minutes at 27°C. It was then washed out with shampoo and dried. The color of the dyed hair swatch was then measured by Minolta CM-3600d. Based on the color (this was already measured before the application of the composition) of the undyed hair swatch and the measured color of the dyed hair swatch, ΔΕ (between the color of the undyed original hair and the color of the dyed hair under the L a b system) was calculated. For the evaluation of hair coloring ability, the following criteria was used.

Hair Coloring Criteria

The evaluation results are shown in Table 3.

It is clear from the experimental data in Table 3 that silicone oils can provide better hair coloring ability than non-silicone oil.

[Oxidative Dye]

[Example 8 and Comparative Example 9] The following compositions according to Example 8 and Comparative Example 9, shown in Table 4, were prepared by mixing the components shown in Table 4. The numerical values for the amounts of the components shown in Table 4 are all based on "% by weight" as active raw materials.

Table 4

[Evaluation]

Each of the compositions according to Example 8 and Comparative Example 9 was mixed with oxidizer with the following composition in a weight ratio of 5: 1 (the compositiomthe oxidizer).

!0

Each of the mixtures was applied onto a swatch of white goat hair in a weight ratio of 6:1 (the composition:the hair swatch). The applied hair swatch was left for 30 minutes at 27°C. It was then washed out with shampoo and dried. The color of the dyed hair swatch was then measured by Minolta CM-3600d. Based on the color (this was already measured before the application of 15 the mixture) of the undyed hair swatch and the measured color of the dyed hair swatch, ΔΕ

(between the color of the undyed original hair and the color of the dyed hair under the L a b system) was calculated. For the evaluation of hair coloring ability, the following criteria was used. 0 Hair Coloring Criteria

The evaluation results are shown in Table 4.

It is clear from the experimental data in Table 4 that silicone oil can provide better hair coloring ability than non-silicone oil.

Claims

A composition, comprising:

(a) at least one silicone oil;

(b) at least one dye;

(c) at least one thickener; and

(d) water,

wherein

The composition according to Claim 1, wherein the (a) silicone oil is selected from the group consisting of polydialkylsiloxanes, polyalkylarylsiloxanes, polydiarylsiloxanes, and organomodified polysiloxanes comprising at least one functional moiety chosen from poly(oxyalkylene) moieties, amine moieties, alkoxy moieties, hydroxylated moieties, acyloxyalkyl moieties, carboxylic acid moieties, hydroxyacylamino moieties, acrylic moieties, polyamine moieties, and oxazoline moieties.

The composition according to Claim 1 or 2, wherein the amount of the (a) silicone oil ranges from 25 to 90% by weight, preferably from 30 to 80%) by weight, and more preferably from 35 to 70% by weight, relative to the total weight of the composition.

The composition according to any one of Claims 1 to 3, wherein the (b) dye is selected from synthetic direct dyes and oxidative dyes.

The composition according to Claim 4, wherein the synthetic direct dyes are selected from the group consisting of cationic direct dyes, nonionic direct dyes, and anionic direct dyes.

The composition according to Claim 4, wherein the oxidative dyes are selected from oxidation bases and couplers.

The composition according to Claim 6, wherein the oxidation bases are selected from ortho- and para-phenylenediamines, double bases, ortho- and para-arninophenols, heterocyclic bases, and acid addition salts thereof.

The composition according to Claim 6, wherein the couplers are selected from meta-aminophenols, meta-phenylenediamines, meta-diphenols, naphthols, heterocyclic couplers, and acid addition salts thereof.

The composition according to any one of Claims 1 to 8 wherein the amount of the (b) dye ranges from 0.001 to 10% by weight, preferably from 0.01 to 5% by weight, and more preferably from 0.1 to 3 % by weight, relative to the total weight of the

composition. The composition according to any one of Claims 1 to 9, wherein the (c) thickener is selected from polysaccharides.

The composition according to any one of Claims 1 to 10 wherein the amount of the (c) thickener ranges from 0.001 to 15% by weight, preferably from 0.01 to 10% by weight, and more preferably from 0.1 to 5% by weight, relative to the total weight of the composition.

The composition according to any one of Claims 1 to 11, further comprising (e) at least one surfactant, preferably at least one nonionic surfactant.

The composition according to Claim 12, wherein the amount of the (e) surfactant ranges from 0.1 to 30% by weight, preferably from 0.5 to 25% by weight, and more preferably from 1 to 20% by weight, relative to the total weight of the composition.

The composition according to any one of Claims lto 13, wherein the composition is intended for dyeing keratin fibers, preferably hair.

A process for keratin fibers, preferably hair, comprising the steps of applying the composition according to any one of Claims 1 to 14 to the keratin fibers.