WO2016207347A1

WO2016207347A1 - Packaging article comprising an envelope and an anhydrous dyeing, bleaching or oxidizing composition comprising a fibrous clay, and a compound chosen from a colouring agent and/or an oxidizing agent; use and process for dyeing and/or bleaching keratin fibres

Info

Publication number: WO2016207347A1
Application number: PCT/EP2016/064661
Authority: WO
Inventors: Chrystel POURILLE
Original assignee: L'oreal
Priority date: 2015-06-25
Filing date: 2016-06-24
Publication date: 2016-12-29
Also published as: FR3037795A1; FR3037795B1

Abstract

Packaging article comprising an envelope and an anhydrous dyeing and/or bleaching and/or oxidizing composition comprising a fibrous clay, and a compound chosen from a colouring agent and/or an oxidizing agent; use and process for dyeing and/or bleaching keratin fibres The present invention relates to a cosmetic packaging article comprising: i) an envelope defining at least one cavity, the envelope comprising water-soluble or liposoluble fibres; and ii) at least one anhydrous composition containing at least one fibrous clay and at least one compound chosen from colouring agents and/or chemical oxidizing agents, it being understood that the composition ii) is in one of the cavities of the envelope i). Another subject of the invention is the use of the packaging article for dyeing and/or bleaching keratin fibres and a process for dyeing and/or bleaching keratin fibres using said article. The use of the packaging article makes it possible to obtain dye compositions which have good dyeing and/or lightening properties, which are easy to apply and which make it possible to obtain powerful colouring and/or bleaching of the hair.

Description

Packaging article comprising an envelope and an anhydrous dyeing, bleaching or oxidizing composition comprising a fibrous clay, and a compound chosen from a colouring agent and/or an oxidizing agent; use and process for dyeing and/or bleaching keratin fibres

The present invention relates to a packaging article for dyeing and/or bleaching keratin fibres, in particular human hair, comprising an oxidation dye precursor, and/or a direct dye for dyeing and/or an anhydrous chemical oxidizing agent.

Many people have sought for a long time to modify the colour of their hair. In the cosmetics industry, oxidizing compositions are generally used in the fields of dyeing, bleaching and permanently reshaping keratin fibres, and in particular human keratin fibres such as the hair.

In hair bleaching, bleaching compositions contain one or more oxidizing agents. Among these oxidizing agents, the ones most conventionally used are hydrogen peroxide or compounds that are capable of producing hydrogen peroxide by hydrolysis, such as urea peroxide or persalts such as perborates, percarbonates and persulfates, hydrogen peroxide and persulfates being particularly preferred.

These compositions may be aqueous compositions containing alkaline agents (amines or aqueous ammonia) that are diluted at the time of use with an aqueous hydrogen peroxide composition.

These compositions may also be formed from anhydrous products, which are powders or pastes, and which contain alkaline compounds (amines and/or alkaline silicates), and a peroxygenated reagent such as ammonium or alkali metal persulfates, perborates or percarbonates, which is diluted at the time of use with an aqueous hydrogen peroxide composition.

However, bleaching powders have a tendency to form dust during their handling, transportation and storage.

Now, the products of which they are composed (alkali metal persulfates and silicates) are aggressive and in particular irritant to the eyes, the respiratory pathways and mucous membranes.

To overcome the problem of the volatility of bleaching powders, less volatile powders have been developed by adding additives for reducing the content of fine particles, and pastes have been developed comprising said pulverulent agents

(peroxygenated salts, alkaline agents, thickeners) in an organic inert liquid support.

However, these less volatile powders and these pastes may prove to be less effective than the simple starting powders. Moreover, pastes, just like powders, nevertheless require certain precautions during their handling, in particular as regards weighing them out in order to mix them with the oxidizing composition, so as to avoid staining clothing.

Moreover, it is known practice to obtain "permanent" or oxidation dyeing with dye compositions containing oxidation dye precursors, which are generally known as oxidation bases, such as ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds. These oxidation bases are initially colourless or weakly coloured compounds, which, when combined with oxidizing products, may give rise to coloured compounds via a process of oxidative condensation.

It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or colouration modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds, such as indole compounds. The variety of the molecules used as oxidation bases and couplers allows a wide range of colours to be obtained.

The permanent dyeing process thus consists in applying, to the keratin fibres, bases or a mixture of bases and couplers with hydrogen peroxide (H₂0₂ or aqueous hydrogen peroxide solution), as oxidizing agent, in leaving them to diffuse, and in then rinsing the fibres. The colourings resulting therefrom have the advantage of being permanent, strong and resistant to external agents, in particular to light, bad weather, washing, perspiration and rubbing.

It is also known practice to dye keratin fibres temporarily with direct dyes, which are coloured and colouring molecules that have affinity for the fibres. The direct dyes generally used are chosen from nitrobenzene, anthraquinone, nitropyridine, azo, methine, azomethine, xanthene, acridine, azine and triarylmethane direct dyes. The presence of such compounds enables the colouring obtained to be further enriched with tints or enables the chromaticity of the colouring obtained to be increased. This direct dyeing may be performed at acidic, neutral or alkaline pH and in the presence or absence of an oxidizing agent.

Dyeing, whether direct dyeing or oxidation dyeing, must moreover satisfy a certain number of requirements. Thus, it must be free of toxicological drawbacks, it must enable the desired shades to be obtained and it must show good resistance to external attacking factors such as light, bad weather, washing, permanent waving, perspiration and rubbing.

The dyeing process must also make it possible to obtain shades that are as unselective as possible, i.e. it must produce the smallest possible colour differences all along the same keratin fibre, which generally comprises areas that are differently sensitized (i.e. damaged) from its end to its root.

The compositions used in the dyeing process must also have good mixing and application properties on keratin fibres, and in particular good rheological properties so as not to run, when they are applied, onto the face, onto the scalp or beyond the areas that it is proposed to dye. Direct dyeing is usually performed in a lightening dyeing process using at least one dye composition comprising a direct dye and at least one oxidizing composition, which are mixed together at the time of use just before application to the fibres. Specifically, it is not possible to store in the same composition all the ingredients except the water, so as to avoid degradation of the hydrogen peroxide in alkaline or neutral aqueous medium, and denaturation of the direct dyes by prolonged contact in oxidizing medium and consequently a reduction of the dyeing power of said dyes on the keratin fibres.

Likewise, dyeing processes which use oxidation dyes are usually carried out using several compositions, at least one dye composition and at least one oxidizing composition, which are mixed extemporaneously just before application of the generally alkaline or neutral final composition to the fibres. In fact, it is not possible to store all the ingredients except the water in the same composition in order to prevent degradation of the hydrogen peroxide in alkaline or neutral aqueous medium, which induces the oxidation-base and coupler condensation reaction.

Thus, according to the usual practice, the dye composition(s), on the one hand, and the oxidizing aqueous composition, on the other hand, which has an acidic pH to ensure the stability of the hydrogen peroxide, are stored separately, and are not placed in contact until the time of use.

The need to use several compositions first entails drawbacks inherent in the storage of several compositions, with a larger storage area.

This moreover entails the need to measure out the compositions before placing them in contact. To overcome this drawback, it may be proposed to use kits (or multicompartment devices), but this nevertheless complicates the use of the compositions and increases the costs. Furthermore, in certain cases, the dye compositions and oxidizing compositions are in different galenical forms, for instance powders, granules, pastes or creams, which may complicate the mixing and the production of a homogeneous final composition (see, for example, US 2007/0006, US 2008/0 263 786, US 2009/0 056 039, US 2010/064 449, EP 23601604, WO 2012/015 034, WO 1 1/059 027, US 201 1/203 604, FR 0 756 173 and EP 2 01 1 474).

In addition, it is seen that the compositions derived from these powders, granules, pastes and creams do not always give compositions with satisfactory textures. Furthermore, the mixtures obtained do not always give the keratin fibres satisfactory colours, in particular in terms of intensity, dyeing power, chromaticity and/or sparingly selective colourings, i.e. colourings that are sparingly homogeneous between the root and the end of the fibre. Moreover, they do not always lead to easy application with a suitable consistency.

Furthermore, during the use of pulverulent dye or bleaching compositions, there may be a risk of the user (clothing or skin surfaces) coming into contact with the dyes and alkaline agents. Finally, using separate oxidizing compositions means that quite concentrated oxidizing solutions must be handled and the steps must be multiplied.

In addition, it is sought to improve the ease of mixing and of application of dye compositions or bleaching compositions in powder or paste form, which are mixed at the time of use with the aqueous oxidizing composition.

The aim of the present invention is to provide an article for treating keratin fibres, in particular for dyeing and/or bleaching keratin fibres, which can solve the problems, in particular the handling problems, of the known compositions of the prior art, by proposing an article comprising an envelope and at least one anhydrous composition comprising at least one fibrous clay and at least one compound chosen from:

a) colouring agents chosen from oxidation dyes, direct dyes, and/or mixtures thereof; and/or

b) chemical oxidizing agents.

This article makes it possible to avoid the handling problems linked to the volatility of the powders or the weighing-out problems by proposing a ready-to-use product, without a step of metering out. It also makes it possible to improve the resistance of the composition to temperature variations, and in particular makes it possible to avoid the problem of destabilization on storage at low temperatures and during transportation including temperature cycles. It also makes it possible to avoid losses of dyeing power and/or of lightening power.

Another object of the present invention is to propose dyeing and/or bleaching compositions for keratin fibres that are easy to mix and to apply and that in particular allow homogeneous distribution of the composition over the hair.

An object of the present invention is therefore to propose a composition for dyeing and/or bleaching keratin fibres which, while preserving good dyeing and/or lightening properties, simultaneously makes it possible to regulate the problems of storage area and of storage-stability of the compositions, which avoids the user coming into any direct contact with the dyes and other ingredients used in the dyeing and/or bleaching, such as the colouring agents and the chemical oxidizing agents, which is easy to use and which does not run outside the areas that it is desired to dye.

This/these aim(s) is/are achieved by the present invention, one subject of which is a cosmetic packaging article comprising:

i) an envelope defining at least one cavity, the envelope comprising water-soluble and/or liposoluble fibres, preferably water-soluble polymer fibres;

ii) at least one anhydrous composition, preferably in paste or powder form, containing at least one fibrous clay and at least one compound chosen from: a) colouring agents chosen from oxidation dyes, direct dyes, and/or mixtures thereof; and/or

b) chemical oxidizing agents;

it being understood that the composition ii) is in one of the cavities defined by the envelope i).

The term "cosmetic packaging article" is intended to mean an article suitable for cosmetic use, in particular for use of the packaging article on keratin fibres and/or the scalp. In particular, the packaging article makes it possible to dye and/or bleach keratin fibres and in particular the hair.

In particular, the anhydrous composition ii) is a dye and/or bleaching and/or oxidizing composition.

Another subject of the invention is a process for dyeing and/or bleaching keratin fibres, in particular human keratin fibres such as the hair, comprising at least one step of using at least one packaging article as defined above.

Another subject of the invention is a process for dyeing and/or bleaching keratin fibres, in particular human keratin fibres such as the hair, comprising the following steps: i) mixing the packaging article of the invention with a composition that is capable of dissolving the packaging article, ii) applying the resulting composition to the keratin fibres, iii) leaving the composition to stand on the fibres, iv) rinsing said fibres, v) optionally shampooing the fibres, rinsing them and drying them, the composition that is capable of dissolving the packaging article possibly containing a colouring agent and/or a chemical oxidizing agent.

Another subject of the invention is the use of the packaging article as defined previously for dyeing and/or bleaching keratin fibres, preferably the hair.

The use of the packaging article makes it possible to obtain keratin fibre dye and/or bleaching compositions of which the consistency is pleasant on use, which are easy to apply and which do not run outside the areas to be treated. In the case of dyeing, the colourings obtained on the keratin fibres have excellent dyeing properties in particular in terms of the chromaticity, selectivity, intensity, strength or persistence, which are identical, comparable to or even better than those of compositions with standard packaging, i.e. in separate liquid form. In the case of bleaching, the bleaching obtained is of good intensity and good uniformity. In addition, the packaging article of the invention makes it possible to no longer have direct contact between the user and the powdered ingredients.

Moreover, the packaging article has a size that is reduced to its strict minimum, very compact, without bulky packaging.

Other characteristics and advantages of the invention will emerge more clearly on reading the description and the examples that follow.

In the text hereinbelow, and unless otherwise indicated, the limits of a range of values are included within that range.

The expression "at least one" is equivalent to the expression "one or more".

A composition is said to be "anhydrous" when it comprises a water content of not more than 3% and preferably not more than 1 % by weight relative to the weight of the composition. Preferably, this water content is not more than 0.5% by weight relative to the weight of the composition. More particularly, the water content ranges from 0 to 1 % by weight and preferably from 0 to 0.5% by weight relative to the total weight of the composition.

The term "anhydrous" is in particular intended to mean that water is preferably not deliberately added to the compositions, but may be present in trace amounts in the various compounds used in the compositions.

The term "anhydrous paste" is intended to mean an anhydrous composition with a viscosity of greater than 5 poises and preferably greater than 10 poises, measured at 25°C and at a shear rate of 1 s^"1; this viscosity may be determined using a cone-plate rheometer.

The term "in anhydrous powder form" is intended to mean an anhydrous composition or ingredient in pulverulent form, which is preferably substantially free of dust (or fine particles). In other words, the particle size distribution of the particles is such that the weight ratio of particles less than or equal to 100 micrometres in size (fines content) and preferably less than or equal to 65 micrometres in size (fines content) is advantageously less than or equal to 5%, preferably less than 2% and more particularly less than 1 % (particle size evaluated using a Retsch AS 200 Digit particle size analyser; oscillation height: 1.25 mm/screening time: 5 minutes). Advantageously, the particle size is between 100 μηη and 3 mm and more particularly between 65 μηη and 2 mm.

According to one preferred embodiment of the invention, the anhydrous composition ii) comprising at least one fibrous clay and at least one compound chosen from chemical oxidizing agents and/or oxidation dyes and/or direct dyes, and/or mixtures thereof, is in paste or powder form and is introduced into one or more cavities formed by the envelope.

The envelope may be constituted of a sheet constituted of water-soluble and/or liposoluble fibres and which is folded on itself, or alternatively the envelope may be constituted of a first sheet that is covered with a second sheet also constituted of water- soluble and/or liposoluble fibres. The sheet folded on itself or the two sheets are then hermetically assembled so that the pastes or powders cannot diffuse out, the pastes or powders thus being hermetically enveloped by the envelope i). The term "water-soluble" is intended to mean soluble in water, in particular in a proportion of at least 10 grams per litre of water, preferably at least 20 g/l and better still at least 50 g/l, at a temperature of less than or equal to 35°C.

The term "liposoluble" is intended to mean soluble in a liquid fatty substance as defined below, in particular in a proportion of at least 10 grams per litre of liquid fatty substance, in particular in a plant oil or mineral oil such as liquid petroleum jelly, preferably at least 20 g/l in a liquid fatty substance, better still at least 50 g/l in a fatty substance, at a temperature of less than or equal to 35°C.

The term "temperature of less than or equal to 35°C" is intended to mean a temperature not exceeding 35°C but greater than or equal to 0°C, for example ranging from more than 1 .0°C to 35°C, better still from 5°C to 30°C and even better still from 10°C to 30°C or 10°C to 20°C. It is understood that all the temperatures are given at atmospheric pressure.

The packaging article according to the invention is preferably water-soluble or liposoluble at a temperature of less than or equal to 35°C.

/^') an envelope comprising water-soluble and/or liposoluble fibres

The cosmetic packaging article according to the invention comprises:

i) an envelope which defines at least one cavity, the cavity or cavities containing:

ii) at least one anhydrous composition containing at least one fibrous clay and at least one compound chosen from:

colouring agents chosen from oxidation dyes, direct dyes, and/or mixtures thereof; and/or

- chemical oxidizing agents.

The packaging article preferably comprises only one cavity.

The envelope of the present invention comprises one or more sheets of water- soluble and/or liposoluble fibres and one or more cavities containing the anhydrous composition ii), the composition ii) being distinct from the sheet or from the envelope. Such an envelope is different from water-soluble or liposoluble thin films in which the composition ii) would be incorporated in the sheet(s) forming the envelope. Relative to these water-soluble or liposoluble thin films, the envelope according to the invention has the advantage of allowing the incorporation of constituents that are incompatible therewith, and of being simpler to use since it does not require any premixing or any dissolution in a solvent of the constituents, or any heating to evaporate the solvent. The process for manufacturing the packaging article of the invention is also faster and less expensive than the process for manufacturing thin films.

Furthermore, when the active agents, in this case in particular the colouring agents and/or the chemical oxidizing agents, are used in dispersion to form a thin film, this may give rise to compatibility problems and mechanical problems (breaking of the film) and may impose limits on the concentration of active agents. In addition, the envelope and the sheets that are useful for the invention have the advantage of allowing wider diversity in the choice of the shape and appearance of the article, since the water- soluble and/or liposoluble sheet(s) may have a variable thickness and a variable density, giving access to a wide variety of shapes and sizes, whereas the thin film is difficult to dry if the thickness is too large, and it is fragile and difficult to manipulate if the size is too large.

Advantageously, the envelope or the sheets are "touch-deformable" , which in particular means that the envelope and the sheets become deformed when they are held and pinched between a user's fingers.

Preferably, the anhydrous composition ii) in powder or paste form is present in a cavity generated by at least two sheets constituting the envelope and defining between them a cavity, said sheets preferably comprising water-soluble fibres.

According to a particular embodiment of the invention, at least one of the sheets of the packaging article is constituted exclusively of water-soluble fibres, and more preferentially all the sheets of the packaging article of the invention are constituted exclusively of water-soluble fibres, preferably water-soluble at a temperature of less than or equal to 30°C.

The term "fibre" is intended to mean any object of which the length is greater than its cross section. In other words, it should be understood as meaning an object of length L and of diameter D such that L is greater and preferably very much greater (i.e. at least three times greater) than D, D being the diameter of the circle in which the cross section of the fibre is inscribed. In particular, the ratio L/D (or aspect ratio) is chosen in the range from 3.5 to 2500, preferably from 5 to 500 and better still from 5 to 150. The cross section of a fibre may have any round, toothed or fluted shape, or alternatively a bean shape, but also multilobate, in particular trilobate or pentalobate, X-shaped, ribbon-shaped, square, triangular, elliptical or the like. The fibres of the invention may or may not be hollow. The fibres used according to the present invention may be of natural, synthetic or even artificial origin. Advantageously, said fibres are of synthetic origin.

A "natural fibre" is by definition a fibre that is naturally present in nature, directly or after mechanical and/or physical treatment. Fibres of animal origin, such as cellulose fibres, in particular extracted from wood, plants or algae, and rayon fibres, are collated in this category.

The "artificial fibres" are either totally synthetic or derived from natural fibres that have been subjected to one or more chemical treatments in order in particular to improve their mechanical and/or physicochemical properties.

The "synthetic fibres" collate fibres obtained by chemical synthesis and are generally fibres constituted of one or more mono-component or multi-component, composite or non-composite polymers and/or copolymers, which are generally extruded and/or drawn to the desired diameter of the fibre.

Preferably, the fibres of the invention are constituted of one or more water-soluble polymers.

The water-soluble polymer(s) of the invention contain water-soluble units in their backbones. The water-soluble units are obtained from one or more water-soluble monomers.

The term "water-soluble monomer" is intended to mean a monomer of which the solubility in water is greater than or equal to 1 % and preferably greater than or equal to 5% at 25°C and at atmospheric pressure (760 mmHg).

Said synthetic water-soluble polymer(s) used in the context of the present invention are advantageously obtained from water-soluble monomers comprising at least one double bond. These monomers may be chosen from cationic, anionic and non-ionic monomers, and mixtures thereof.

As water-soluble monomers that may be used as precursors of the water-soluble units, alone or as a mixture, examples that may be mentioned include the following monomers, which may be in free or salified form:

- (meth)acrylic acid,

- styrenesulfonic acid,

- vinylsulfonic acid and (meth)allylsulfonic acid,

- vinylphosphonic acid,

- N-vinylacetamide and N-methyl-N-vinylacetamide,

- N-vinylformamide and N-methyl-N-vinylformamide,

- N-vinyllactams comprising a cyclic alkyl group containing from 4 to 9 carbon atoms, such as N-vinylpyrrolidone, N-butyrolactam and N-vinylcaprolactam,

- maleic anhydride,

- itaconic acid,

- vinyl alcohol of formula CH₂=CHOH,

- vinyl ethers of formula CH₂=CHOR in which R is a linear or branched, saturated or unsaturated hydrocarbon-based radical containing from 1 to 6 carbons,

- dimethyldiallylammonium halides (chloride),

- quaternized dimethylaminoethyl methacrylate (DMAEMA),

- (meth)acrylamidopropyltrimethylammonium halides (chloride) (APTAC and MAPTAC),

- methylvinylimidazolium halides (chloride),

- 2-vinylpyridine and 4-vinylpyridine,

- acrylonitrile,

- glycidyl (meth)acrylate,

- vinyl halides (chloride) and vinylidene chloride,

- vinyl monomers of formula (I) below: H₂C=C(R)-C(O)-X (I)

in which formula (I):

- R is chosen from H and (CrC₆)alkyl such as methyl, ethyl and propyl;

- X is chosen from:

- alkoxy of -OR' type in which R' is a linear or branched, saturated or unsaturated hydrocarbon-based radical containing from 1 to 6 carbon atoms, optionally substituted with at least one halogen atom (iodine, bromine, chlorine or fluorine); a sulfonic (-S0₃ ^"), sulfate (-SO4^"), phosphate (-P0₄H₂); hydroxyl (-OH); primary amine (-NH₂); secondary amine (-NHR₆), tertiary amine (-NR₆R₇) or quaternary amine (-N⁺R₆R₇R8) group with R₆, R₇ and R₈ being, independently of each other, a linear or branched, saturated or unsaturated hydrocarbon-based radical containing 1 to 6 carbon atoms, with the proviso that the sum of the carbon atoms of R' + R₆ + R₇ + Re does not exceed 6;

- groups -NH₂, -NHR' and -NR'R" in which R' and R" are, independently of each other, linear or branched, saturated or unsaturated hydrocarbon-based radicals containing 1 to 6 carbon atoms, with the proviso that the total number of carbon atoms of R' + R" does not exceed 6, said R' and R" being optionally substituted with one halogen atom (iodine, bromine, chlorine or fluorine); a hydroxyl (-OH); sulfonic (-S0₃ ^"), sulfate (-S0₄ ^"), phosphate (-P0₄H₂); primary amine (-NH₂); secondary amine (-NHR₆), tertiary amine (- NR₆R₇) and/or quaternary amine (-N⁺R₆R₇R8) group with R₆, R₇ and R₈ being, independently of each other, a linear or branched, saturated or unsaturated hydrocarbon- based radical containing 1 to 6 carbon atoms, with the proviso that the sum of the carbon atoms of R' + R" + R₆ + R₇ + Re does not exceed 6. As compounds corresponding to this formula, examples that may be mentioned include Ν,Ν-dimethylacrylamide and N,N- diethylacrylamide;

- and mixtures thereof.

Anionic monomers that may in particular be mentioned include (meth)acrylic acid, acrylamido-2-methylpropanesulfonic acid, itaconic acid and alkali metal, alkaline-earth metal or ammonium salts thereof or salts thereof derived from an organic amine such as an alkanolamine.

Non-ionic monomers that may in particular be mentioned include (meth)acrylamide,

N-vinylformamide, N-vinylacetamide, hydroxypropyl (meth)acrylate and the vinyl alcohol of formula CH₂=CHOH.

The cationic monomers are preferably chosen from quaternary ammonium salts derived from a diallylamine and those corresponding to formula (II) below:

H₂C=C(Ri)-D-N⁺R₂R₃R4, X^"

in which formula (II):

• Ri represents a hydrogen atom or a methyl group,

• R₂ and R₃, which may be identical or different, represent a hydrogen atom or a linear or branched C1-C4 alkyl group,

• R₄ represents a hydrogen atom or a linear or branched C1-C4 alkyl group or an aryl group,

• D represents the following divalent unit: -(Y)_n-(A)- in which:

- Y represents an amide function, an ester (O-C(O) or C(O)-O), a urethane or a urea, A represents a linear or branched, cyclic or acyclic C1-C10 alkylene group, which may be substituted or interrupted with a divalent aromatic or heteroaromatic group. The alkylene groups may be interrupted with an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom; the alkylene may be interrupted with a ketone function, an amide, an ester (O-C(O) or C(O)-O), a urethane or a urea,

- n is an integer ranging from 0 to 1 ,

X^" represents an anionic counterion, for instance a chloride or a sulfate.

Examples of water-soluble cationic monomers that may in particular be mentioned include the following compounds, and also salts thereof: dimethylaminoethyl, (meth)acryloyloxyethyltrimethylammonium,

(meth)acryloyloxyethyldimethylbenzylammonium, N- [dimethylaminopropyl](meth)acrylamide, (meth)acrylamidopropyltrimethylammonium, (meth)acrylamidopropyldimethylbenzylammonium, dimethylaminohydroxypropyl, (meth)acryloyloxyhydroxypropyltrimethylammonium,

(meth)acryloyloxyhydroxypropyldimethylbenzylammonium and dimethyldiallylammonium (meth)acrylate.

Preferably, the polymer of use according to the invention is polymerized from at least one cationic monomer as defined above.

Preferably, the polymers are polymerized from the following monomers comprising at least one double bond as follows:

- 0 to 30 mol% of acrylic acid,

- 0 to 95.5 mol% of acrylamide, and

- 0.5 mol% to 100 mol% of at least one cationic monomer represented in formula (II) as defined above.

As polymers that are particularly preferred in the invention, mention may be made in particular of those polymerized from:

- 10% of acryloyloxyethyldimethylbenzylammonium chloride and 90% of acrylamide, 30% of acryloyloxytrimethylammonium chloride, 50% of acryloyloxyethyldimethylbenzylammonium chloride and 20% of acrylamide,

- 10% of acryloyloxyethyltrimethylammonium chloride and 90% of acrylamide,

- 30% of diallyldimethylammonium chloride and 70% of acrylamide,

- 30% of acrylic acid and 70% of acrylamide.

According to a particular embodiment, the polymers are polymerized from a cationic monomer and acrylic acid, the number of moles of the cationic monomer being greater than the number of moles of acrylic acid.

As water-soluble polymers derived from natural products, mention may be made of polysaccharides, i.e. polymers bearing a sugar unit or sugar units.

The term "sugar unit" is intended to mean a unit derived from a carbohydrate of formula C_n(H₂0)_n-i or (CH₂0)_n, which may be optionally modified by substitution and/or by oxidation and/or by dehydration. The sugar units that may be included in the composition of the polymers of the invention are preferably derived from the following sugars: glucose, galactose, arabinose, rhamnose, mannose, xylose, fucose, fructose, anhydrogalactose, galacturonic acid, glucuronic acid, mannuronic acid, galactose sulfate or anhydrogalactose sulfate.

The polymers bearing a sugar unit or sugar units according to the invention may be of natural or synthetic origin. They can be non-ionic, anionic, amphoteric or cationic. The base units of the polymers bearing a sugar unit of the invention may be monosaccharides or disaccharides.

Mention may in particular be made, as polymers capable of being employed, of the following native gums, and also their derivatives:

a) tree or shrub exudates, including:

- gum arabic (branched polymer of galactose, arabinose, rhamnose and glucuronic acid);

- ghatti gum (polymer derived from arabinose, galactose, mannose, xylose and glucuronic acid);

- karaya gum (polymer derived from galacturonic acid, galactose, rhamnose and glucuronic acid);

- gum tragacanth (or tragacanth) (polymer of galacturonic acid, galactose, fucose, xylose and arabinose);

b) gums derived from algae, including:

- agar (polymer derived from galactose and anhydrogalactose);

- alginates (polymers of mannuronic acid and of glucuronic acid);

- carrageenans and furcellerans (polymers of galactose sulfate and of anhydrogalactose sulfate);

c) gums resulting from seeds or tubers, including:

- guar gum (polymer of mannose and galactose);

- locust bean gum (polymer of mannose and galactose);

- fenugreek gum (polymer of mannose and galactose);

- tamarind gum (polymer of galactose, xylose and glucose);

- konjac gum (polymer of glucose and mannose) in which the main constituent is glucomannan, a polysaccharide of high molecular weight (500 000 < M_gi_ucomannan < 2 000 000) composed of D-mannose and D-glucose units with a branch every 50 or 60 units approximately;

d) microbial gums, including: - xanthan gum (polymer of glucose, mannose acetate, mannose/pyruvic acid and glucuronic acid);

- gellan gum (polymer of partially acylated glucose, rhamnose and glucuronic acid);

- scleroglucan gum (glucose polymer);

- biosaccharide gum (polymer of galacturonic acid, fucose and D-galactose), for example the product sold under the name Fucogel 1.5P from Solabia (polysaccharide rich in fucose (20%) at 1.1 % in water and stabilized (1 .5% phenoxyethanol));

e) plant extracts, including:

- cellulose (glucose polymer);

- starch (glucose polymer);

- inulin (polymer of fructose and glucose).

These polymers can be physically or chemically modified. Mention may in particular be made, as physical treatment, of the temperature. Chemical treatments that may be mentioned include esterification, etherification, amidation or oxidation reactions. These treatments make it possible to result in polymers which can be non-ionic, anionic, cationic or amphoteric.

Preferably, these chemical or physical treatments are applied to guar gums, locust bean gums, starches and celluloses.

The non-ionic guar gums that may be used according to the invention may be modified with Ci-C₆ hydroxyalkyl groups. Mention may be made, among the hydroxyalkyl groups, of the hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.

These guar gums are well known from the state of the art and can, for example, be prepared by reacting corresponding alkene oxides, such as, for example, propylene oxides, with the guar gum, so as to obtain a guar gum modified with hydroxypropyl groups.

The degree of hydroxyalkylation preferably varies from 0.4 to 1 .2 and corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functional groups present on the guar gum.

Such non-ionic guar gums optionally modified with hydroxyalkyl groups are sold, for example, under the trade names Jaguar HP8, Jaguar HP60 and Jaguar HP120 by Rhodia Chimie.

The guar gums modified with cationic groups which can more particularly be used according to the invention are guar gums comprising trialkylammonium cationic groups. Preferably, from 2% to 30% by number of the hydroxyl functional groups of these guar gums carry trialkylammonium cationic groups. More preferably still, from 5% to 20% by number of the hydroxyl functional groups of these guar gums are branched with trialkylammonium cationic groups. Mention may very particularly be made, among these trialkylammonium groups, of the trimethylammonium and triethylammonium groups. More preferably still, these groups represent from 5% to 20% by weight, relative to the total weight of the modified guar gum.

According to the invention, use may be made of guar gums modified with 2,3- epoxypropyltrimethylammonium chloride.

These guar gums modified with cationic groups are products already known per se and are, for example, described in Patents US 3 589 578 and US 4 031 307. Such products are moreover sold in particular under the trade names Jaguar C13 S, Jaguar C 15 and Jaguar C 17 by Rhodia Chimie.

Use may be made, as modified locust bean gum, of the cationic locust bean gum containing hydroxypropyltrimonium groups, such as Catinal CLB 200 provided by Toho.

The starch molecules used in the present invention may originate from any plant source of starch, in particular cereals and tubers; more particularly, they may be starches from corn, rice, cassava, barley, potato, wheat, sorghum, pea, oat or tapioca. Use may also be made of the hydrolysates of the abovementioned starches. The starch is preferably derived from potato.

The starches can be chemically or physically modified, in particular by one or more of the following reactions: pregelatinization, oxidation, crosslinking, esterification, etherification, amidation or heat treatments.

Preferably, the composition according to the invention comprises at least starch or a starch modified by at least one of the following reactions: pregelatinization, oxidation, crosslinking, esterification, etherification, amidation, heat treatments.

More particularly, these reactions can be carried out in the following way:

- pregelatinization by splitting the starch granules (for example drying and cooking in a drying drum);

- oxidation with strong oxidizing agents, resulting in the introduction of carboxyl groups into the starch molecule and in the depolymerization of the starch molecule (for example by treating an aqueous starch solution with sodium hypochlorite);

- crosslinking with functional agents capable of reacting with the hydroxyl groups of the starch molecules, which will thus be bonded together (for example with glyceryl and/or phosphate groups);

- esterification in alkaline medium for the grafting of functional groups, in particular Ci-C₆ acyl (acetyl), Ci-C₆ hydroxyalkyl (hydroxyethyl or hydroxypropyl), carboxymethyl or octenylsuccinic.

Monostarch phosphates (of the type Am-0-PO-(OX)₂), distarch phosphates (of the type Am-O-PO-(OX)-O-Am) or even tristarch phosphates (of the type Am-0-PO-(0-Am)₂) or mixtures thereof may in particular be obtained by crosslinking with phosphorus compounds, Am meaning starch and X in particular denoting alkali metals (for example sodium or potassium), alkaline earth metals (for example calcium or magnesium), ammonium salts, amine salts, for instance those of monoethanolamine, diethanolamine, triethanolamine, 3-amino-1 ,2-propanediol, or ammonium salts derived from basic amino acids such as lysine, arginine, sarcosine, ornithine or citrulline.

The phosphorus compounds can, for example, be sodium tripolyphosphate, sodium orthophosphate, phosphorus oxychloride or sodium trimetaphosphate.

Use will preferably be made of distarch phosphates or compounds rich in distarch phosphate, such as the product sold under the references Prejel VA-70-T AGGL (gelatinized hydroxypropyl cassava distarch phosphate), Prejel TK1 (gelatinized cassava distarch phosphate) and Prejel 200 (gelatinized acetyl cassava distarch phosphate) by Avebe, or Structure Zea from National Starch (gelatinized corn distarch phosphate).

A preferred starch is a starch that has undergone at least one chemical modification such as at least one esterification.

According to the invention, amphoteric starches comprising one or more anionic groups and one or more cationic groups may also be used. The anionic and cationic groups can be bonded to the same reactive site of the starch molecule or to different reactive sites; they are preferably bonded to the same reactive site. The anionic groups can be of carboxylic, phosphate or sulfate type, preferably of carboxylic type. The cationic groups can be of primary, secondary, tertiary or quaternary amine type.

The amphoteric starches are in particular chosen from the compounds having the following formulae:

^{R R}

St - 0 - (CH₂)_N - N

(I) R' R

R R" ^R\ , R"

N N

I I

St - O - C— C— COOM St - O - C— C— COOM

H₂ H H H₂

('") (IV)

in which formulae (I) to (IV):

St-0 represents a starch molecule;

R, which may be identical or different, represents a hydrogen atom or a methyl radical;

· R', which may be identical or different, represents a hydrogen atom, a methyl radical or a group -C(0)-OH;

n is an integer equal to 2 or 3;

M, which may be identical or different, denotes a hydrogen atom, an alkali metal or alkaline-earth metal such as Na, K or Li, a quaternary ammonium NH₄, or an organic amine,

" represents a hydrogen atom or a Ci-Ci₈ alkyl radical.

These compounds are in particular described in US 5 455 340 and US 4 017 460. Use is in particular made of the starches of formulae (II) or (III); and preferably starches modified with 2-chloroethylaminodipropionic acid, that is to say the starches of formula (II) or (III) in which R, R', R" and M represent a hydrogen atom and n is equal to 2. The preferred amphoteric starch is a starch chloroethylamidodipropionate. The celluloses and cellulose derivatives can be anionic, cationic, amphoteric or non-ionic.

Among these derivatives, cellulose ethers, cellulose esters and cellulose ester ethers are distinguished.

Mention may be made, among the cellulose esters, of inorganic cellulose esters (cellulose nitrates, sulfates or phosphates), organic cellulose esters (cellulose monoacetates, triacetates, amidopropionates, acetate butyrates, acetate propionates or acetate trimellitates), and mixed organic/inorganic cellulose esters, such as cellulose acetate butyrate sulfates and cellulose acetate propionate sulfates.

Mention may be made, among the cellulose ester ethers, of hydroxypropyl methylcellulose phthalates and ethylcellulose sulfates.

Among the non-ionic cellulose ethers that may be mentioned are alkylcelluloses such as methylcelluloses and ethylcelluloses (for example Ethocel Standard 100 Premium from Dow Chemical); hydroxyalkylcelluloses such as hydroxymethylcelluloses and hydroxyethylcelluloses (for example Natrosol 250 HHR sold by Aqualon) and hydroxypropylcelluloses (for example Klucel EF from Aqualon); mixed hydroxyalkyl- alkylcelluloses such as hydroxypropylmethylcelluloses (for example Methocel E4M from Dow Chemical), hydroxyethylmethylcelluloses, hydroxyethylethylcelluloses (for example Bermocoll E 481 FQ from Akzo Nobel) and hydroxybutylmethylcelluloses.

Mention may be made, among the anionic cellulose ethers, of carboxyalkylcelluloses and their salts. Mention may be made, as examples, of carboxymethylcelluloses, carboxymethyl methylcelluloses (for example Blanose 7M from Aqualon) and carboxymethyl hydroxyethylcelluloses, and also their sodium salts.

Mention may be made, among the cationic cellulose ethers, of crosslinked or non- crosslinked quaternized hydroxyethylcelluloses. The quaternizing agent may in particular be diallyldimethylammonium chloride (for example Celquat L200 from National Starch). Another cationic cellulose ether that may be mentioned is hydroxypropyltrimethylammonium hydroxyethyl cellulose (for example Ucare Polymer JR 400 from Amerchol).

Among the associative polymers bearing a sugar unit or sugar units, mention may be made of celluloses or derivatives thereof, modified with groups comprising at least one fatty chain, such as alkyl, arylalkyi or alkylaryl groups or mixtures thereof in which the alkyl groups are of C8-C22; non-ionic alkylhydroxyethylcelluloses such as the products Natrosol Plus Grade 330 CS and Polysurf 67 (Ci₆ alkyl) sold by the company Aqualon; quaternized alkylhydroxyethylcelluloses (cationic), such as the products Quatrisoft LM 200, Quatrisoft LM-X 529-18-A, Quatrisoft LM-X 529-18-B (C_i2 alkyl) and Quatrisoft LM-X 529-8 (Ci₈ alkyl) sold by the company Amerchol, the products Crodacel QM and Crodacel QL (Ci2 alkyl) and Crodacel QS (Ci₈ alkyl) sold by the company Croda, and the product Softcat SL 100 sold by the company Amerchol; non-ionic nonoxynylhydroxyethylcelluloses such as the product Amercell HM-1500 sold by the company Amerchol; non-ionic alkylcelluloses such as the product Bermocoll EHM 100 sold by the company Berol Nobel.

As associative polymers bearing a sugar unit or sugar units derived from guar, mention may be made of hydroxypropyl guars modified with a fatty chain, such as the product Esaflor HM 22 (modified with a C22 alkyl chain) sold by the company Lamberti; the product Miracare XC 95-3 (modified with a C14 alkyl chain) and the product RE 205- 146 (modified with a C₂₀ alkyl chain) sold by Rhodia Chimie.

The polymer(s) bearing a sugar unit or sugar units of the invention are preferably chosen from guar gums, locust bean gums, xanthan gums, starches and celluloses, in their modified form (derivatives) or unmodified.

Preferably, the polymers bearing a sugar unit or sugar units according to the invention are non-ionic.

More preferably, the polymer(s) bearing a sugar unit or sugar units of the invention are chosen from modified non-ionic guar gums, in particular modified with Ci-C₆ hydroxyalkyl groups.

The polymers described above more particularly have a weight-average molecular weight of greater than 1 000 000 and preferably between 1 000 000 and 50 000 000. The molecular weight is determined by the RSV (Reduced Specific Viscosity) method as defined in "Principles of Polymer Chemistry" Cornell University Press, Ithaca, NY 1953 Chapter VII "Determination of molecular weight" pp. 266-316.

The fibres may be spun, carded or twisted. Advantageously, the fibres used in the context of the present invention are spun. The mean diameter of the fibres used according to the present invention, which may be identical or different, is less than 500 μηη. Advantageously, such a diameter is less than 200 μηη, preferably less than 100 μηη or even less than 50 μηη.

Mention may be made more particularly of water-soluble fibres that include fibres based on polyvinyl alcohol, fibres of polysaccharides such as glucomannans, starches or celluloses such as carboxymethylcelluloses, polyalginic acid fibres, polylactic acid fibres and polyalkylene oxide fibres, and also mixtures thereof. More preferentially, the water- soluble fibre(s) used in the invention are chosen from PVA-based fibres.

The fibres of the envelope or of the sheets are generally entangled. As indicated above, the term "envelope or sheet comprising water-soluble fibres" is intended to mean an envelope or sheets which may be constituted entirely of water-soluble fibres or a sheet which may comprise both water-soluble fibres and fibres that are insoluble in water at a temperature of less than or equal to 35°C, the soluble fibres necessarily being in a larger amount than the insoluble fibres. The sheet of fibres should comprise at least 60% by weight, preferably at least 70% and better still at least 80% by weight of soluble fibres relative to the total weight of fibres. It may thus comprise, for example, more than 95% by weight, or even more than 99% by weight and even 100% by weight of water-soluble fibres relative to the total weight of fibres in the envelope or the sheets.

When the sheet of fibres contains insoluble fibres, the latter fibres may be made of any material usually used as insoluble fibres; they may be, for example, silk fibre, cotton fibre, wool fibre, flax fibre, polyamide (Nylon®) fibre, polylactic acid fibre, modified cellulose (rayon, viscose or rayon acetate) fibre, poly-p-phenyleneterephthalamide fibre, in particular Kevlar® fibre, polyolefin fibre and in particular polyethylene or polypropylene fibre, glass fibre, silica fibre, aramid fibre, carbon fibre, in particular in graphite form, Teflon® fibre, insoluble collagen fibre, polyester fibre, polyvinyl or polyvinylidene chloride fibre, polyethylene terephthalate fibre, and fibres formed from a mixture of the compounds mentioned above, for instance polyamide/polyester or viscose/polyester fibres.

In addition, the envelope and the sheets of the invention may be woven or nonwoven.

According to a particular embodiment, the envelope and the sheets of the invention are woven. In the context of the present invention, a "woven" material results from an organized assembly of fibres, in particular of water-soluble polymeric fibres, and more particularly of an intercrossing, in the same plane, of said fibres, arranged in the warp direction and of fibres arranged perpendicular to the warp fibres, in the weft direction. The binding obtained between these warp and weft fibres is defined by a weave.

Such a woven material results from an operation directed towards assembling the fibres in an organized manner such as weaving per se, but may also result from knitting.

More particularly, the two layers or sheets comprising the woven polymeric water- soluble fibres that constitute the envelope of the packaging article of the invention do not comprise any other additional layer superposed thereon.

According to another particularly advantageous mode of the invention, the envelope and the sheets are nonwoven.

For the purposes of the present invention, the expression "nonwoven" is intended to mean a substrate comprising fibres, in particular water-soluble polymeric fibres, in which substrate the individual fibres are arranged in a disordered manner in a structure in the form of a sheet and which are neither woven nor knitted. The fibres of the nonwoven are generally bonded together, either under the effect of a mechanical action (for example needle punching, air jet, water jet, etc.), or under the effect of a thermal action, or by addition of a binder.

Such a nonwoven is, for example, defined by standard ISO 9092 as a web or sheet of directionally or randomly orientated fibres, bonded by friction and/or cohesion and/or adhesion, excluding paper and products obtained by weaving, knitting, tufting or stitching incorporating binding yarns or filaments.

A nonwoven differs from a paper by virtue of the length of the fibres used. In paper, the fibres are shorter. However, there are nonwovens based on cellulose fibre, which are manufactured by a wet-laid process and that have short fibres as in paper. The difference between a nonwoven and a paper is generally the absence of hydrogen bonding between the fibres in a nonwoven.

Very preferentially, the fibres used in the context of the present invention are chosen from synthetic fibres such as PVA fibres. In particular, the envelope and sheets of the invention are nonwoven, and preferentially made of nonwoven PVA fibres.

To produce the nonwoven water-soluble sheet(s) of the envelope of the packaging article, use is preferably made of PVA fibres that are soluble in water at a temperature of less than or equal to 35°C, for instance the fibres sold by the Japanese company Kuraray under the name Kuralon K-ll, and particularly the grade WN2 which is soluble at and above 20°C. These fibres are described in document EP-A-636 716 which teaches the manufacture of PVA fibres that are soluble in water at temperatures not exceeding 100°C, by spinning and drawing the polyvinyl alcohol polymer in dry or wet form in the presence of solvents participating in the dissolution and solidification of the fibre. The fibre thus obtained may lead to the production of woven or nonwoven substrates. According to a particular mode of the invention, the PVA fibres of the examples of EP-A- 636 716 are used, in particular Example 2 and Comparative Example 1 : commercial product Solvron SS.

These fibres may also be prepared from a solution to be spun, by dissolving a water-soluble PVA-based polymer in a first organic solvent, spinning the solution in a second organic solvent to obtain solidified filaments and wet-drawing of the filaments from which the first solvent is removed, and which are then dried and subjected to a heat treatment. The cross section of these fibres may be substantially circular. These fibres have a tensile strength of at least 2.7 g/dtex (3 g/d). Patent application EP-A-0 636 716 describes such PVA-based water-soluble fibres and the process for manufacturing them. For example, the fibres may also be formed by extrusion and deposited on a conveyor to form a sheet of fibres which is then consolidated via a standard fibre bonding technique, for instance needle punching, hot-bonding, calendering or air-through bonding, in which technique the water-soluble sheet passes through a tunnel in which hot air is blown, or hydroentanglement directed towards bonding the fibres via the action of fine jets of water at very high pressure, which cannot be applied to fibres of which the dissolution temperature is too low pressure.

As has been seen previously, the invention is not limited to the use of PVA, and use may also be made of fibres made of other water-soluble materials, provided that these materials dissolve in water having the desired temperature, for example the polysaccharide fibres sold under the name Lysorb by the company Lysac Technologies, Inc. or other fibres based on polysaccharide polymers such as glucomannans or starch.

The sheets of the envelope may comprise a mixture of different fibres that are soluble in water at various temperatures (up to 35°C).

The fibres may be composite, and they may comprise, for example, a core and a sheath not having the same nature, for example formed from different grades of PVA.

According to a particular embodiment of the invention, the sheet(s) of the envelope is (are) a nonwoven comprising water-soluble fibres, alone or as a mixture with insoluble fibres as indicated above, with not more than 40% by weight of insoluble fibres relative to the total weight of the fibres constituting the sheet. Preferably, the nonwoven is constituted essentially of water-soluble fibres, i.e. it does not contain any insoluble fibres.

The envelope may have any shape that is suitable for the intended use, for example a rectangular, circular or oval shape, and it preferably has dimensions that enable it to be held between at least two fingers. Thus, the envelope or the sheets may have, for example, an ovoid shape from about 2 to 10 cm long and from about 0.5 to 4 cm wide, or a circular disc shape from about 2 to 10 cm in diameter, or a square shape with a side length from about 5 to 15 cm, or a rectangular shape with a length from about 5 to 25 cm, it being understood that it may have any other shape and size that are suitable for the desired use.

Advantageously, the envelope and the sheets have a low thickness, the sheets possibly being constituted of several layers. Preferably, the thickness of the envelope and of the sheets ranges from 3% to 99.9% of its other dimensions. This thickness is in particular less than 100 mm. The envelope and the sheets are thus substantially flat, thin slices.

The surface delimiting the cavity(ies) has an area generally less than 625 cm², for example between 400 cm² and 0.025 cm².

Use may be made, for example, of an envelope and sheets as defined in French patent application FR 12/61 120 filed on 22 November 2012.

The article according to the present invention may comprise one or more water- soluble nonwoven sheets and envelope.

Preferentially, the amount of envelope present in the article according to the invention is inclusively between 0.5% and 20.0% by weight relative to the total weight of said article, advantageously inclusively between 1 .0% and 10.0%, particularly inclusively between 2.0% and 5.0% and more particularly 3% by weight relative to the total weight of the packaging article.

Figure 1 a) is a cross section of a particular embodiment of the packaging article comprising the envelope i) constituted of two sheets, which are preferably water-soluble, 1 1 and 12, bonded together in a peripheral region 14. Preferably, the two sheets are joined by any suitable fixing means such as glueing, welding, in particular heat-welding, and in particular by entanglement. The first sheet 1 1 also has a free central region D arranged facing a free central region D of the second sheet 12. These two central regions delimit a central cavity; said cavity contains an anhydrous composition ii) as previously defined 13 comprising at least one fibrous clay and at least one compound chosen from chemical oxidizing agents and/or oxidation dyes, and/or direct dyes, and/or mixtures thereof optionally mixed with other additional ingredients.

The sheets 1 1 and 12 have a closed outer perimeter 15. The shape of the outer perimeter 15 is, for example, rounded, such as circular or elliptical, or polygonal, such as square, rectangular or triangular, preferably circular.

Figure 1 b) shows a top view of the packaging article as described in Figure 1 a), in which part D corresponds to the cavity or "central region" in which is found the anhydrous composition ii) as defined previously 13, and d corresponds to the peripheral region hermetically joining the two sheets 1 1 and 12.

Figure 1 c) shows a cross section of a particular embodiment of the packaging article, comprising an envelope constituted of two sheets 1 1 and 12, which are preferably water- soluble, and comprising an additional sheet 16, which is preferably water-soluble, and optionally other additional sheets 17, which are preferably water-soluble, which define several cavities in which are housed the ingredients such as the composition ii) as defined previously comprising at least one fibrous clay 18, and at least one compound 19 chosen from colouring agents, and/or chemical oxidizing agents as a powder 20, as defined hereinafter.

The first sheet 1 1 has a thickness smaller than its other dimensions, for example less than 10% of its maximum transverse dimension D+2d.

The thickness of the first sheet 1 1 is, for example, less than 10 mm and in particular between 0.1 mm and 3 mm. Its maximum transverse dimension D+d is, for example, less than 100 mm, and is in particular inclusively between 10 mm and 60 mm.

The first sheet 1 1 thus forms a web, for example of nonwoven, which itself may be constituted of several webs of nonwoven that are consolidated together.

The second sheet 12 also has a closed outer perimeter 15. The outer perimeter 15 of the first layer 1 1 has a shape substantially identical to the outer perimeter 15 of the second layer 12.

The second sheet 12 has a thickness smaller than its other dimensions, for example less than 10% of its maximum transverse dimension D+2d.

The thickness of the second sheet 12, which is preferably water-soluble, is, for example, less than 10 mm and in particular between 0.1 mm and 3 mm. Its maximum transverse dimension D+2d is less than 100 mm, and is in particular between 10 mm and 60 mm.

The thickness is advantageously measured according to the standard EDANA WSP 120.1 (5).

The second sheet 12 is advantageously a nonwoven.

The first sheet 1 1 and the second sheet 12, which may be identical or of different thicknesses, densities and/or compositions, are preferably nonwovens that are water- soluble at a temperature of less than or equal to 35°C. The sheets and nonwoven envelope are soluble in an aqueous solution, such as water. The nonwoven sheets and envelope are preferentially made of PVA.

As a variant, the second sheet may be formed by the first sheet folded on itself 1 1 ' shown in Figure 1 d) in cross section and Figure 1 e) in top view. The sheet is folded on itself along the folding axis and which defines a cavity in which is found a composition ii) comprising at least one colouring agent 18' and/or at least one chemical oxidizing agent as defined below, preferably in powder form, and/or excipients as defined below, preferably in powder form 19', optionally separated by one or more water-soluble sheets 16'. The sheet 1 1 ', once filled with the ingredients 19' and with the water-soluble sheet(s) 16', is folded along the axis e, forming a folding zone 15' and then joined at a peripheral region 14, the shaded part of Figure e), preferably via any suitable fixing means such as glueing, welding, in particular heat-welding, and in particular by entanglement. The thickness of the water-soluble sheet 1 1 ' and the transverse dimensions satisfy the same criteria as those defined for the sheet 1 1 or 12 of Figure 1 b).

The fibres forming the first sheet 1 1 or 1 1 ' and the second sheet 12, and the additional sheets 16, 16' and 17, are preferably water-soluble, i.e. they are constituted of water-soluble fibres. These fibres are, for example, nonwoven water-soluble fibres such as PVA fibres, polysaccharide fibres, glucomannans or starches, or any other polymer or compound that is capable of forming water-soluble fibres or yarns, obtained, for example, by extrusion.

The sheets 1 1 , 1 1 ' and 12 and the optional additional sheets 16, 16' and 17, which are preferably made of nonwoven, generally have a basis weight of less than or equal to 60 g/m², or even less than or equal to 50 g/m² and better still less than or equal to 45 g/m². In a variant, the basis weight of at least one layer may be greater than 60 g/m².

The packaging articles comprising water-soluble fibres according to the invention are preferably soluble in water or in an aqueous composition with a dissolution time of the packaging article preferably of not more than one hour.

Process for preparing the packaging article:

The envelope i) delimits or defines a cavity that is filled with an anhydrous composition ii) comprising at least one compound chosen from colouring agents, and/or chemical oxidizing agents, preferably in powder or paste form; the article is then closed by folding the envelope i) on itself with its contents, followed by assembly at its periphery, for example by glueing or welding, preferably by heat-welding, or alternatively, if the article contains an envelope constituted of two sheets, the anhydrous composition ii), preferably in powder or paste form, is placed on the first sheet, and the article is closed by means of a second sheet which covers the ingredients of the composition ii) placed on the first sheet and which is assembled, for example, by glueing or welding at its periphery, preferably by heat-welding at its periphery, so as to obtain a hermetic article, which does not allow the powders or pastes contained in said article to pass into the atmosphere. When the envelope and the sheets comprise several water-soluble sheets of nonwovens, these nonwovens may be assembled in particular by heat-welding at their periphery. Preferably, the heat-welding is performed with entanglement of the fibres of the parts of the envelope to be welded. /^'/^') Anhydrous composition ii)

The packaging article according to the invention also comprises at least one anhydrous composition ii). Said composition ii) is in one of the cavities defined by the envelope i) previously described.

The composition ii) is preferably in paste or powder form. It is preferably in powder form. The anhydrous composition ii) comprises at least one fibrous clay and at least one compound chosen from:

b) chemical oxidizing agents.

Fibrous Clay:

The anhydrous composition ii) comprises at least one fibrous clay.

The clay(s) present in the composition ii) of the invention may be natural or synthetic. Natural clay is a sedimentary rock composed to a large extent of specific minerals, silicates generally of aluminium. Clays, and in particular fibrous clays, are products that are already well known per se, which are described, for example, in the publication Mineralogie des argiles [Mineralogy of Clays], S. Caillere, S. Henin, M. Rautureau, 2nd Edition 1982, Masson.

Preferably, in the context of the present invention, use is made of clays which are cosmetically compatible with and acceptable for the hair, the skin and/or the scalp.

Fibrous clays have a pseudo-layer structure, and are made up of continuous hexagonal layers of oxygen, alternately separated by two compactly assembled layers of oxygen, the stacking of which forms octahedra but which extend in a long ribbon, growth being limited to one dimension. These ribbons are arranged alternately above or below the continuous layer of oxygen which is hexagonally assembled, such that the structure has, in section, the appearance of a hollow brick.

Two families of fibrous clays are distinguished: the sepiolite family and the palygorskite family.

Preferably, the fibrous clay is chosen from sepiolite, palygorskite, attapulgite (which is part of the palygorskite family), and/or mixtures thereof. Preferably, the fibrous clay is sepiolite, for example the sepiolite Pangel HV sold by the company Tolsa. The fibrous clays according to the invention may optionally be modified.

Preferably, the fibrous clay(s) is (are) present in the anhydrous composition ii) in a total content ranging from 1 % to 80% by weight, in particular from 2% to 80% by weight, preferably from 5% to 60%, and better still from 5% to 40% by weight, relative to the total weight of the anhydrous composition ii).

Colouring agents

In particular, according to a first embodiment, the anhydrous composition ii) comprises at least one colouring agent chosen from oxidation dyes, direct dyes, and/or mixtures thereof.

The colouring agent(s) used in the composition according to the invention may be oxidation dyes (also known as oxidation dye precursors) and/or direct dyes, which may be of synthetic or natural origin.

Oxidation dyes

According to a particular embodiment of the invention, the composition comprises at least one oxidation dye.

For the purposes of the invention, the term "oxidation dye", also referred to as an

"oxidation dye precursor", is intended to mean a species that is capable of generating a coloured molecule via a process of oxidative condensation with itself or with one or more other compounds.

The oxidation dye precursors are chosen from oxidation bases and couplers, and mixtures thereof.

Preferably, the oxidation dyes comprise an oxidation base or a mixture thereof. The oxidation bases may be chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases, and the addition salts thereof.

Preferentially, the oxidation base(s) of the invention are chosen from para- phenylenediamines and heterocyclic bases.

Among the para-phenylenediamines, examples that may be mentioned include para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3- dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para- phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para- phenylenediamine, Ν,Ν-diethyl-para-phenylenediamine, N,N-dipropyl-para- phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(p-hydroxyethyl)-para- phenylenediamine, 4-N,N-bis(p-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(p- hydroxyethyl)amino-2-chloroaniline, 2-p-hydroxyethyl-para-phenylenediamine, 2-fluoro- para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(p-hydroxypropyl)-para- phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, 2-methoxymethyl-para- phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N-ethyl-N-(p- hydroxyethyl)-para-phenylenediamine, N-(p,y-dihydroxypropyl)-para-phenylenediamine, N-(4'-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-β- hydroxyethyloxy-para-phenylenediamine, 2-p-acetylaminoethyloxy-para- phenylenediamine, N-(p-methoxyethyl)-para-phenylenediamine, 4- aminophenylpyrrolidine, 2-thienyl-para-phenylenediamine, 2-p-hydroxyethylamino-5- aminotoluene and 3-hydroxy-1 -(4'-aminophenyl)pyrrolidine, and the addition salts thereof with an acid.

Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-p-hydroxyethyl-para- phenylenediamine, 2-p-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para- phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para- phenylenediamine, N,N-bis(p-hydroxyethyl)-para-phenylenediamine, 2-chloro-para- phenylenediamine, 2-p-acetylaminoethyloxy-para-phenylenediamine and 2- methoxymethyl-para-phenylenediamine, and the addition salts thereof with an acid, are particularly preferred.

Among the bis(phenyl)alkylenediamines, examples that may be mentioned include N,N'-bis(p-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1 ,3-diaminopropanol, N,N'-bis(p- hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4- aminophenyl)tetramethylenediamine, N,N'-bis(p-hydroxyethyl)-N,N'-bis(4- aminophenyl)tetramethylenediamine, N,N'-bis(4- methylaminophenyl)tetramethylenediamine, N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'- methylphenyl)ethylenediamine and 1 ,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, and the addition salts thereof.

Among the para-aminophenols, examples that may be mentioned include para- aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-chlorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2- hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(p-hydroxyethyl-aminomethyl)phenol and 4-amino-2-fluorophenol, and the addition salts thereof with an acid.

Among the ortho-aminophenols, examples that may be mentioned include 2- aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2- aminophenol, and the addition salts thereof.

Among the heterocyclic bases, mention may be made in particular of pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, for instance 2,5- diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine and 3,4-diaminopyridine, and the addition salts thereof.

Other pyridine oxidation bases that are useful in the present invention are the 3- aminopyrazolo[1 ,5-a]pyridine oxidation bases or the addition salts thereof, described, for example, in patent application FR 2 801 308.

Examples that may be mentioned include pyrazolo[1 ,5-a]pyrid-3-ylamine, 2- acetylaminopyrazolo[1 ,5-a]pyrid-3-ylamine, 2-(morpholin-4-yl)pyrazolo[1 ,5-a]pyrid-3- ylamine, 3-aminopyrazolo[1 ,5-a]pyridine-2-carboxylic acid, 2-methoxypyrazolo[1 ,5- a]pyrid-3-ylamine, (3-aminopyrazolo[1 ,5-a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[1 ,5- a]pyrid-5-yl)ethanol, 2-(3-aminopyrazolo[1 ,5-a]pyrid-7-yl)ethanol, (3-aminopyrazolo[1 ,5- a]pyrid-2-yl)methanol, 3,6-diaminopyrazolo[1 ,5-a]pyridine, 3,4-diaminopyrazolo[1 ,5- a]pyridine, pyrazolo[1 ,5-a]pyridine-3,7-diamine, 7-(morpholin-4-yl)pyrazolo[1 ,5-a]pyrid-3- ylamine, pyrazolo[1 ,5-a]pyridine-3,5-diamine, 5-(morpholin-4-yl)pyrazolo[1 ,5-a]pyrid-3- ylamine, 2-[(3-aminopyrazolo[1 ,5-a]pyrid-5-yl)(2-hydroxyethyl)amino]ethanol, 2-[(3- aminopyrazolo[1 ,5-a]pyrid-7-yl)(2-hydroxyethyl)amino]ethanol, 3-aminopyrazolo[1 ,5- a]pyridin-5-ol, 3-aminopyrazolo[1 ,5-a]pyridin-4-ol, 3-aminopyrazolo[1 ,5-a]pyridin-6-ol, 3- aminopyrazolo[1 ,5-a]pyridin-7-ol, 2-p-hydroxyethoxy-3-aminopyrazolo[1 ,5-a]pyridine and 2-(4-dimethylpiperazinium-1 -yl)-3-aminopyrazolo[1 ,5-a]pyridine, and also the addition salts thereof. More particularly, the oxidation bases according to the invention are chosen from 3- aminopyrazolo[1 ,5-a]pyridines preferably substituted in position 2 with:

a) a (di)(Ci-C₆)(alkyl)amino group, the alkyl groups possibly being substituted with one or more hydroxyl, amino or imidazolium groups;

b) a cationic or non-cationic 5- to 7-membered heterocycloalkyl group comprising from 1 to 3 heteroatoms, optionally substituted with one or more (CrC₆)alkyl groups such as di(Ci-C₄)alkylpiperazinium;

c) a (CrC₆)alkoxy group optionally substituted with one or more hydroxyl groups, such as β-hydroxyalkoxy, and also the addition salts thereof.

Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in patents DE 2359399, JP 88169571 , JP 05-63124 and EP 0 770 375 or patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4- hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6- diaminopyrimidine, 2,5,6-triaminopyrimidine and the addition salts thereof, and the tautomeric forms thereof, when a tautomeric equilibrium exists.

Among the pyrazole derivatives mention may be made of the compounds described in patents DE 3843892 and DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, for instance 4,5-diamino-1 - methylpyrazole, 4,5-diamino-1 -(p-hydroxyethyl)pyrazole, 3,4-diaminopyrazole, 4,5- diamino-1 -(4'-chlorobenzyl)pyrazole, 4,5-diamino-1 ,3-dimethylpyrazole, 4,5-diamino-3- methyl-1 -phenylpyrazole, 4,5-diamino-1 -methyl-3-phenylpyrazole, 4-amino-1 ,3-dimethyl- 5-hydrazinopyrazole, 1 -benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1 - methylpyrazole, 4,5-diamino-1 -tert-butyl-3-methylpyrazole, 4,5-diamino-1 -(β- hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1 -ethyl-3-methylpyrazole, 4,5-diamino-1 - ethyl-3-(4'-methoxyphenyl)pyrazole, 4,5-diamino-1 -ethyl-3-hydroxymethylpyrazole, 4,5- diamino-3-hydroxymethyl-1 -methylpyrazole, 4,5-diamino-3-hydroxymethyl-1 - isopropylpyrazole, 4,5-diamino-3-methyl-1 -isopropylpyrazole, 4-amino-5-(2'- aminoethyl)amino-1 ,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1 -methyl-3,4,5- triaminopyrazole, 3,5-diamino-1 -methyl-4-methylaminopyrazole and 3,5-diamino-4-(p- hydroxyethyl)amino-1 -methylpyrazole, and the addition salts thereof. Preferably, the heterocyclic oxidation bases of the invention are chosen from 4,5-diaminopyrazoles such as 4,5-diamino-1 -(p-hydroxyethyl)pyrazole. Use may also be made of 4,5-diamino-1 -(p- methoxyethyl)pyrazole.

Use will preferably be made of a 4,5-diaminopyrazole and even more preferentially of 4,5-diamino-1 -(p-hydroxyethyl)pyrazole and/or a salt thereof.

Pyrazole derivatives that may also be mentioned include diamino-N,N- dihydropyrazolopyrazolones and in particular those described in patent application FR-A- 2 886 136, such as the following compounds and the addition salts thereof: 2,3-diamino- 6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-ethylamino-6,7-dihydro- 1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-isopropylamino-6,7-dihydro-1 H,5H- pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-(pyrrolidin-1 -yl)-6,7-dihydro-1 H,5H-pyrazolo[1 ,2- a]pyrazol-1 -one, 4,5-diamino-1 ,2-dimethyl-1 ,2-dihydropyrazol-3-one, 4,5-diamino-1 ,2- diethyl-1 ,2-dihydropyrazol-3-one, 4,5-diamino-1 ,2-bis(2-hydroxyethyl)-1 ,2-dihydropyrazol- 3-one, 2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 - one, 2-amino-3-dimethylamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2,3- diamino-5,6,7,8-tetrahydro-1 H,6H-pyridazino[1 ,2-a]pyrazol-1 -one, 4-amino-1 ,2-diethyl-5- (pyrrolidin-1 -yl)-1 ,2-dihydropyrazol-3-one, 4-amino-5-(3-dimethylaminopyrrolidin-1 -yl)-1 ,2- diethyl-1 ,2-dihydropyrazol-3-one or 2,3-diamino-6-hydroxy-6,7-dihydro-1 H,5H- pyrazolo[1 ,2-a]pyrazol-1 -one.

Use will preferably be made of 2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2- a]pyrazol-1 -one and/or a salt thereof.

Heterocyclic bases that will preferentially be used include 4,5-diamino-1 -(p- hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 - one and/or a salt thereof.

Preferably, the total content of oxidation bases used in the context of the anhydrous composition ii) is between 0.001 % and 20% by weight of the total weight of the composition ii) of the packaging article, preferably from 0.01 % to 10% by weight, and preferably from 0.1 % to 6% by weight, relative to the total weight of the composition.

The couplers that are conventionally used for the dyeing of keratin fibres may be chosen from the meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and also the addition salts thereof.

Examples that may be mentioned include 1 ,3-dihydroxybenzene, 1 ,3-dihydroxy-2- methylbenzene, 4-chloro-1 ,3-dihydroxybenzene, 1 -hydroxy-3-aminobenzene, 2-methyl-5- aminophenol, 3-amino-2-chloro-6-methylphenol, 2-methyl-5-hydroxyethylaminophenol, 2,4-diamino-1 -(3-hydroxyethyloxy)benzene, 2-amino-4-(3-hydroxyethylamino)-1 - methoxybenzene, 1 ,3-diaminobenzene, 1 ,3-bis(2,4-diaminophenoxy)propane, 3- ureidoaniline, 3-ureido-1 -dimethylaminobenzene, sesamol, thymol, 1 -β- hydroxyethylamino-3,4-methylenedioxybenzene, a-naphthol, 2-methyl-1 -naphthol, 6- hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine, 6- hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1 -Ν-(β- hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-bis(3-hydroxyethylamino)toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1 -H-3-methylpyrazol-5-one, 1 -phenyl- 3-methylpyrazol-5-one, 2,6-dimethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 2,6-dimethyl[3,2-c]- 1 ,2,4-triazole and 6-methylpyrazolo[1 ,5-a]benzimidazole, the addition salts thereof with an acid, and mixtures thereof.

In general, the addition salts of the oxidation bases and couplers that may be used within the context of the invention are in particular chosen from the addition salts with an acid such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

Preferably, the colouring agent is an oxidation dye, preferably chosen from oxidation bases such as para-phenylenediamines, bis(phenyl)alkylenediamines, para- aminophenols, ortho-aminophenols and heterocyclic bases, and the addition salts thereof, and couplers, chosen from meta-phenylenediamines, meta-aminophenols, meta- diphenols, naphthalene-based couplers and heterocyclic couplers, and also the addition salts thereof; and mixtures thereof.

In the anhydrous composition ii) of the present invention, the oxidation coupler(s) are generally present in an amount included in the range from 0.001 % to 20% by total weight of the composition ii) of the packaging article, preferably from 0.01 % to 10% by weight, and preferably from 0.1 % to 6% by weight, relative to the total weight of the composition. In general, the addition salts of the oxidation bases and couplers that may be used within the context of the invention are in particular chosen from the addition salts with an acid such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates. DIRECT DYES

According to another particular embodiment of the invention, the composition ii) of the packaging article comprises, as agent, at least one direct dye. The direct dye(s) may be synthetic or natural dyes, chosen from ionic or non-ionic species, preferably cationic or non-ionic species.

Preferably, said direct dyes are in anhydrous powder or paste form.

According to a first embodiment, the composition ii) does not comprise any oxidation dye as a mixture with said direct dye(s).

According to a second embodiment, the direct dye(s) is (are) mixed with one or more oxidation dyes in the composition ii), in the same cavity. According to another variant, the direct dye(s) is (are) in a cavity of the packaging article separated from the oxidation dye(s) by one or more sheets as defined previously defining a cavity in which said direct dye(s) is (are) housed.

According to one variant, when the packaging article uses at least one colouring agent and at least one chemical oxidizing agent, the direct dye(s) is (are) separated from the oxidation dyes by a sheet.

The direct dye(s) may be chosen from synthetic direct dyes and natural direct dyes. A synthetic direct dye is understood to be any direct dye that does not exist in the natural state, including dyes obtained semi-synthetically. Examples of suitable synthetic direct dyes that may be mentioned include azo, methine, carbonyl, azine, xanthene, nitro(hetero)aryl, tri(hetero)arylmethane, (metallo)porphyrin and phthalocyanine direct dyes, alone or as mixtures.

More particularly, the synthetic azo direct dyes include an -N=N- function in which the two nitrogen atoms are not simultaneously part of a ring. However, it is not excluded for one of the two nitrogen atoms of the sequence -N=N- to be part of a ring.

Examples of azo direct dyes that may be mentioned include the following dyes, described in Colour Index International, 3rd edition:

- Disperse Red 17

- Basic Red 22

- Basic Red 76

- Basic Yellow 57

- Basic Brown 16

- Basic Brown 17

- Disperse Black 9.

The direct dyes of the methine family are more particularly compounds comprising at least one sequence chosen from >C=C< and -N=C< in which the two atoms are not simultaneously part of a ring. However, it is pointed out that one of the nitrogen or carbon atoms of the sequences may be part of a ring.

More particularly, the methine dyes are derived from methine, azomethine, hydrazono, mono- and diarylmethane, indoamine (or diphenylamine), indophenol, indoaniline and (hemi)cyanine compounds, such as styryl, streptocyanine, carbocyanine, azacarbocyanine, diazacarbocyanine and tetraazacarbocyanine, such as tetraazapentamethine, dyes, and optical and geometric isomers thereof.

Among the azo, azomethine, methine or tetraazapentamethine direct dyes that may be used according to the invention, mention may be made of the cationic dyes described in patent applications WO 95/15144, WO 95/01772 and EP 714954; FR 2189006, FR 2285851 , FR 2140205, EP 1378544, EP 1674073.

Among the indoamine dyes that may be used according to the invention, mention may be made of the following compounds:

- 2-p-hydroxyethlyamino-5-[bis(p-4'-hydroxyethyl)amino]anilino-1 ,4-benzoquinone;

- 2-p-hydroxyethylamino-5-(2'-methoxy-4'-amino)anilino-1 ,4-benzoquinone;

- 3-N-(2'-chloro-4'-hydroxy)phenylacetylamino-6-methoxy-1 ,4-benzoquinone imine;

- 3-N-(3'-chloro-4'-methylamino)phenylureido-6-methyl-1 ,4-benzoquinone imine; - 3-[4'-N-(ethyl,carbamylmethyl)amino]phenylureido-6-methyl-1 ,4-benzoquinone imine.

Among the dyes of tetraazapentamethine type that may be used according to the invention, mention may be made of the following compounds given in the table below:

X^" representing an anion preferably chosen from chloride, iodide, methyl sulfate, ethyl sulfate, acetate and perchlorate.

As regards the synthetic direct dyes of the carbonyl family, examples that may be mentioned include dyes chosen from quinone, acridone, benzoquinone, anthraquinone, naphthoquinone, benzanthrone, anthranthrone, pyranthrone, pyrazolanthrone, pyrimidinoanthrone, flavanthrone, idanthrone, flavone, (iso)violanthrone, isoindolinone, benzimidazolone, isoquinolinone, anthrapyridone, pyrazoloquinazolone, perinone, quinacridone, quinophthalone, indigoid, thioindigo, naphthalimide, anthrapyrimidine, diketopyrrolopyrrole and coumarin dyes.

Among the quinone direct dyes, mention may be made of the following dyes:

- Disperse Red 15

- Solvent Violet 13

- Disperse Violet 1

- Disperse Violet 4

- Disperse Blue 1

- Disperse Violet 8

- Disperse Blue 3 - Disperse Red 1 1

- Disperse Blue 7

- Basic Blue 22

- Disperse Violet 15

- Basic Blue 99

and also the following compounds:

- 1 -N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone;

- 1 -aminopropylamino-4-methylaminoanthraquinone;

- 1 -aminopropylaminoanthraquinone;

- 5-p-hydroxyethyl-1 ,4-diaminoanthraquinone;

- 2-aminoethylaminoanthraquinone;

- 1 ,4-bis(p,y-dihydroxypropylamino)anthraquinone.

As regards the synthetic direct dyes of the azine family, mention may be made in particular of azine, fluorindine, acridine, (di)oxazine and (di)thiazine dyes.

Examples of azine dyes that may be mentioned include the following compounds:

- Basic Blue 17

- Basic Red 2.

As regards the synthetic direct dyes of the xanthene family, mention may be made in particular of xanthene, thioxanthene and pyronine dyes.

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

Among the nitrobenzene direct dyes that may be used according to the invention, mention may be made in a nonlimiting manner of the following compounds:

- 1 ,4-diamino-2-nitrobenzene;

- 1 -amino-2 nitro-4-3-hydroxyethylaminobenzene;

- 1 -amino-2 nitro-4-bis(p-hydroxyethyl)aminobenzene;

- 1 ,4-bis(3-hydroxyethylamino)-2-nitrobenzene;

- 1-3-hydroxyethylamino-2-nitro-4-bis(p-hydroxyethylamino)benzene;

- 1 -3-hydroxyethylamino-2-nitro-4-aminobenzene;

- 1 -p-hydroxyethylamino-2-nitro-4-(ethyl)(3-hydroxyethyl)aminobenzene;

- 1 -amino-3-methyl-4-p-hydroxyethylamino-6-nitrobenzene;

- 1 -amino-2-nitro-4-p-hydroxyethylamino-5-chlorobenzene;

- 1 ,2-diamino-4-nitrobenzene;

- 1 -amino-2-p-hydroxyethylamino-5-nitrobenzene;

- 1 ,2-bis(p-hydroxyethylamino)-4-nitrobenzene;

- 1 -amino-2-tris(hydroxymethyl)methylamino-5-nitrobenzene;

- 1 -hydroxy-2-amino-5-nitrobenzene;

- 1 -hydroxy-2-amino-4-nitrobenzene;

- 1 -hydroxy-3-nitro-4-aminobenzene; - 1 -hydroxy-2-amino-4,6-dinitrobenzene;

- 1 -p-hydroxyethyloxy-2-p-hydroxyethylamino-5-nitrobenzene;

- 1 -methoxy-2-p-hydroxyethylamino-5-nitrobenzene;

- 1 -p-hydroxyethyloxy-3-methylamino-4-nitrobenzene;

- 1 - p,y-dihydroxypropyloxy-3-methylamino-4-nitrobenzene;

- 1 -p-hydroxyethylamino-4-p,y-dihydroxypropyloxy-2-nitrobenzene;

- 1 -p,y-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene;

- 1 -p-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene;

- 1 -p-hydroxyethylamino-3-methyl-2-nitrobenzene;

- 1 -p-aminoethylamino-5-methoxy-2-nitrobenzene;

- 1 -hydroxy-2-chloro-6-ethylamino-4-nitrobenzene;

- 1 -hydroxy-2-chloro-6-amino-4-nitrobenzene;

- 1 -hydroxy-6-bis(p-hydroxyethyl)amino-3-nitrobenzene;

- 1 -p-hydroxyethylamino-2-nitrobenzene;

- 1 -hydroxy-4-p-hydroxyethylamino-3-nitrobenzene.

Among the triarylmethane dyes that may be used according to the invention, mention may be made of the following compounds:

- Basic Green 1

- Basic Violet 3

- Basic Violet 14

- Basic Blue 7

- Basic Blue 26

As regards the (metallo)porphyrin or phthalocyanine synthetic direct dyes, use may be made of cationic or non-cationic compounds, optionally comprising one or more metals or metal ions, for instance alkali metals and alkaline-earth metals, zinc and silicon.

Examples of particularly suitable synthetic direct dyes that may be mentioned include nitrobenzene dyes; azo, methine, azomethine, hydrazono or styryl direct dyes; azacarbocyanines such as tetraazacarbocyanines (tetraazapentamethines); quinone direct dyes, and in particular anthraquinone, naphthoquinone or benzoquinone direct dyes; azine direct dyes; xanthene direct dyes; triarylmethane direct dyes; indoamine direct dyes, indigoid direct dyes, phthalocyanine direct dyes and porphyrin direct dyes, alone or as mixtures.

These dyes may be monochromophoric dyes (i.e. comprising only one dye) or polychromophoric, preferably di- or trichromophoric; the chromophores possibly being identical or different, and from the same chemical family or otherwise. It should be noted that a polychromophoric dye comprises a plurality of groups each derived from a molecule that absorbs in the visible region between 400 and 800 nm. Furthermore, this absorbance of the dye does not require any prior oxidation thereof, or combination with any other chemical species. In the case of polychromophoric dyes, the chromophores are connected together by means of at least one linker L, which may be cationic or non-cationic.

The linker L is preferably a linear, branched or cyclic C1-C2₀ alkyl chain which is optionally interrupted and/or terminated with at least i) a heteroatom (such as nitrogen N(R), N⁺R, R', Q^", oxygen or sulfur), ii) a group C(O), C(S), S(O), or S(0)₂ or iii) a combination thereof, optionally interrupted with at least one heterocycle which may or may not be fused to a phenyl nucleus, and which comprises at least one quaternized nitrogen atom forming part of said ring system, and optionally at least one other heteroatom (such as oxygen, nitrogen or sulfur), optionally interrupted with at least one substituted or unsubstituted phenyl or naphthyl group, optionally at least one quaternary ammonium group substituted with two C1-C15 alkyl groups which are optionally substituted; the linker does not contain a nitro, nitroso or peroxo group, and R and R', which may be identical or different, represent a hydrogen atom or a Ci-C₆ alkyl group which is optionally substituted, preferably with at least one hydroxyl group, and Q^" represents an organic or mineral anionic counterion such as a halide or an alkyl sulfate.

If the heterocycles or aromatic nuclei are substituted, they are substituted, for example, with one or more CrC₈ alkyl groups optionally substituted with a hydroxyl, C C₂ alkoxy, C₂-C₄ hydroxyalkoxy, acetylamino or amino group substituted with one or two Ci-C₄ alkyl groups, optionally bearing at least one hydroxyl group, or the two groups possibly forming, with the nitrogen atom to which they are attached, a 5- or 6-membered heterocycle, optionally comprising another nitrogen or non-nitrogen heteroatom; a halogen atom; a hydroxyl group; a Ci-C₂ alkoxy group; a C₂-C₄ hydroxyalkoxy group; an amino group; an amino group substituted with one or two identical or different Ci-C₄ alkyl groups, optionally bearing at least one hydroxyl group.

According to a particularly advantageous embodiment of the invention, the dye(s) are chosen from (poly)azo dyes such as (di)azo dyes; hydrazono dyes; (poly)methine dyes such as styryl dyes; anthraquinone dyes and naphthalimide dyes. Preferably, these dyes are (poly)cationic.

According to an even more preferred embodiment of the invention, the dyes are chosen from cationic dyes known as "basic dyes".

Mention may be made of the cationic hydrazono dyes of formulae (I) and (Γ), the azo dyes (II) and (ΙΓ) and the diazo dyes (III) below:

Het⁺-C(R^a)=N-N(R^b)- Het⁺-N(R^a)-N=C(R^b)- Het⁺-N=N-Ar,

Ar, Q-(l) Ar, Q-(l') Q-(ll)

Ar₊-N=N-Ar", Q_

and Het⁺-N=N-Ar'

(II¹) -N=N-Ar, Q^"

(III) in which formulae (I), (Γ), (II), (II') and (III):

Het⁺ represents a cationic heteroaryl group, preferably bearing an intracyclic cationic charge, such as imidazolium, indolium or pyridinium, optionally substituted with one or more (Ci-C₈) alkyl groups such as methyl;

Ar⁺ represents an aryl group, such as phenyl or naphthyl, bearing an exocyclic cationic charge, preferentially ammonium, particularly tri(CrC₈ alkyl)ammonium such as trimethylammonium;

Ar represents an aryl group, in particular phenyl, which is optionally substituted, preferentially with one or more electron-donating groups such as i) optionally substituted Ci-C₈ alkyl, ii) optionally substituted Ci-C₈ alkoxy, iii) (di)(Ci-C₈ alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, iv) aryl(Ci-C₈ alkyl)amino, or v) optionally substituted N-(Ci-C₈ alkyl)-N-aryl(Ci-C₈ alkyl)amino, or alternatively Ar represents a julolidine group;

- Ar' is an optionally substituted divalent (hetero)arylene group such as phenylene, particularly para-phenylene, or naphthalene, which are optionally substituted, preferably with one or more Ci-C₈ alkyl, hydroxyl or Ci-C₈ alkoxy groups;

Ar" is an optionally substituted (hetero)aryl group such as phenyl or pyrazolyl, which are optionally substituted, preferably with one or more Ci-C₈ alkyl, hydroxyl, (di)(Ci-C₈ alkyl)amino, Ci-C₈ alkoxy or phenyl groups;

R^a and R^b, which may be identical or different, represent a hydrogen atom or a Ci-C₈ alkyl group, which is optionally substituted, preferentially with a hydroxyl group;

or alternatively the substituent R^a with a substituent of Het⁺ and/or R^b with a substituent of Ar form, together with the atoms that bear them, a (hetero)cycloalkyl;

particularly, R^a and R^b represent a hydrogen atom or a CrC₄ alkyl group, which is optionally substituted with a hydroxyl group;

Q^" represents an organic or mineral anionic counterion, such as a halide or an alkyl sulfate.

In particular, the dyes of the invention are cationically charged, intracyclic, azo and hydrazono dyes of formulae (I), (Γ) and (II) as defined previously. The dyes of formulae (I), (Γ) and (II) described in patent applications WO 95/15144, WO 95/01772 and EP 714954 are more particularly preferred.

Dyes of the invention are preferably chosen from the following compounds:

(1-1 ) (11-1 ) in which formulae (1-1 ) and (11-1 ):

R¹ represents a Ci-C₄ alkyl group such as methyl;

R² and R³, which may be identical or different, represent a hydrogen atom or a C C₄ alkyl group such as methyl; and

R⁴ represents a hydrogen atom or an electron-donating group such as optionally substituted Ci-C₈ alkyl, optionally substituted Ci-C₈ alkoxy, or (di)(CrC₈ alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group; particularly, R⁴ is a hydrogen atom;

- Z represents a CH group or a nitrogen atom, preferentially CH,

Q^" is as defined previously.

In particular, the dyes of formulae (1-1 ) and (11-1 ) are chosen from Basic Red 51 , Basic Yellow 87 and Basic Orange 31 or their derivatives:

where Q^" is as defined previously, and represents in particular a halide such as a chloride, or an alkyl sulfate such as methyl sulfate or mesityl.

Mention may also be made of 1 -(4'-aminodiphenylazo)-2-methyl-4-bis(p- hydroxyethyl)aminobenzene.

Among the polychromophoric dyes, mention may be made more particularly of the symmetrical or non-symmetrical di- or trichromophoric azo and/or azomethine (hydrazone) dyes, comprising on the one hand at least one 5- or 6-membered aromatic heterocycle, optionally fused, which comprises at least one quaternized nitrogen atom forming part of said heterocycle, and optionally at least one other heteroatom (such as nitrogen, sulfur or oxygen), and, on the other hand, at least one optionally substituted phenyl or naphthyl group optionally bearing at least one group OR in which R represents a hydrogen atom, an optionally substituted Ci-C₆ alkyl group, an optionally substituted phenyl nucleus, or at least one group N(R')₂ with R', which may be identical or different, representing a hydrogen atom, an optionally substituted Ci-C₆ alkyl group or an optionally substituted phenyl nucleus; the groups R' possibly forming, with the nitrogen atom to which they are attached, a saturated, 5- or 6-membered heterocycle, or else one and/or both of the groups R' may each form a saturated, 5- or 6-membered heterocycle with the carbon atom of the aromatic ring that is ortho to the nitrogen atom.

Aromatic cationic heterocycles that may preferably be mentioned include 5- or 6- membered rings containing 1 to 3 nitrogen atoms and preferably 1 or 2 nitrogen atoms, one being quaternized; said heterocycle moreover being optionally fused to a benzene nucleus. It should similarly be noted that the heterocycle may optionally comprise another heteroatom other than nitrogen, for instance sulfur or oxygen.

If the heterocycles or phenyl or naphthyl groups are substituted, they are substituted, for example, with one or more Ci-C₈ alkyl groups optionally substituted with a hydroxyl, CrC₂ alkoxy, C₂-C₄ hydroxyalkoxy, acetylamino or amino group substituted with one or two C C₄ alkyl groups, optionally bearing at least one hydroxyl group, or the two groups possibly forming, with the nitrogen atom to which they are attached, a 5- or 6- membered heterocycle, optionally comprising another nitrogen or non-nitrogen heteroatom; a halogen atom; a hydroxyl group; a Ci-C₂ alkoxy group; a C₂-C₄ hydroxyalkoxy group; an amino group; an amino group substituted with one or two identical or different d-C₄ alkyl groups, optionally bearing at least one hydroxyl group.

These polychromophores are connected together via at least one linker L as defined previously.

The bonding between the linker L and each chromophore generally takes place via a heteroatom substituent on the phenyl or naphthyl nucleus or via the quaternized nitrogen atom of the cationic heterocycle.

The dye may comprise identical or different chromophores.

As examples of such dyes, reference may be made in particular to patent applications EP 1 637 566, EP 1 619 221 , EP 1 634 926, EP 1 619 220, EP 1 672 033, EP 1 671 954, EP 1 671 955, EP 1 679 312, EP 1 671 951 , EP 167 952, EP 167 971 , WO 06/063 866, WO 06/063 867, WO 06/063 868, WO 06/063 869, EP 1 408 919, EP 1 377 264, EP 1 377 262, EP 1 377 261 , EP 1 377 263, EP 1 399 425, EP 1 399 1 17, EP 1 416 909, EP 1 399 1 16 and EP 1 671 560.

It is equally also possible to use cationic synthetic direct dyes which are mentioned in the following patent applications: EP 1 006 153, which describes dyes comprising two chromophores of anthraquinone type connected via a cationic linker; EP 1 433 472, EP 1 433 474, EP 1 433 471 and EP 1 433 473, which describe identical or different dichromophoric dyes, connected via a cationic or non-cationic linker, and also EP 6 291 333, which in particular describes dyes comprising three chromophores, one of them being an anthraquinone chromophore, to which are attached two chromophores of azo or diazacarbocyanine type or an isomer thereof. The term "natural dyes" is intended to mean any dye or dye precursor that is naturally occurring and that is produced either by extraction (and possibly purification) from a plant or animal matrix, optionally in the presence of natural compounds such as ash or ammonia, or by chemical synthesis.

Natural dyes that may be mentioned include lawsone, henna, curcumin, chlorophyllin, alizarin, kermesic acid, purpurin, purpurogallin, indigo, Tyrian purple, sorghum, carminic acid, catechin, epicatechin, juglone, bixin, betanin, quercetin, chromene dyes and chroman dyes, including haematein and brazilein, and laccaic acids, alone or as a mixture.

Preferably, the natural dyes used in the invention are chosen from curcumin, chlorophyllin, chromene dyes, chroman dyes and laccaic acids.

According to the invention, the terms "chromene dye" and "chroman dye" mean dyes which comprise in their structure at least one bicycle of formula (IV) below:

IV the intracyclic bond representing a carbon-carbon single bond or a carbon- carbon double bond, as illustrated by formula IV-1 denoting the chromene family and formula IV-2 denoting the chroman family below:

IV-1 IV-2

More particularly, the dyes having in their structure a bicycle of formula (IV) are chosen from the dyes having the following formulae:

- formula (V), comprising in its structure the bicycle of formula IV-2,

in which:

i) represents a carbon-carbon single bond or a carbon-carbon double bond, the sequence of these bonds denoting two carbon-carbon single bonds and two carbon-carbon double bonds, said bonds being conjugated,

ii) X represents a group:

// /

HO-C or 0=C

\ \

iii) R¹, R², R³, R⁴, R⁵ and R⁶, which may be identical or different, represent, independently of each other, a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted alkoxy group or an optionally substituted acyloxy group,

and also the tautomeric and/or mesomeric forms thereof, the stereoisomers thereof, the addition salts thereof with a cosmetically acceptable acid or base, and the hydrates thereof, and

- formula (VI), comprising in its structure the bicycle of formula IV-1 :

in which:

- Rii , Ri2, Ri3, Ri6, Ri9 and R₂o, which may be identical or different, represent, independently of each other, a hydrogen atom or a C₁-C4 alkyl group,

- R-I4, R-I5, R-I7 and Ri₈, which may be identical or different, represent, independently of each other, a hydrogen atom, a hydroxyl group or a C₁-C4 alkoxy group, and also the tautomeric and/or mesomeric forms thereof, the stereoisomers thereof, the addition salts thereof with a cosmetically acceptable acid or base, and the hydrates thereof.

As regards the dyes of formula (V) as defined previously, they may be in two tautomeric forms noted (Va) and (Vb):

The alkyi groups mentioned in the preceding definitions of the substituents are linear or branched, saturated hydrocarbon groups, generally Ci-C₂o, particularly C1-C1₀ and preferably Ci-C₆, such as methyl, ethyl, propyl, butyl, pentyl and hexyl.

The alkoxy groups are alkyl-oxy groups with alkyi groups as defined previously and preferably the alkoxy groups are C1-C1₀, such as methoxy, ethoxy, propoxy and butoxy.

The alkyi or alkoxy groups, when they are substituted, may be substituted with at least one substituent borne by at least one carbon atom, chosen from:

a halogen atom;

a hydroxyl group;

a C1-C2 alkoxy group;

a C1-C1₀ alkoxycarbonyl group;

C2-C4 (poly)hydroxyalkoxy group;

an amino group;

a 5- or 6-membered heterocycloalkyl group;

an optionally cationic 5- or 6-membered heteroaryl group, preferentially imidazolium, optionally substituted with a (CrC₄)alkyl group, preferentially methyl;

an amino group substituted with one or two identical or different Ci-C₆ alkyi groups, optionally bearing at least:

^* a hydroxyl group,

^* an amino group optionally substituted with one or two optionally substituted C1-C3 alkyi groups, it being possible for said alkyi groups to form, with the nitrogen atom to which they are attached, a saturated or unsaturated and optionally substituted 5- to 7- membered heterocycle, optionally comprising at least one other nitrogen or non-nitrogen heteroatom, ^* a quaternary ammonium group -N⁺R'R"R"', M^" for which R', R" and R"\ which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl group; and M^" represents the counterion of the corresponding organic or mineral acid or of the corresponding halide;

* or an optionally cationic 5- or 6-membered heteroaryl group, preferentially imidazolium, optionally substituted with a (C1-C4) alkyl group, preferentially methyl;

an acylamino group (-NR-COR') in which the group R is a hydrogen atom or a C1-C4 alkyl group optionally bearing at least one hydroxyl group and the group R' is a Ci-C₂ alkyl group;

- a carbamoyl group ((R)₂N-CO-) in which the groups R, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl group optionally bearing at least one hydroxyl group;

an alkylsulfonylamino group (R'S0₂-NR-) in which the group R represents a hydrogen atom or a C1-C4 alkyl group optionally bearing at least one hydroxyl group and the group R' represents a C1-C4 alkyl group, or a phenyl group;

an aminosulfonyl group ((R)₂N-S0₂-) in which the groups R, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl group optionally bearing at least one hydroxyl group;

- a carboxylic group in acid or salified form (preferably with an alkali metal or a substituted or unsubstituted ammonium);

a cyano group;

a nitro group;

a carboxyl or glycosylcarbonyl group;

- a phenylcarbonyloxy group optionally substituted with one or more hydroxyl groups;

a glycosyloxy group; and

a phenyl group optionally substituted with one or more hydroxyl groups. The term "glycosyl group" is intended to mean a group originating from a mono- or polysaccharide.

Preferably, the alkyl or alkoxy groups of formula (V) are unsubstituted.

According to one particular embodiment of the invention, the dyes of formula (V) comprise a group R⁶ which represents a hydroxyl group.

In one preferred variant, X represents a group 0=C.

Another particular embodiment of the invention relates to the dyes of formula (V), for which the group R¹ represents a hydrogen atom or a hydroxyl group.

More particularly, the dyes of formula (V) are chosen from haematein and brazilein.

Brazilein is a conjugated form of a chroman compound of formula IV-2. The tautomeric structures (Va) and (Vb) illustrated above are found in the scheme below.

Brazilein and haematein or the haematoxylin/haematein and brazilin/brazilein pairings may be obtained synthetically or by extraction of plants known to be rich in these dyes.

The dyes of formula (V) may be used in the form of extracts. Use may be made of the following plant extracts (genus and species): Haematoxylon campechianum, Haematoxylon brasiletto, Caesalpinia echinata, Caesalpinia sappan, Caesalpinia spinosa and Caesalpinia brasiliensis.

The extracts are obtained by extracting the various plant parts, for instance the roots, the wood, the bark or the leaves.

According to one particular embodiment of the invention, the natural dyes of formula (V) are obtained from logwood, pernambuco wood, sappan wood and Brazil wood.

The salts of the dyes of formulae (V) and (VI) of the invention may be salts of cosmetically acceptable acids or bases.

The acids may be mineral or organic. Preferably, the acid is hydrochloric acid, which results in chlorides.

The bases may be mineral or organic. In particular, the bases are alkali metal hydroxides such as sodium hydroxide which leads to sodium salts.

Preferably, the dye(s) of formulae (V) and (VI) included in the composition according to the invention are derived from plant extracts. Use may also be made of mixtures of plant extracts. The natural extracts of the dyes according to the invention may be in the form of powders or liquids. Preferably, the extracts are provided in powder form.

In another variant of the invention, the natural dyes are chosen from laccaic acids.

For the purposes of the present invention, the term "laccaic acid" is intended to mean a compound having in its structure a unit of the type:

Preferably, the laccaic acids of the invention are of formula (VII) below:

(VII)

with R-i denoting a phenyl group substituted with at least one hydroxyl group, and preferably with a hydroxyl group that is advantageously in the ortho position relative to the bond attaching it to the fused nuclei.

In particular, the phenyl group Ri comprises, besides a hydroxyl group, at least one group -CH₂R₂, R₂ denoting an acetamidomethyl (CH₃CONHCH₂-), hydroxymethyl (HOCH₂-) or 2-aminoacetic acid group (H0₂C(NH₂)CH-).

Preferentially, the laccaic acids of the invention are chosen from laccaic acids A, B, C and D, or mixtures thereof, and more particularly chosen from A, B and C, or mixtures thereof.

A laccaic acid according to the invention that may in particular be used is the dye CI Natural Red 25, CI 75450, CAS - 60687-93-6, which is often referred to as laccaic acid. This is a dye of natural origin originating from the secretions of an insect, Coccus laccae (Lacifer Lacca Kerr), which is generally found on the twigs of certain trees native to South-East Asia.

CI Natural Red 25 generally contains two major constituents in its composition: laccaic acid A and laccaic acid B. It may also contain a small amount of laccaic acid C.

It is obviously also possible to use the purified forms of the laccaic acids of formula (VII).

Even more preferentially, the natural direct dyes are chosen from haematein and brazilein.

Examples of suitable direct dyes that may be mentioned include azo direct dyes; (poly)methine dyes such as cyanins, hemicyanins and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes, and natural direct dyes, alone or as mixtures.

Among the natural direct dyes that can be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechualdehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orceins. Use may also be made of extracts or decoctions containing these natural dyes and in particular henna-based extracts or poultices.

When they are present, the direct dye(s) more particularly represent from 0.001 % to 20% by weight of the total weight of the composition ii) or of the compositions contained in the packaging article, preferably from 0.01 % to 10% by weight, and preferably from 0.1 % to 6% by weight relative to the total weight. When they are present, the colouring agent(s) more particularly represent a total content of from 0.001 % to 20% by weight of the total weight of the composition ii) or of the compositions contained in the packaging article, preferably from 0.01 % to 10% by weight, and preferably from 0.1 % to 6% by weight relative to the total weight.

According to one embodiment of the invention, the packaging article is free of direct dye.

CHEMICAL OXIDIZING AGENT

The anhydrous composition ii) of the packaging article of the invention may comprise one or more chemical oxidizing agents, preferably in powder or paste form.

The term "chemical oxidizing agent" is intended to mean an oxidizing agent other than atmospheric oxygen.

More particularly, the chemical oxidizing agent(s) is (are) chosen from peroxygenated salts, for instance persulfates, perborates, peracids and precursors thereof, percarbonates of alkali metals or alkaline-earth metals, such as sodium carbonate peroxide also known as sodium percarbonate and peracids and precursors thereof; peroxygenated salts, for instance persulfates, perborates, peracids and precursors thereof, percarbonates of alkali metals or alkaline-earth metals such as sodium carbonate peroxide also known as sodium percarbonate and peracids and precursors thereof: alkali metal bromates or ferricyanides, hydrogen peroxide-generating solid chemical oxidizing agents such as urea peroxide and polymeric complexes that can release hydrogen peroxide, in particular those comprising a heterocyclic vinyl monomer such as polyvinylpyrrolidone/H₂02 complexes, in particular in the form of powders; oxidases that produce hydrogen peroxide in the presence of a suitable substrate (for example glucose in the case of glucose oxidase or uric acid with uricase).

Preferably, the chemical oxidizing agent(s) is (are) chosen from percarbonates of alkali metals or alkaline-earth metals, preferably such as sodium carbonate peroxide, also known as sodium percarbonate.

According to one particular embodiment, the oxidizing agent is chosen from complexes of hydrogen peroxide and of polymer containing as monomer at least one heterocyclic vinyl monomer.

More particularly, the heterocyclic vinyl monomer is chosen from monomers comprising a 4- to 6-membered heterocycle, optionally fused to a benzene ring and comprising from 1 to 4 identical or different intracyclic heteroatoms; the number of intracyclic heteroatoms being less than the number of ring members of the heterocycle. Preferably, the number of intracyclic heteroatoms is 1 or 2.

More particularly, the heteroatom(s) are chosen from sulfur, oxygen and nitrogen, preferably from nitrogen and oxygen. In accordance with an even more advantageous embodiment of the invention, the monomer comprises at least one intracyclic nitrogen atom.

The vinyl heterocycle may optionally be substituted with one or more C1-C4 and preferably Ci-C₂ alkyl groups.

Preferably, the heterocyclic monomer is chosen from /V-vinyl monomers.

Among the monomers that may be envisaged, mention may be made of the following optionally substituted monomers: N-vinylpyrrolidone, vinylcaprolactam, N- vinylpiperidone, N-vinyl-3-morpholine, N-vinyl-4-oxazolinone, 2-vinylpyridine, 4- vinylpyridine, 2-vinylquinoline, 1 -vinylimidazole and 1 -vinylcarbazole. Preferably, the monomer is optionally substituted N-vinylpyrrolidine.

According to a particularly advantageous embodiment of the invention, the polymer is a homopolymer.

However, it is not excluded to use a copolymer. In such a case, the comonomer(s) are chosen from vinyl acetate, (meth)acrylic acids, (meth)acrylamides and C1-C4 alkyl esters of (meth)acrylic acid, which may be substituted or unsubstituted.

The polymer participating in this complex is preferably water-soluble. It may have variable average molecular weights, preferably between 10³ and 3x10⁶ g/mol and preferably between 10³ and 2x10⁶ g/mol. It is also possible to use mixtures of such polymers.

Advantageously, said complex comprises from 10% to 30% by weight, more particularly from 13% to 25% by weight and preferably from 18% to 22% by weight of hydrogen peroxide relative to the total weight of the complex.

According to an even more advantageous variant of the invention, in this complex, the mole ratio between the heterocyclic vinyl monomer(s) and the hydrogen peroxide ranges from 0.5 to 2 and preferably from 0.5 to 1.

This complex is advantageously in the form of a substantially anhydrous powder. Complexes of this type are in particular described in US 5 008 106, US 5 077 047, EP 832 846, EP 714 919, DE 4344131 and DE 195 45 380 and the other polymer complexes described in US 5 008 093, US 3 376 1 10 and US 5 183 901.

Examples of complexes that may be mentioned include products such as

Peroxydone K-30, Peroxydone K-90 and Peroxydone XL-10 and also complexes formed with hydrogen peroxide and one of the following polymers such as Plasdone K-17, Plasdone K-25, Plasdone K-29/32, Plasdone K-90, Polyplasdone INF-10, Polyplasdone XL-10, Polyplasdone XL, Plasdone S-630, Styleze 2000 Terpolymer and the series of Ganex copolymers, sold by the company ISP. According to one particular embodiment of the invention, the anhydrous composition ii) of the packaging article contains one or more solid chemical oxidizing agent(s).

According to one particular embodiment, the chemical oxidizing agent(s) is (are) chosen from a) urea peroxide, b) polymer complexes that can release hydrogen peroxide, chosen from polyvinylpyrrolidone/H202 complexes; c) perborates and d) percarbonates; preferably, the packaging article contains as chemical oxidizing agents one or more percarbonates.

The composition ii) of the packaging article according to the invention advantageously contains from 1 % to 80% by weight of chemical oxidizing agent, preferably from 5% to 70% by weight and preferably from 10% to 60% by weight, relative to the total weight of the composition ii).

Preferably, when the composition ii) comprises at least one colouring agent chosen from oxidation dyes, direct dyes and/or mixtures thereof, preferably from oxidation dyes, then the dyeing process preferably uses at least one chemical oxidizing agent.

In a first variant of this process, the chemical oxidizing agent may also be present in the composition ii) as a mixture with the colouring agent.

In a second variant of this process, the chemical oxidizing agent may be present in an anhydrous composition ii') which is in a cavity of the envelope other than that comprising the anhydrous composition ii) of the packaging article according to the invention.

According to a third variant of this process, the packaging article does not comprise any oxidizing agent.

According to this variant, if it is necessary to perform the colouring in the presence of an oxidizing agent, then the packaging article may be either first dissolved in an aqueous composition to which is then added at least one chemical oxidizing agent, or directly dissolved in an oxidizing composition comprising at least one chemical oxidizing agent. In this case, the oxidizing agent may be a chemical oxidizing agent such as hydrogen peroxide.

The chemical oxidizing agent may also be added to the aqueous composition in the form of a packaging article as previously defined in a composition which is inside a cavity of an envelope not containing any colouring agent.

OTHER INGREDIENTS

The anhydrous composition ii) of the packaging article may contain other ingredients.

ALKALINE AGENT In particular, the composition ii) may contain one or more alkaline agents. The alkaline agent(s) may be in the packaging article either combined with the oxidation dyes, or separated from the dyes by one or more sheets as defined previously.

The alkaline agent(s) are more particularly chosen from silicates and metasilicates such as alkali metal metasilicates, carbonates or hydrogen carbonates of alkali metals or alkaline-earth metals, such as lithium, sodium, potassium, magnesium, calcium or barium, and mixtures thereof.

Preferably, the alkaline agent(s) are chosen from alkali metal silicates, metasilicates and carbonates, and mixtures thereof.

The concentration of alkaline agents advantageously represents from 0.01 % to

40% by weight and preferably from 0.1 % to 30% by weight relative to the total weight of the composition(s) contained in the packaging article.

STARCH

According to one advantageous embodiment, the anhydrous composition ii) of the packaging article comprises at least one starch or one modified starch, preferably at least one modified starch.

The starches that can be used in the composition ii) of the packaging article of the present invention can originate from any plant starch source, in particular cereals and tubers; more particularly, they can be starches from maize, rice, cassava, barley, potato, wheat, sorghum, pea, oat or tapioca. Use may also be made of the hydrolysates of the abovementioned starches. The starch is preferably derived from potato.

The starches can be chemically or physically modified. Preferably, the starch used in the present invention is modified by at least one of the following reactions: pregelatinization, oxidation, crosslinking, esterification, etherification, amidation, heat treatments.

Preferably, said starch(es) is (are) modified by at least one of the following reactions: pregelatinization, oxidation, crosslinking and/or esterification

More particularly, these reactions can be carried out in the following way:

- crosslinking with functional agents capable of reacting with the hydroxyl groups of the starch molecules, which will thus be bonded together (for example with glyceryl and/or phosphate groups); - esterification in alkaline medium for the grafting of functional groups, in particular Ci-C₆ acyl (acetyl), Ci-C₆ hydroxyalkyl (hydroxyethyl or hydroxypropyl), carboxymethyl or octenylsuccinic.

Preferably, the starch used in the present invention is modified by crosslinking, preferably with phosphate groups, and/or by esterification, preferably by grafting functional groups, in particular CrC₆ acyl (acetyl), Ci-C₆ hydroxyalkyl (hydroxyethyl, hydroxypropyl), carboxymethyl and/or octenylsuccinic groups.

Use will preferentially be made of distarch phosphates or compounds rich in distarch phosphate, such as the product sold under the references Prejel VA-70-T AGGL (gelatinized hydroxypropyl cassava distarch phosphate) or the gelatinized cassava distarch phosphate sold under the reference Prejel TK1 or the gelatinized acetyl cassava distarch phosphate sold under the reference Prejel 200 by the company Avebe, or the pregelatinized hydroxypropyl corn distarch phosphate compound, the INCI name of which is hydroxypropyl starch phosphate, sold under the referencer Structure Zea by Akzo Nobel.

Preferably, pregelatinized hydroxypropyl corn distarch phosphate is used.

The amphoteric starches are in particular chosen from the compounds having the following formulae: St - 0 - (CH₂)_n - N

(I) R' R

R' R' R'

\ \ R'

N N

St - O - C— C— COOM St - O - C— C— COOM

H₂ H

(III) (IV)

in which formulae (I) to (IV):

St-0 represents a starch molecule;

R', which may be identical or different, represents a hydrogen atom, a methyl radical or a group -C(0)-OH;

n is an integer equal to 2 or 3;

R" represents a hydrogen atom or a Ci-Ci₈ alkyl radical.

These compounds are in particular described in US 5 455 340 and US 4 017 460. Use is in particular made of the starches of formulae (II) or (III); and preferably starches modified with 2-chloroethylaminodipropionic acid, that is to say the starches of formula (II) or (III) in which R, R', R" and M represent a hydrogen atom and n is equal to 2. The preferred amphoteric starch is a starch chloroethylamidodipropionate.

Preferably, use is made of pregelatinized hydroxypropyl corn distarch phosphate, for example sold by Akzo Nobel, and/or sodium carboxymethyl starch, for example sold by Roquette, and/or sodium starch glycolate, for example sold under the reference Explotab, and/or partially pregelatinized starches, for instance those sold under the references Starch 1500 or Lycotab. Use is preferably made of pregelatinized hydroxypropyl corn distarch phosphate and/or sodium carboxymethyl starch.

Thus, use is preferably made of a starch modified by at least one of the following reactions: pregelatinization, oxidation, crosslinking, esterification, etherification, amidation, heat treatments, preferably chosen from pregelatinized hydroxypropyl corn distarch phosphate and/or sodium carboxymethyl starch and/or sodium starch glycolate and/or partially pregelatinized starches. The concentration of starch, preferably of modified starch as previously defined, advantageously represents from 1 % to 80% by total weight, preferably from 1 % to 50% by weight, and preferably from 2% to 25% by weight, of the total weight of the composition(s) contained in the packaging article.

CELLULOSE AND CELLULOSE DERIVATIVES

According to one advantageous embodiment, the anhydrous composition ii) of the packaging article comprises at least one cellulose, and/or cellulose derivatives.

The celluloses and cellulose derivatives can be anionic, cationic, amphoteric or non-ionic.

Mention may be made, among the cellulose esters, of inorganic cellulose esters

(cellulose nitrates, sulfates or phosphates), organic cellulose esters (cellulose monoacetates, triacetates, amidopropionates, acetate butyrates, acetate propionates or acetate trimellitates), and mixed organic/inorganic cellulose esters, such as cellulose acetate butyrate sulfates and cellulose acetate propionate sulfates.

Mention may be made, among the anionic cellulose ethers, of carboxyalkylcelluloses and their salts. Mention may be made, as examples, of carboxymethylcelluloses, for example crosslinked sodium carboxymethylcelluloses, for instance sodium croscarmelloses,carboxymethylmethylcelluloses (for example Blanose 7M from the company Aqualon) and carboxymethylhydroxyethylcelluloses, and also sodium salts thereof. Among the anionic cellulose ethers, use is preferably made of crosslinked sodium carboxymethylcelluloses, preferably sodium croscarmellose.

Among the cationic cellulose ethers, mention may be made of hydroxyethylcelluloses. Among the cationic cellulose ethers, mention may be made of crosslinked or non-crosslinked quaternized hydroxyethylcelluloses. The quaternizing agent may in particular be diallyldimethylammonium chloride (for example Celquat L200 from National Starch). Another cationic cellulose ether that may be mentioned is hydroxypropyltrimethylammonium hydroxyethyl cellulose (for example Ucare Polymer JR 400 from Amerchol).

Preferably, the celluloses and/or the cellulose derivatives are chosen from:

microcrystalline celluloses, microcrystalline cellulose derivatives for instance the microcrystalline cellulose Avicel PH 105 NF sold by FMC Corporation; and/or

crosslinked sodium carboxymethyl celluloses, preferably sodium croscarmellose. The total concentration of cellulose, and/or of cellulose derivatives, advantageously represents from 0.01 % to 40% by total weight, and preferably from 0.1 % to 30% by weight, of the total weight of the composition(s) contained in the packaging article.

CROSSLINKED POLYVINYLPYRROLIDONE:

According to one particular embodiment, the composition ii) of the packaging article according to the invention comprises at least one crosslinked polyvinylpyrrolidone, preferably crospovidone c).

Mention may for example be made of those sold under the references Kollidon CL, Polyplasdone, or PVP XL.

Preferably, the total concentration of crosslinked polyvinylpyrrolidone(s) represents from 0.01 % to 40% by total weight, and preferably from 0.1 % to 30% by weight, of the total weight of the composition(s) contained in the packaging article. Preferably, the composition ii) of the article according to the invention comprises one or more additional compound(s) chosen from:

starches and/or starches modified by at least one of the following reactions: pregelatinization, oxidation, crosslinking, esterification, etherification, amidation, heat treatments, preferably pregelatinized hydroxypropyl corn distarch phosphate; cellulose and/or a cellulose derivative, preferably microcrystalline cellulose; and/or crosslinked sodium carboxymethylcelluloses, preferably sodium croscarmellose; crosslinked polyvinylpyrolidones, preferably crospovidone;

mixtures thereof.

AMMONIUM SALTS

According to one particular embodiment of the invention, the composition ii) of the packaging article contains one or more ammonium salts. The ammonium salt(s) that may be in the packaging article is (are) either combined with the oxidation dyes, or combined with the direct dyes, or separated from the dyes by one or more water-soluble sheets as defined previously defining a cavity in which said salt(s) is (are) housed.

According to a particular variant, the packaging article comprises one or more ammonium salts chosen from ammonium halides such as ammonium chloride, ammonium sulfate, ammonium phosphate and ammonium nitrate.

In accordance with an even more advantageous embodiment of the invention, the ammonium salt is ammonium chloride or ammonium sulfate.

The concentration of ammonium salt(s), if they are present, is advantageously between 0.01 % and 40% by weight relative to the total weight of the composition(s) contained in the packaging article, and preferably from 0.1 % to 30% by weight relative to the total weight of the composition(s) contained in the packaging article.

LIQUID FATTY SUBSTANCES

Preferably, when the composition ii) is in paste form, it also comprises one or more liquid fatty substances.

For the purposes of the present invention, the term "liquid" is intended to mean any compound that is capable of flowing at ambient temperature, generally between 15°C and 40°C, and at atmospheric pressure, under the action of its own weight.

Examples of liquid fatty substances that may be mentioned include the polydecenes of formula Cio_nH[₍20n)+2] in which n ranges from 3 to 9 and preferably from 3 to 7, esters and in particular esters of fatty alcohols or of fatty acids, sugar esters or diesters of Ci₂- C₂4 fatty acids, cyclic esters, cyclic ethers, silicone oils, mineral oils, plant oils or animal oils, or mixtures thereof. Preferably, the liquid fatty substance(s) are chosen from the polydecenes of formula Cio_nH[(20n)+2] in which n ranges from 3 to 9 and preferably from 3 to 7, esters of fatty alcohols or of fatty acids, liquid petroleum jelly and liquid paraffin, and mixtures thereof.

Preferably, one or more mineral oil(s) may be in the packaging article, in particular combined with the oxidation dye(s), for instance liquid paraffin or petroleum jelly, preferably petroleum jelly.

In the composition(s) contained in the packaging article, the content of liquid fatty substance(s), if they are present, advantageously ranges from 10% to 50% by weight relative to the weight of the composition(s) contained in the packaging article, and preferably from 20% to 50% by weight relative to the weight of the composition(s) contained in the packaging article.

The anhydrous composition according to the invention in paste form comprising a liquid fatty substance may be advantageously prepared by dispersing, under mechanical action, all of the compounds that are in powder form in the liquid fatty substance, in which the other liquid compounds of the composition have been predispersed or premixed.

The paste may also be prepared by extrusion, by introducing the liquid and solid phases of the composition into an extruder and then mixing them at a temperature below 25°C using a co-rotating twin-screw system composed of transportation and blending elements.

THICKENING POLYMERS

According to one particular embodiment, the packaging article of the invention comprises one or more thickening polymer(s), these polymer(s) possibly being in said article either with the colouring agent(s) and/or the chemical oxidizing agent(s) or separated from the other ingredients by one or more water-soluble sheet(s) as defined previously.

In particular, the thickening polymers are different from the starches and the celluloses described previously.

Advantageously, the thickening polymers are chosen from the following polymers:

(a) non-ionic amphiphilic polymers comprising at least one fatty chain and at least one hydrophilic unit;

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

(c) crosslinked acrylic acid homopolymers;

(d) crosslinked homopolymers of 2-acrylamido-2-methylpropanesulfonic acid, and crosslinked acrylamide copolymers thereof which are partially or totally neutralized; (e) ammonium acrylate homopolymers or copolymers of ammonium acrylate and of acrylamide;

(f) dimethylaminoethyl methacrylate homopolymers quaternized with methyl chloride or dimethylaminoethyl methacrylate copolymers quaternized with methyl chloride and acrylamide;

(g) polysaccharides such as:

(g1 ) scleroglucan gums (biopolysaccharide of microbial origin);

(g2) gums derived from plant exudates, such as gum arabic, ghatti gum, karaya gum or gum tragacanth; and

(g4) guar gums and derivatives; or

It should be noted that, in the case of the present invention, the thickening polymers act on the viscosity of the ready-to-use composition, i.e. the composition resulting from the mixing of the packaging article according to the invention with an aqueous composition.

According to the invention, amphiphilic polymers are more particularly hydrophilic polymers that are capable, in the medium of the composition, and more particularly an aqueous medium, of reversibly combining with each other or with other molecules.

Their chemical structure more particularly comprises at least one hydrophilic region and at least one hydrophobic region. The term "hydrophobic group" is intended to mean a radical or polymer bearing a saturated or unsaturated, linear or branched hydrocarbon- based chain, comprising at least 8 carbon atoms, preferably at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 18 to 30 carbon atoms. Preferentially, the hydrocarbon-based group is derived from a monofunctional compound. By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also denote a hydrocarbon-based polymer, for instance polybutadiene.

The thickening polymers are preferably used in an amount that may range from 0.01 % to 15% by weight relative to the weight of the composition(s) contained in the packaging article, and preferably from 0.1 % to 10% by weight relative to the weight of the composition(s) contained in the packaging article.

SURFACTANTS

According to one particular embodiment, the packaging article of the invention comprises one or more surfactants. These surfactants may be in said article either in the anhydrous composition ii), or separated from the other ingredients by one or more water- soluble sheets as defined previously, which define a cavity in which the surfactant(s) is (are) housed. Preferably, the surfactant(s) is (are) with the dye(s) and/or the chemical oxidizing agent(s) in the packaging article. For the purposes of the present invention, the term "surfactant" is intended to mean an agent comprising at least one hydrophilic group and at least one lipophilic group in its structure, and which is preferably capable of reducing the surface tension of water, and comprising in its structure, as optional repeating units, only alkylene oxide units and/or sugar units and/or siloxane units. Preferably, the lipophilic group is a fatty chain comprising from 8 to 30 carbon atoms.

This or these surfactants may be chosen from anionic, amphoteric, non-ionic and cationic surfactants, or mixtures thereof. More particularly, the surfactants are chosen from non-ionic and anionic surfactants.

The surfactants that are suitable for implementing the present invention are in particular the following:

(a) Anionic surfactant(s):

The term "anionic surfactant" is intended to mean a surfactant comprising, as ionic or ionizable groups, only anionic groups. These anionic groups are preferably chosen from the groups -C(0)OH, -C(0)0-, -S0₃H, -S(0)₂0^", -OS(0)₂OH, -OS(0)₂0^", -P(0)OH₂, -P(0)₂0^", -P(0)0₂ ^", -P(OH)₂, =P(0)OH, -P(OH)0^", =P(0)0^", =POH and =PO^", the anionic parts comprising a cationic counterion such as those derived from an alkali metal, an alkaline-earth metal, an amine or an ammonium.

As examples of anionic surfactants that may be used in the composition according to the invention, mention may be made of alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, oolefin sulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfoacetates, acylsarcosinates, acylglutamates, alkyl sulfosuccinamates, acylisethionates and N-acyltaurates, polyglycoside polycarboxylic acid and alkyl monoester salts, acyl lactylates, salts of D-galactoside uronic acids, salts of alkyl ether carboxylic acids, salts of alkylaryl ether carboxylic acids, salts of alkylamido ether carboxylic acids; and the corresponding non-salified forms of all these compounds; the alkyl and acyl groups of all these compounds comprising from 6 to 24 carbon atoms and the aryl group denoting a phenyl group.

These compounds can be oxyethylenated and then preferably comprise from 1 to

50 ethylene oxide units.

The salts of C₆-C₂₄ alkyl monoesters of polyglycoside-polycarboxylic acids may be chosen from C₆-C₂₄ alkyl polyglycoside-citrates, C₆-C₂₄ alkyl polyglycoside-tartrates and C₆-C₂₄ alkyl polyglycoside-sulfosuccinates.

When the anionic surfactant(s) are in salt form, they may be chosen from alkali metal salts such as the sodium or potassium salt and preferably the sodium salt, ammonium salts, amine salts and in particular amino alcohol salts or alkaline-earth metal salts such as magnesium salts. Examples of amino alcohol salts that may in particular be mentioned include monoethanolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2-methyl-1 -propanol salts, 2- amino-2-methyl-1 ,3-propanediol salts and tris(hydroxymethyl)aminomethane salts.

Use is preferably made of alkali metal or alkaline-earth metal salts, and in particular sodium or magnesium salts.

Among the anionic surfactants mentioned, use is preferably made of (C₆-C₂4)alkyl sulfates, (C₆-C₂4)alkyl ether sulfates comprising from 2 to 50 ethylene oxide units, in particular in the form of alkali metal, ammonium, amino alcohol and alkaline-earth metal salts, or a mixture of these compounds.

In particular, it is preferred to use (Ci₂-C₂o)alkyl sulfates, (Ci₂-C₂₀)alkyl ether sulfates comprising from 2 to 20 ethylene oxide units, in particular in the form of alkali metal, ammonium, amino alcohol and alkaline-earth metal salts, or a mixture of these compounds. Better still, it is preferred to use sodium lauryl ether sulfate, in particular those containing 2.2 mol of ethylene oxide, more preferentially (Ci₂-C₂₀)alkyl sulfates such as an alkali metal lauryl sulfate such as sodium lauryl sulfate.

(b) Amphoteric surfactant(s):

The amphoteric or zwitterionic surfactant(s) of the invention are preferably non- silicone, and are in particular derivatives of optionally quaternized aliphatic secondary or tertiary amines, in which derivatives the aliphatic group is a linear or branched chain comprising from 8 to 22 carbon atoms, said amine derivatives containing at least one anionic group, for instance a carboxylate, sulfonate, sulfate, phosphate or phosphonate group. Mention may be made in particular of (C₈-C₂₀)alkyl betaines, sulfobetaines, (C₈- C₂o)alkylamido(C₃-C₈)alkyl betaines and (C₈-C₂o)alkylamido(C6-C₈)alkyl sulfobetaines.

Among the amphoteric or zwitterionic surfactants mentioned above, use is preferably made of (C₈-C₂₀)alkylbetaines such as cocoylbetaine, and (C₈- C₂₀)alkylamido(C₃-C₈)alkylbetaines such as cocamidopropylbetaine, and mixtures thereof. More preferentially, the amphoteric or zwitterionic surfactant(s) are chosen from cocamidopropylbetaine and cocoylbetaine.

(c) Cationic surfactant(s):

The cationic surfactant(s) that may be used in the composition according to the invention comprise, for example, optionally polyoxyalkylenated primary, secondary or tertiary fatty amine salts, quaternary ammonium salts, and mixtures thereof.

Among the cationic surfactants that may be present in the composition according to the invention, it is more particularly preferred to choose from cetyltrimethylammonium, behenyltrimethylammonium and dipalmitoylethylhydroxyethylmethylammonium salts, and mixtures thereof, and more particularly behenyltrimethylammonium chloride, cetyltrimethylammonium chloride and dipalmitoylethylhydroxyethylammonium methosulfate, and mixtures thereof.

(d) non-ionic surfactant(s):

Examples of non-ionic surfactants that may be used in the composition used according to the invention are described, for example, in the Handbook of Surfactants by M.R. Porter, published by Blackie & Son (Glasgow and London), 1991 , pp. 1 16-178.

Examples of non-ionic surfactants that may be mentioned include:

- oxyalkylenated (C₈-C₂4)alkylphenols;

- saturated or unsaturated, linear or branched, oxyalkylenated or glycerolated C₈-C₃o alcohols;

- saturated or unsaturated, linear or branched, oxyalkylenated C₈-C₃o amides;

- esters of saturated or unsaturated, linear or branched, C₈-C₃o acids and of polyethylene glycols;

- polyoxyethylenated esters of saturated or unsaturated, linear or branched, C₈-C₃o acids and of sorbitol;

- fatty acid esters of sucrose;

- (C₈-C₃₀)alkylpolyglycosides, (C₈-C₃₀)alkenylpolyglycosides, optionally oxyalkylenated (0 to 10 oxyalkylene units) and comprising 1 to 15 glucose units, (C₈-C₃₀)alkylglucoside esters;

- saturated or unsaturated, oxyethylenated plant oils;

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

- N-(C₈-C₃₀)alkylglucamine and N-(C₈-C₃₀)acylmethylglucamine derivatives;

- aldobionamides;

- amine oxides;

- oxyethylenated and/or oxypropylenated silicones.

The surfactants containing a number of moles of ethylene oxide and/or of propylene oxide ranging advantageously from 1 to 100, more particularly from 2 to 100, preferably from 2 to 50 and more advantageously from 2 to 30. Advantageously, the non-ionic surfactants do not comprise any oxypropylene units.

In accordance with a preferred embodiment of the invention, the non-ionic surfactants are chosen from oxyethylenated C₈-C₃₀ alcohols comprising from 1 to 100 mol and more particularly from 2 to 100 mol of ethylene oxide; polyoxyethylenated esters of saturated or unsaturated, linear or branched C₈-C₃₀ acids and of sorbitan comprising from 1 to 100 mol and better still from 2 to 100 mol of ethylene oxide.

As examples of monoglycerolated or polyglycerolated non-ionic surfactants, monoglycerolated or polyglycerolated C₈-C₄o alcohols are preferably used.

In particular, the monoglycerolated or polyglycerolated C₈-C₄o alcohols preferably correspond to formula (A8) below: R₂₉0-[CH₂-CH(CH₂OH)-0]_m-H (A8) in which formula (A8):

- R₂9 represents a linear or branched C₈-C₄o and preferably C₈-C₃o alkyl or alkenyl radical; and

- m represents a number ranging from 1 to 30 and preferably from 1 to 10.

As examples of compounds of formula (A8) that are suitable within the context of the invention, mention may be made of lauryl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcohol comprising 1 .5 mol of glycerol, oleyl alcohol comprising 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 of formula (A8) 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 alcohols may coexist in the form of a mixture.

Among the monoglycerolated or polyglycerolated alcohols, it is more particularly preferred to use the C₈/Ci₀ alcohol containing 1 mol of glycerol, the C₁₀/C₁₂ alcohol containing 1 mol of glycerol and the C₁₂ alcohol containing 1 .5 mol of glycerol.

Preferentially, the non-ionic surfactant used in the process of the invention in the composition is a monooxyalkylenated or polyoxyalkylenated, particularly monooxyethylenated or polyoxyethylenated, or monooxypropylenated or polyoxypropylenated, non-ionic surfactant, or a combination thereof, more particularly monooxyethylenated or polyoxyethylenated, monoglycerolated or polyglycerolated surfactants and alkylpolyglucosides.

Even more preferentially, the non-ionic surfactants are chosen from polyoxyethylenated sorbitan esters, polyoxyethylenated fatty alcohols and alkylpolyglucosides, and mixtures thereof.

The surfactant(s) when they are present, more particularly represent from 0.01 % and 60% by weight relative to the total weight of the composition(s) included in the packaging article, preferably between 0.5% and 30% by weight and even more preferentially between 1 % and 20% by weight of the composition(s) included in the packaging article. Cationic or amphoteric substantive polymers

According to a particular embodiment, the packaging article of the invention comprises one or more cationic or amphoteric substantive polymers. These polymers may be found in said article either with the colouring agent(s) and/or the chemical oxidizing agent(s), or separated from the other ingredients by one or more water-soluble sheets as defined previously, which define a cavity in which the substantive polymer(s) are housed. Preferably, ix) are found with the oxidation dye(s) in the packaging article. More particularly, the substantive polymers are chosen from cationic polymers.

The substantive nature (i.e. the capacity for deposition onto the hair) of the polymers is conventionally determined using the test described by Richard J. Crawford, Journal of the Society of Cosmetic Chemists, 1980, 31 - (5) - pages 273 to 278 (detection with Red 80 acid dye).

These substantive polymers are in particular described in the literature in patent application EP-A-0 557 203.

Among the substantive polymers of the dimethyldiallylammonium halide homopolymer or copolymer type that may be used according to the invention, mention may be made in particular of:

- diallyldimethylammonium chloride polymers such as Polyquaternium-6;

- the copolymers of diallyldimethylammonium chloride and of acrylic acid such as that with proportions (80/20 by weight) sold under the name Merquat 280 Dry by the company

Calgon;

- copolymers of dimethyldiallylammonium chloride and of acrylamide.

Among the substantive polymers of the methacryloyloxyethyltrimethylammonium halide polymer type that may be used according to the invention, mention may be made in particular of the products that are known in the CTFA dictionary (5th edition, 1993) as Polyquaternium 37, Polyquaternium 32 and Polyquaternium 35, which correspond respectively, as regards Polyquaternium 37, to crosslinked poly(methacryloyloxyethyltrimethylammonium chloride), in dispersion at 50% in mineral oil, and sold under the name Salcare SC95 by the company Allied Colloids; as regards Polyquaternium 32, to the crosslinked copolymer of acrylamide and methacryloyloxyethyltrimethylammonium chloride (20/80 by weight), in dispersion at 50% in mineral oil, and sold under the name Salcare SC92 by the company Allied Colloids; and as regards Polyquaternium 35, to the methosulfate of the methacryloyloxyethyltrimethylammonium/methacryloyloxyethyldimethylacetylammonium copolymer.

The substantive polymers of the quaternary polyammonium type that can be used according to the invention are as follows:

- polymers constituted of repeating units corresponding to formula (□) below: -(CH3)2N+-(CH2)3-(CH3)2N+-(CH2)6-, 2X- with X-, which may be identical or different, representing an anionic counterion as defined previously, in particular a halide such as CI-, these polymers being prepared and described in French patent 2 270 846; preference is given to the polymers with repeating units of formula (□) of which the molecular weight, determined by gel permeation chromatography, is between 9500 and 9900; - polymers constituted of repeating units corresponding to formula (β) below:

-(CH3)2N⁺-(CH2)3-(CH3)2N⁺-(CH₂)3- 2X^" with X^" as defined for (a), these polymers being prepared and described in French patent 2 270 846; preference is given to the polymers with repeating units of formula (β) of which the molecular weight, determined by gel permeation chromatography, is about 1200;

polymers constituted of repeating units corresponding to formula (γ) below: -(CH₃)₂N⁺-(CH₂)_p-N(H)-C(0)-G-N(H)-(CH₂)_p-(CH₃)₂N⁺-(CH₂)₂-0-(CH₂)₂-, 2X^" in which p denotes an integer ranging from 1 to 6 approximately, G may represent a bond or a group -(CH₂)_r-C(0)- in which r denotes an integer equal to 4 or 7, these polymers being prepared and described in patents US 4 157 388, 4 390 689, 4 702 906 and 4 719 282; preference is given to the polymers with repeating units of formula (γ) of which the molecular weight is less than 100 000 and preferably less than or equal to 50 000.

Additional compounds

The packaging article of the invention may also comprise other additives conventionally used in cosmetics.

The packaging article may thus comprise fillers such as clays other than the fibrous clays; binders such as vinylpyrrolidone; lubricants such as polyol stearates or alkali metal or alkaline-earth metal stearates; hydrophilic or hydrophobic silicas; pigments; matt-effect agents or opacifiers such as titanium oxides; antioxidants such as erythorbic acid; reducing agents such as sodium metabisulfite; penetrants or sequestrants such as ethylenediaminetetraacetic acid or salts thereof; moisture absorbers such as amorphous silicas, certain polyacrylates that are crosslinked or modified with hydrophobic groups, for instance the products Luquasorb 1010 from BASF, Polytrap 6603 Adsorber from Amcol; buffers; dispersants; film-forming agents; preservatives; vitamins; fragrances; ceramides; conditioning agents other than the substantive polymers and the cationic surfactants mentioned above.

The composition ii) according to the invention may also comprise clays which are not in fibrous form, for instance smectites, illites, kaolinites, glauconites, chlorites and/or vermiculites, and mixtures thereof.

Preferably, the anhydrous composition ii) comprises one or more additional compound(s) chosen from:

starches and/or starches modified by at least one or more of the following reactions: pregelatinization, oxidation, crosslinking, esterification, etherification, amidation, heat treatments, preferably pregelatinized hydroxypropyl corn distarch phosphate;

celluloses and/or a cellulose derivative, preferably microcrystalline cellulose; mixtures thereof.

The composition in accordance with the invention may also comprise agents for controlling the release of oxygen, such as magnesium carbonate or magnesium oxide.

The additives and the oxygen-release control agents as defined previously may be present in an amount, for each of them, of between 0.01 % and 40% by weight and preferably between 0.1 % and 30% by weight relative to the total weight of the composition. Dyeing and/or bleaching process

Another subject of the invention is a process for dyeing and/or bleaching keratin fibres, in particular human keratin fibres such as the hair, comprising the following steps: i) mixing the packaging article as defined previously with a composition that is capable of dissolving the envelope of the packaging article, ii) applying the resulting composition to the keratin fibres, iii) leaving the composition to stand on the fibres, iv) rinsing said fibres, v) optionally shampooing the fibres, rinsing them and drying them.

It is clearly understood that, depending on the nature of the envelopes, the composition capable of dissolving the envelope will be water or an aqueous composition when the envelope predominantly or solely contains a hydrophilic envelope, and the composition capable of dissolving the envelope will be an anhydrous organic composition or an aqueous composition comprising at least one liquid fatty substance or at least one organic solvent other than liquid fatty substances such as lower monoalcohols, for example ethanol, or such as polyols, for example propylene glycol or glycerol, when the article predominantly or solely contains lipophilic sheets and envelope.

Thus, the aqueous composition may simply be water. The aqueous composition may optionally comprise at least one polar solvent. Among the polar solvents that may be used in this composition, mention may be made of organic compounds that are liquid at ambient temperature (25°C) and at least partially water-miscible.

Examples that may be mentioned more particularly include alkanols such as ethyl alcohol, isopropyl alcohol, aromatic alcohols such as benzyl alcohol and phenylethyl alcohol, or polyols or polyol ethers, for instance ethylene glycol monomethyl, monoethyl or monobutyl ether, propylene glycol or ethers thereof, for instance propylene glycol monomethyl ether, butylene glycol, dipropylene glycol, and also diethylene glycol alkyl ethers, for instance diethylene glycol monoethyl ether or monobutyl ether.

More particularly, if one or more solvents are present, their respective content in the aqueous composition ranges from 0.5% to 20% and preferably from 2% to 10% by weight relative to the weight of said aqueous composition.

According to one advantageous variant, the packaging article comprises at least one chemical oxidizing agent as defined previously. The dyeing process as defined previously then uses in the first step an aqueous composition which optionally comprises at least one basifying agent as defined previously or optionally at least one ingredient chosen from direct dyes, in particular cationic direct dyes, preferentially those bearing a charge which are cationic, intracyclic, styryl, azo and hydrazono dyes, particularly azo and hydrazono dyes; ammonium salts, preferably chosen from ammonium halides such as ammonium chloride, ammonium sulfate, ammonium phosphate and ammonium nitrate; organic fatty substances, preferably chosen from mineral oils, in particular liquid petroleum jelly; thickening polymers; surfactants, preferably non-ionic or anionic surfactants, chosen in particular from (Ci₂- C₂o)alkyl sulfates and (Ci₂-C₂o)alkyl ether sulfates comprising from 2 to 20 ethylene oxide units, in particular in the form of alkali metal salts, ammonium salts, amino alcohol salts and alkaline-earth metal salts, or a mixture of these compounds; preferably (Ci₂-C₂₀)alkyl sulfates such as an alkali metal lauryl sulfate such as sodium lauryl sulfate; and cationic or amphoteric substantive polymers as defined previously.

These optional additives may be present in the packaging article.

Preferentially, the dyeing and/or bleaching process as defined previously is such that the dilution ratio of one or more packaging articles as defined previously/the composition capable of dissolving the article(s), expressed on a weight basis, is inclusively between 10/90 and 90/10 and preferably between 10/90 and 50/50. Preferentially, this ratio is 20/80.

When the composition capable of dissolving the article is an aqueous hydrogen peroxide solution, it preferably has a pH of less than 7. The acidic pH ensures the stability of the hydrogen peroxide in the composition. It may be obtained using acidifying agents, for instance hydrochloric acid, acetic acid, etidronic acid, phosphoric acid, lactic acid or boric acid, and it may be conventionally adjusted by adding either basifying agents, for instance aqueous ammonia, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, 1 ,3-diaminopropane, an alkali metal or ammonium (bi)carbonate, an organic carbonate such as guanidine carbonate, or an alkali metal hydroxide, all these compounds, needless to say, possibly being taken alone or as a mixture.

The pH of the resulting mixture is usually inclusively between 7 and 12. Preferably, the pH of said mixture is usually inclusively between 7.5 and 1 1.

Once the mixing has been performed to obtain the ready-to-use composition, this composition is applied to the wet or dry human keratin fibres.

The leave-on time is generally of the order of between 1 minute and 1 hour and preferably from 10 to 30 minutes. The working temperature of the process is conventionally between ambient temperature (between 15 and 25°C) and 80°C and preferably between ambient temperature and 60°C.

At the end of the treatment, the human keratin fibres are optionally rinsed with water, washed with shampoo, rinsed again with water, and then dried or left to dry.

The examples that follow illustrate the invention without, however, limiting its scope.

EXAMPLES

The following compositions were prepared. The values are expressed as grams of active material for a composition total of 100 grams.

When there is an envelope i) according to the invention, the compound of the envelope appears on the last line of the ingredients of the composition.

Example 1 : Composition A (dyeing composition )

In particular, the following dye compositions comprising at least one oxidation dye were prepared.

N,N-BIS(2-HYDROXYETHYL)- p-PHENYLENEDIAMINE 0.12

SULFATE

RESORCINOL 0.85

m-AMINOPHENOL 0.24 18.2

TOLUENE-2,5-DIAMINE

36.4 SULFATE

GLYCOL DISTEARATE 2

LIQUID PETROLEUM JELLY 4

CETEARYL ALCOHOL 1 1.5

OLEA EUROPAEA (OLIVE)

0.2

FRUIT OIL

FRAGRANCE 0.95

HEXADIMETHRINE

4

CHLORIDE

POLYQUATERNIUM-6 3.7

CARBOMER 0.4

WATER q.s. 100

PROPYLENE GLYCOL 10

LAURIC ACID 3

LAURETH-12 7

DECETH-3 10

SODIUM LAURYL SULFATE 6.1

Oleth-30 4

ASCORBIC ACID 0.25

Total 100.00 100.00

Nonwoven of polyvinyl alcohol (PVA)

fibres with a mean diameter of about

9 10 microns (VILMED M601/023 sold

by FREUNDENBERG)

Composition B (compositions with oxidizing agent)

In particular, the following oxidizing compositions comprising at least one oxidizing agent were prepared. Composition B1 Composition B2

(Oxidizing (oxidizing composition in powder

Composition B (oxidizing agent) the form of composition in conventional 20 an envelope i)) vol cream) (according to the (reference) invention)

PENTASODIUM PENTETATE 0.15

HYDROGEN PEROXIDE 12

SODIUM PERCARBONATE 36

SODIUM STAN NATE 0.04

PHOSPHORIC ACID qs pH 2.2

TETRASODIUM

0.02

PYROPHOSPHATE

SEPIOLITE 18

MICROCRYSTALLINE

45

CELLULOSE

WATER qs 100

GLYCEROL 0.5

TRIDECETH-2 CARBOXAMIDE

0.85

MEA

CETEARYL ALCOHOL (and)

2.85

CETEARETH-25

Total 100.00 100.00

Nonwoven of polyvinyl alcohol (PVA)

fibres with a mean diameter of about 10

1 microns (VILMED M601/023 sold by

FREUNDENBERG)

Composition C

The following compositions (composition ii) comprising a fibrous clay, a colouring agent and an oxidizing agent in powder form) were prepared.

Composition

C1 according

Composition (shade 3 + powdered

to the

oxidizing agent)

invention

included inside an

envelope i)

SORBITOL 1 1

AMMONIUM SULFATE 3.7

SODIUM CARBONATE PEROXIDE 42.1

SEPIOLITE 18.3

m-AMINOPHENOL 2.2

TOLUENE-2,5-DIAMINE SULFATE 4.4

MICROCRYSTALLINE

16.5

CELLULOSE

SODIUM LAURYL SULFATE 0.7

Total 100.00

Nonwoven of polyvinyl alcohol (PVA)

fibres with a mean diameter of about 10

1 .1

microns (VILMED M601/023 sold by

FREUNDENBERG)

Composition D (water)

The water used is, for example, tap water.

//) Protocol for preparing the compositions and the packaging article

The comparative aqueous compositions outside the invention are prepared conventionally.

The packaging article is prepared in two stages: in a first stage, the powdered ingredients are selected, including the oxidation dyes. The mixture of the powdered ingredients is then homogenized. In a second stage, the envelope is prepared from PVA which is in the form of two nonwoven sheets joined together at the periphery, but leaving a part gaping allowing the introduction of ingredients. This double sheet is in the form of a disc (5 cm in diameter and 3 mm thick).

The mixture of said powdered ingredients is then introduced between the two PVA sheets of the disc, and the gaping part is then closed.

///) Protocol for evaluating the technical effect of said compositions The packaging article of the invention weighing 3.3 g is mixed according to the indications in the table below, in a 1 :9 (weight/weight) ratio in a bowl or a heating bowl.

The mixture is applied to the hair, with a leave-on time of 30 minutes.

The hair is rinsed and is then optionally shampooed, shampooing preferably being performed, and the hair is then dried.

a. Results of the evaluation

Examples of mixtures

The values are expressed in gram(s) for a total mixture of 100 g or according to the procedure above. The article of the invention is, for example, mixed (M2) with an aqueous composition (preferentially tap water) in a ratio of 27.80 g of powdered oxidizing agent (weight of the envelope + oxidizing composition) + 3.30 g (weight of the envelope + dye composition) + 68.90 g of water in a bowl or a heating bowl.

The mixture obtained is uniform, easy to work and luscious, with no tacky appearance and in particular with easy rinsing which is much better than the existing products (conventional oxidation dye).

The mixture is applied to hair with a leave-on time of between 5 minutes and 1 hour and preferably between 10 minutes and 40 minutes.

Compositio

Compositi Compsoiti

Composi Composi n B1

on B2 on C1

tion A1 tion A2 20 vol

oxidizing (dye Compositi dye dye oxidizing

Mixtures powder + oxidizing on D1

outside according cream

according agent in (water) the to the outside the

to the powder

invention invention invention

invention form)

Mixture

M1

40 60

outside

the invention

Mixture

M2

according 3.30 27.80 68.90 to the

invention

Mixture

M3

according 27.30 72.70 to the

invention

The mixture M2 results in dyeing properties comparable to conventional dyeing, in particular in terms of intensity and chromaticity; the dyeing result is very satisfactory. Furthermore, the ready-to-use mixture is easy and very pleasant to apply, and easy to localize. It should be noted that the process is very easy to perform since it is a matter of dissolving the packaging article. It was also observed that the colour obtained is very uniform from the root to the end of the hairs. Easy rinsing, much better than with the conventional oxidation dyes, is also observed. Example 2 : Compositions E (bleaching compositions)

In particular, the following bleaching compositions were prepared:

Composition E1 according to the invention comprising fibrous clay, in an envelope comprising PVA fibres;

- Comparative Composition E2 out of the invention comprising fibrous clay, in an envelope comprising PVA Film;

Comparative Composition E3 out of the invention comprising non fibrous clay, in an envelope comprising PVA fibres.

Composition E1 Composition E2 Composition E3

(Bleaching (Bleaching (Bleaching composition in composition in composition in

Compositions E

an envelope i) an envelope i) an envelope i) according to the out of the out of the

invention) invention) invention)

Potassium persulfate 54 54 54

Sodium persulfate 8 8 8

Sodium silicate 20 20 20

The packaging article is prepared in two stages, in a first stage, the powdered ingredients are selected, including the persulfate. The mixture of the powdered ingredients is then homogenized. In a second stage, the envelope is prepared from PVA which are in the form of two nonwoven laps (for compositions E1 and E3) or film laps (for composition E2) joined together at the periphery, but leaving a part gaping allowing the introduction of ingredients. This double lap is in the form of a disc (5 cm in diameter and 3 mm thick).

The mixture of the said powdered ingredients is then introduced between the two PVA laps of the disc, and the gaping part is then closed.

At the time of treatment each of composition E1 , E2 and E3 is mixed an oxidizing composition (aqueous oxydant 40 volume (12% H202)) with the weight ratio of 1 parts of composition E1 , E2 and E3, for 1 ,5 part of the oxidizing composition in a bowl until total solubilization of the ingredients and homogeneity of the mixture. Each mixture E1 + Oxydant 40 vol, Mixture E2 + Oxydant 40 vol and Mixture E3 + oxydant 40 vol is then applied on HT2 natural dark brown hair with a bath ratio of 10 g of mixture for 1 g of lock, with a leave-on time of 50 minutes at 33 °C. The hair is rinsed and is then shampooed, and the hair is then dried.

Results

With composition E1 according to the invention, the mixture with the oxydant 40 volume is easy to realize, and homogeneous. The mixture obtained is easy to work and easy to apply on the lock of hair.

With comparative composition E2 out of the invention, the mixture with the oxydant

40 volume is not homogeneous and comprises lumps. Because of the presence of the lumps, the mixture is less easy to apply on the hair, than composition E1.

With comparative composition E3 out of the invention, the mixture with the oxydant 40 volume is easy to realize and homogeneous. The mixture obtained is not thick enough and less easy to apply and to localize on the lock of hair than composition E1 .

The bleaching results of these three mixtures are very satisfactory.

Claims

1 . Cosmetic packaging article comprising:

i) an envelope defining at least one cavity, the envelope comprising water-soluble and/or liposoluble fibres;

ii) at least one anhydrous composition containing at least one fibrous clay and at least one compound chosen from: colouring agents and/or chemical oxidizing agents;

it being understood that the composition ii) is in one of the cavities of the envelope i).

2. Article according to the preceding claim, in which the anhydrous composition ii) is in paste or powder form.

3. Article according to Claim 1 or 2, in which the envelope i) predominantly comprises water-soluble polymer fibres.

4. Article according to Claim 1 or 2, in which the envelope i) comprises natural, artificial or synthetic water-soluble polymer fibres, preferably chosen from polyvinyl alcohol (PVA) fibres, polysaccharide fibres, polylactic acid fibres and polyalkylene oxide fibres, and mixtures thereof.

5. Article according to any one of the preceding claims, in which the envelope i) comprises water-soluble polymer fibres chosen from polysaccharides, particularly chosen from glucomannans, starches, alginates and celluloses, and preferably carboxymethyl starch.

6. Article according to any one of the preceding claims, in which the envelope i) comprises synthetic water-soluble polymer fibres, preferably chosen from PVA fibres.

7. Article according to any one of the preceding claims, in which the envelope i) is a nonwoven.

8. Article according to one of Claims 1 to 7, in which the envelope i) comprises liposoluble polymer fibres.

9. Article according to any one of the preceding claims, in which the envelope i) comprises spun, carded or twisted fibres, with a diameter, which may be identical or different, of less than 500 μηι, advantageously less than 200 μηι, preferably less than 100 μηι, or even less than 50 μηι and/or for which the tensile strength of said fibres is at least 2.7 g/dtex (3 g/d).

10. Article according to any one of the preceding claims, in which the envelope i) represents an amount inclusively between 0.5% and 20.0% by weight relative to the total weight of said article, advantageously between 1 .0% and 10.0%, particularly between 2.0% and 5.0% and more particularly 3% by weight relative to the total weight of the packaging article.

1 1 . Article according to any one of the preceding claims, in which the anhydrous composition ii) comprises at least one colouring agent chosen from oxidation dyes, preferably chosen from one or more oxidation bases chosen from para- phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho- aminophenols and heterocyclic bases, and the addition salts thereof, optionally combined with one or more couplers chosen from meta-phenylenediamines, meta- aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and also the addition salts thereof.

12. Article according to any one of Claims 1 to 10, in which the anhydrous composition ii) comprises at least one colouring agent chosen from direct dyes, preferably chosen from azo direct dyes; (poly)methine dyes such as cyanins, hemicyanins and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes, and natural direct dyes, alone or as mixtures; lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechualdehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orceins.

13. Article according to any one of the preceding claims, in which the anhydrous composition ii) comprises at least one anhydrous oxidizing agent, chosen in particular from a) urea peroxide, b) polymer complexes that can release hydrogen peroxide, chosen from polyvinylpyrrolidone/H₂0₂ complexes; c) oxidases, e) perborates and f) percarbonates; the packaging article preferably contains one or more percarbonates.

14. Article according to the preceding claim, in which the anhydrous composition ii) comprises from 1 % to 80% by weight of chemical oxidizing agent, preferably from 5% to 70% by weight and preferably from 10% to 60% by weight, relative to the total weight of the composition ii).

15. Article according to any one of the preceding claims, in which the fibrous clay is chosen from sepiolite, palygorskite, attapulgite and mixtures thereof, preferably sepiolite.

16. Article according to any one of the preceding claims, in which the anhydrous composition ii) comprises a total content of fibrous clay ranging from 1 % to 80% by weight, in particular from 2% to 80% by weight, preferably from 5% to 60%, and better still from 5% to 40% by weight, relative to the total weight of the anhydrous composition ii).

17. Article according to any one of the preceding claims, in which the anhydrous composition ii) comprises one or more additional compound(s) chosen from:

mixtures thereof.

18. Article according to any one of the preceding claims, which comprises at least one alkaline agent, in particular chosen from silicates and metasilicates such as alkali metal metasilicates, carbonates or hydrogen carbonates of alkali metals or alkaline-earth metals, such as lithium, sodium, potassium or magnesium, and mixtures thereof.

19. Article according to any one of the preceding claims, which comprises at least one additional ingredient chosen from liquid fatty substances, preferably chosen from mineral oils, in particular liquid petroleum jelly; thickening polymers; surfactants, preferably non-ionic or anionic surfactants, chosen in particular from (Ci₂-C₂o)alkyl sulfates and (Ci₂-C₂o)alkyl ether sulfates comprising from 2 to 20 ethylene oxide units, in particular in the form of alkali metal salts, ammonium salts, amino alcohol salts and alkaline-earth metal salts, or a mixture of these compounds; preferably (Ci₂-C₂₀)alkyl sulfates such as an alkali metal lauryl sulfate such as sodium lauryl sulfate; and cationic or amphoteric substantive polymers.

20. Packaging article according to any one of the preceding claims, in which the envelope i) is constituted of two water-soluble or liposoluble sheets (1 1 , 12), which are preferably water-soluble, joined together at a peripheral region (14), the two sheets preferably being joined by any suitable fixing means such as gluing, welding, in particular heat-welding, in particular by entanglement; the first sheet (1 1 ) also has a free central region (D) arranged facing a free central region (D) of the second sheet (12); these two central regions defining a central cavity, said central cavity containing an anhydrous composition ii) (13) comprising at least one fibrous clay and at least one compound chosen from colouring agents and/or the chemical oxidizing agents as defined in any one of the preceding claims, optionally mixed with other ingredients as defined according to any one of Claims 17 to19; the sheets (1 1 , 12) have a closed outer periphery (15) of which the shape is, for example, rounded, such as circular or elliptical or polygonal, such as square, rectangular or triangular, preferably circular.

21 . Packaging article according to the preceding claim, which also comprises a sheet (16), which is preferably water-soluble, and optionally other additional water- soluble or liposoluble sheet(s) (17), which are preferably water-soluble, which define one or more cavities, separating the anhydrous composition ii) (18) as defined in Claims 1 to 20 from the other ingredients (19) or (20) as defined in any one of Claims 18 to 20.

22. Packaging article according to Claim 20 or 21 , in which the first sheet (1 1 ), which is preferably water-soluble, the second sheet (12), which is preferably water- soluble, and optionally the additional sheets (16) and (17), which are preferably water- soluble, have a thickness smaller than their other dimensions, in particular less than 10% of their maximum transverse dimensions D+2d; preferentially, the thickness of the first sheet (1 1 ), which is preferably water-soluble, and of the second sheet, which is preferably water-soluble, is in particular less than 10 mm and in particular between 0.1 mm and 3 mm, and their maximum transverse dimensions D+2d being less than 100 mm, and in particular being inclusively between 10 mm and 60 mm.

23. Packaging article according to any one of Claims 20 to 22, in which the first sheet (1 1 ), which is preferably water-soluble, is a nonwoven and in which the second sheet (12), which is preferably water-soluble, is a nonwoven and also has a closed outer periphery (15); the outer periphery (15) of the first layer (1 1 ) is substantially identical in shape to the outer periphery (15) of the second layer (12).

24. Use of the packaging article according to any one of the preceding claims, for dyeing and/or bleaching keratin fibres, in particular human keratin fibres such as the hair.

25. Process for dyeing and/or bleaching keratin fibres, in particular human keratin fibres such as the hair, comprising at least one step of using at least one packaging article as defined in any one of Claims 1 to 23.

26. Process for dyeing and/or bleaching keratin fibres, in particular human keratin fibres such as the hair, comprising the following steps: i) mixing the packaging article as defined in any one of Claims 1 to 23 with a composition that is capable of dissolving the packaging article, ii) applying the resulting composition to the keratin fibres, iii) leaving the composition to stand on the fibres, iv) rinsing said fibres, v) optionally shampooing the fibres, rinsing them and drying them.

27. Process according to Claim 26, in which the composition that is capable of dissolving the article is an aqueous composition or an organic composition comprising at least one liquid fatty substance.

28. Process according to either of Claims 26 or 27, in which the composition that is capable of dissolving the packaging article is aqueous.

29. Process according to any one of Claims 26 to 28, in which the anhydrous composition ii) comprises at least one colouring agent, preferably an oxidation dye, and the composition that is capable of dissolving the envelope of the packaging article contains an oxidizing agent, preferably hydrogen peroxide.

30. Process according to Claim 26, in which the anhydrous oxidizing agent in paste or powder form is contained in a second packaging article as defined in any one of Claims 21 to 23.

31 . Process according to any one of Claims 26 to 30, in which the dilution ratio of the packaging article(s)/the composition that is capable of dissolving the packaging article(s), this ratio being expressed on a weight basis, is inclusively between 10/90 and 50/50, and is preferentially 20/80.