FR3117023A1 - Anhydrous solid composition comprising the particular combination of a sulphated surfactant and an amphoteric surfactant - Google Patents

Abstract

Title: Anhydrous solid composition comprising the particular combination of a sulfated surfactant and an amphoteric surfactant The present invention relates to an anhydrous solid composition intended in particular for washing and/or conditioning keratin fibers, in particular human keratin fibers such as hair, and which comprises a particular combination of at least one anionic surfactant of sulfate type and at least one amphoteric surfactant, in a particular weight ratio. The invention also relates to a packaging article containing said anhydrous solid composition, as well as methods of cosmetic treatment of keratin fibers, in particular human keratin fibers such as hair using said anhydrous solid composition or said conditioning article. The invention further relates to the use of said anhydrous solid composition or said conditioning article for washing and/or conditioning keratin fibers, in particular human keratin fibers such as hair.

Description

Anhydrous solid composition comprising the particular combination of a sulphated surfactant and an amphoteric surfactant

The present invention relates to an anhydrous solid composition intended in particular for washing and/or conditioning keratin fibres, in particular human keratin fibers such as the hair, and which comprises a particular combination of at least one anionic surfactant of the sulphate type and of at least one amphoteric surfactant, according to a particular weight ratio.

The invention also relates to a conditioning article containing said anhydrous solid composition, as well as methods for the cosmetic treatment of keratin fibres, in particular human keratin fibers such as the hair, using said anhydrous solid composition or said conditioning article.

The invention further relates to the use of said anhydrous solid composition or of said conditioning article for washing and/or conditioning keratin fibres, in particular human keratin fibers such as the hair.

In the field of hair hygiene, products for washing keratin fibers are generally intended to clean said fibers while providing them with good cosmetic properties. Conventional products, such as shampoos, most often come in a more or less thickened liquid form. Due to their liquid texture, these products can however have various disadvantages, and in particular prove to be difficult to dose.

Indeed, the more liquid they are, the more they tend to escape between the fingers, making their dosage difficult and resulting in waste. These products can also leak out of their packaging, which can cause inconvenience to the consumer when these products come into contact with clothing or objects, for example when moving.

In order to modify the texture of these products, and in particular to make it more compact, thickeners are generally used. The addition of these compounds is however often done to the detriment of the cosmetic effects of the compositions. The use of these thicker compositions also require a lot of rinsing water in order to eliminate the excess product on the fibres. However, in many countries where access to water is restricted, the rinsing time and consequently the quantity of water necessary to properly rinse the product are key indicators of the qualities of use of a composition.

In order to overcome some of these problems, new solid cosmetic formulations, in particular shampoos in the form of solid granules or powder, have been developed. However, these new formulations do not always bring complete satisfaction. Those in the form of loose powder can indeed pose problems of volatility, grip and/or dosage, while those in the form of agglomerates, such as granules for example, can tend to disintegrate or disintegrate with difficulty in the presence of water. Thus, the latter do not always make it possible to obtain a rapid onset of foam and/or a satisfactory abundance of foam, adversely impacting their use and their spreading on the keratin fibres. They can also be difficult to remove by rinsing and sometimes even leave unpleasant residues on the fibers for the consumer. These formulations may also not give complete satisfaction in terms of cosmetic performance, in particular in terms of suppleness, feel, softness, shine and detangling.

Thus, there is a real need to provide a composition in solid form having an improved environmental profile, that is to say requiring little water throughout its use. The composition must not only be easy to grip, disintegrate easily and have good foaming properties, in particular as regards start-up, abundance and density, but it must also be quick to rinse out without leaving residues on the keratin fibres.

The composition must also have good detergent power while conferring satisfactory cosmetic properties, in particular in terms of suppleness, feel, softness, shine and disentangling.

It has now been discovered that an anhydrous solid composition comprising a particular combination of at least one anionic surfactant of sulfate type and at least one amphoteric surfactant, according to a particular weight ratio, made it possible to achieve the objectives set out above. , and in particular to propose a composition in solid form combining good qualities of use, good detergent power with improved foam properties, without however requiring large amounts of water.

The subject of the present invention is therefore an anhydrous solid composition comprising:
(i) one or more sulfate-type anionic surfactants, and
(ii) one or more amphoteric or zwitterionic surfactants;
the weight ratio between the total content of anionic surfactant(s) of sulfate type (i) and the total content of amphoteric or zwitterionic surfactant(s) (ii) being greater than or equal to 3.

The particular combination of the compounds of the invention makes it possible to obtain a solid composition that is easy to sample, handle and dose. Indeed, the composition thus obtained has a cohesion or granulation such that the gripping and metering properties are improved. The composition can then be packaged in the form of a single dose, a particularly interesting form, for example when traveling or practicing a sport (lighter bags, limitation of the risks of leakage, reduction of waste).

This composition also breaks down quickly on contact with water and makes it possible to easily and quickly obtain a firm, creamy and abundant foam, of a quality comparable to the foam obtained with a conventional liquid shampoo composition. This foam can then be distributed easily and evenly over the keratin fibers.

Furthermore, the composition of the invention rinses off quickly without leaving any unpleasant residues on the fibers and gives them, after rinsing, a natural and clean feel. The fibers treated with the composition of the invention also have good cosmetic properties, in particular in terms of softness, suppleness and touch. They are also well individualized and thus easier to disentangle.

A subject of the present invention is also a method for the cosmetic treatment, in particular of washing and/or conditioning, of keratin fibres, in particular human keratin fibers such as the hair, comprising the application to said keratin fibers of a solid composition anhydrous as defined above; the anhydrous solid composition being applied directly to said keratinous fibers or after having been previously moistened with water.

The present invention also relates to the use of an anhydrous solid composition as defined above for washing and/or conditioning keratin fibres, in particular human keratin fibers such as the hair.

The present invention also relates to a packaging article comprising:
- an envelope defining at least one cavity, the envelope comprising one or more water-soluble and/or fat-soluble compounds;
- an anhydrous solid composition as defined above;
it being understood that the anhydrous solid composition is in one of the cavities defined by the envelope.

This packaging article makes it possible in particular to solve the problems of dosing the anhydrous solid composition. It also makes it easy to store and transport. In particular, the packaging article of the invention offers better protection of the composition against humidity.

The conditioning article can also make it possible to obtain a final composition for washing and/or conditioning keratin fibers that is thicker in the hand, which can be in the form of a cream. It can also act as a foam booster. Indeed, the volume of foam obtained after dilution of the packaging article can be greater than the volume of foam obtained after dissolution of the anhydrous solid composition alone.

The present invention further relates to the use of a conditioning article as defined above for washing and/or conditioning keratin fibers, in particular human keratin fibers such as the hair.

The present invention also relates to a method for the cosmetic treatment, in particular of washing and/or conditioning, of keratin fibres, in particular human keratin fibers such as the hair, comprising a step of implementing a conditioning article as defined above.

Preferably, said cosmetic treatment process comprises the following steps:
i) mixing the packaging article in a composition capable of dissolving, in whole or in part, the envelope of the said packaging article,
ii) applying the composition obtained in step i) to the keratin fibres,
iii) possibly allow a pause,
iv) rinsing said keratinous fibres,
v) optionally drying said keratinous fibres.

Other objects, characteristics, aspects and advantages of the invention will appear even more clearly on reading the description and the example which follow.

In what follows, and unless otherwise indicated, the limits of a domain of values are included in this domain, in particular in the expressions “included between” and “ranging from … to …”.

Furthermore, the expression “at least one” used in the present description is equivalent to the expression “one or more”.

By “anhydrous composition”, is meant a composition comprising a water content of less than 5% by weight, preferably less than 4% by weight, relative to the weight of the composition. Preferably, this water content is less than 3% by weight, relative to the weight of the composition.

In particular, the composition does not include any water added during its preparation, any residual water present possibly coming from the raw materials used during the preparation.

The anhydrous solid composition according to the invention can be in the form of powder, paste, particles (for example spherical particles such as small beads or granules), compressed tablet, stick or loaf. Preferably, the composition according to the invention is in the form of a powder or of particles.

By "powder" is meant a composition in powder form, preferably essentially free of dust (or fine particles). In other words, the particle size distribution of the particles is such that the weight rate of the particles which have a size less than or equal to 50 micrometers (fines rate), preferably less than or equal to 45 micrometers (fines rate), is advantageously less than or equal to equal to 5% by weight, preferably less than 3% by weight and more particularly less than 1% by weight, relative to the total weight of the particles (size of the particles evaluated by means of a RETSCH AS 200 DIGIT particle sizer; Height of oscillation: 1.25 mm / sieving time: 5 minutes).

By "paste" is meant a composition having a viscosity greater than 5 poise (0.5Pa.s), and preferably greater than 10 poise (1Pa.s), measured at 25° C. and at a shear rate of 1 s ^-1 ; this viscosity being able to be determined by means of a Coneplan rheometer.

By “particles”, we mean small split objects formed of solid particles aggregated together, of variable shapes and sizes. They can be regular or irregular in shape. They can in particular be of spherical shape (such as granules, granules, balls), square, rectangular, or elongated such as rods. Most preferred are spherical particles.

Advantageously, the size of the powders or particles is comprised, in its largest dimension, between 45 μm and 5 mm, preferably between 50 μm and 2 mm, more preferentially between 50 μm and 1 mm, and better still between 60 μm and 600 μm.

When the anhydrous solid composition according to the invention is not in the form of powder or particles, it preferably has a penetration force at 25° C. and 1 atm, greater than or equal to 200 g, preferably greater than or equal to 300g, more preferably greater than or equal to 400g, and better still greater than or equal to 500g. The penetration force is determined by penetrometry. The texture analysis measurements are carried out at 25° C. using a Stable Micro Systems TA.XT Plus texturometer. The penetrometry experiments are carried out with a metal rod provided with a screwed tip, said tip being a 2mm P/2N needle for the upper part, connected to the measuring head. The piston sinks into the sample at a constant speed of 1 mm/s, over a height of 5 mm. The force exerted on the piston is recorded and the average value of the force is calculated.

The anhydrous solid composition according to the invention may be in the form of a compressed anhydrous solid composition, in particular using a manual or mechanical press. Preferably, the hardness of the compressed anhydrous solid composition is between 10 and 300 N, more preferably between 15 and 200 N, and better still between 15 and 100 N.

The density of the anhydrous solid composition according to the present invention is preferably between 0.1 and 1, more preferably between 0.2 and 0.8, and better still between 0.3 and 0.6.

A determined quantity (mass, m) of powder is placed in a graduated cylinder. The test piece is then tapped 2500 times automatically. The volume (v) thus obtained is read on the test specimen and the density (d) is then determined according to the formula d=m/v.

Sulphate-type anionic surfactants

The anhydrous solid composition according to the present invention comprises one or more anionic surfactants of sulfate type.

By "sulfate-type anionic surfactant" is meant, within the meaning of the present invention, an anionic surfactant comprising one or more sulfate functions (-OSO ₃ H or -OSO ₃ ^- ).

Such surfactants can advantageously be chosen from alkyl sulphates, alkyl ether sulphates, alkylamidosulphates, alkylamidoether sulphates, alkylaryl-polyether sulphates, monoglyceride-sulphates; as well as their salts and their mixtures; the alkyl groups of these compounds comprising in particular from 8 to 30 carbon atoms, preferably from 8 to 26, and more preferably from 10 to 22 carbon atoms; the aryl group preferably denoting a phenyl or benzyl group; these compounds possibly being polyoxyalkylenated, in particular polyoxyethylenated and then preferably comprising from 1 to 50 ethylene oxide units, and more preferably from 2 to 10 ethylene oxide units.

Preferably, the anionic surfactant(s) of sulfate type are chosen from:
- alkyl sulphates, in particular C ₈ to C ₂₆ , and preferably C ₁₀ to C ₂₂ ,
- alkyl ether sulphates, in particular C ₈ to C ₂₆ , and preferably C ₁₀ to C ₂₂ , preferably comprising from 1 to 10 ethylene oxide units;
in particular in the form of alkali or alkaline-earth metal, ammonium or aminoalcohol salts, and
their mixtures.

When the sulfate-type anionic surfactant(s) are in the form of a salt, said salt may be chosen from alkali metal salts, such as sodium or potassium salt, ammonium salts, amine salts, and in particular amino alcohols, salts of alkaline earth metals, such as the magnesium salt, and mixtures thereof.

As examples of salts of amino alcohols, mention may be made of mono-, di- and triethanolamine salts, mono-, di- or tri-isopropanolamine salts, 2-amino 2-methyl 1-propanol, 2- amino 2-methyl 1,3-propanediol and tris(hydroxymethyl)amino methane.

Salts of alkali metals or alkaline earth metals, and in particular sodium or magnesium salts, are preferably used.

Preferably, the anionic surfactant(s) of sulphate type are chosen from (C10-C22) alkyl sulphates of sodium, triethanolamine, magnesium or ammonium, alkyl (C10-C22) ether sulphates of sodium, ammonium or magnesium, oxyethylenated, for example with 1 or 2.2 moles of ethylene oxide, and mixtures thereof.

Better still, the anionic surfactant(s) of sulphate type are chosen from alkyl (C10-C22) sulphates of sodium, triethanolamine, ammonium or magnesium, such as the compound marketed under the name TEXAPON Z95P by the company BASF of INCI name sodium lauryl sulphate.

Advantageously, the anionic surfactant(s) of sulphate type are chosen from sodium lauryl sulphate, ammonium lauryl sulphate and mixtures thereof.

The total content of the anionic surfactant(s) of sulfate type, present in the anhydrous solid composition according to the invention, preferably ranges from 1 to 80% by weight, more preferably from 10 to 75% by weight, better still from 30 to 70% by weight, and better still from 35 to 70% by weight, relative to the total weight of the composition.

The anhydrous solid composition according to the invention may optionally also comprise one or more additional anionic surfactants, different from the sulphate-type anionic surfactants defined above.

The additional anionic surfactant(s) which can be used according to the present invention are preferably chosen from anionic surfactants of the sulfonate type, anionic surfactants of the carboxylic type and mixtures thereof.

By "sulfonate-type anionic surfactant" is meant, within the meaning of the present invention, an anionic surfactant comprising one or more sulphonic or sulphonate (-SO ₃ H or -SO ₃ ^- ) functions, possibly comprising one or more carboxylic or carboxylate (-COOH or -COO ^- ), and not comprising a sulphate function.

By "carboxylate-type anionic surfactant" is meant, within the meaning of the present invention, an anionic surfactant comprising one or more carboxylic or carboxylate functions (-COOH or -COO ^- ), and not comprising a sulphonic or sulphonate function (-SO ₃ H or -SO ₃ ^- ) and containing no sulphate function.

Such additional anionic surfactants can advantageously be chosen from alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, alpha-olefin-sulfonates, paraffin-sulfonates, alkylsulfosuccinates, alkylethersulfosuccinates, alkylamidesulfosuccinates, alkylsulfoacetates, sulfolaurates, N-acyltaurates , acylisethionates, acyllactates, N-acylglycinates, N-acylsarcosinates, N-acylglutamates, alkyl ether carboxylates, alkyl glucose carboxylates, alkyl glucoside tartrates, alkyl glucoside citrates, in salified forms or not, and their mixtures; the alkyl groups of these compounds comprising in particular from 8 to 30 carbon atoms, preferably from 8 to 26, and more preferably from 10 to 22 carbon atoms; the aryl group preferably denoting a phenyl or benzyl group; these compounds possibly being polyoxyalkylenated, in particular polyoxyethylenated and then preferably comprising from 1 to 50 ethylene oxide units, and more preferably from 2 to 10 ethylene oxide units.

Advantageously, the additional anionic surfactant(s) are chosen from:
- anionic surfactants of the carboxylate type, preferably from N-acyl(C ₈ -C ₃₀ )glutamates, and in particular stearoylglutamates, lauroylglutamates and cocoylglutamates, N-acyl(C ₈ -C ₃₀ )sarcosinates, and in particular palmitoylsarcosinates, stearoylsarcosinates, lauroylsarcosinates, cocoylsarcosinates; and mixtures thereof; in particular in the form of alkali or alkaline-earth metal, ammonium, amine or aminoalcohol salts;
- anionic surfactants of sulfonate type, preferably from acylisethionates, and more preferably from acyl(C ₈ -C ₃₀ )isethionate used in the form of salts, and better still in the form of alkali metal or alkaline earth metal salts, and in particular sodium or magnesium salts; And
- their mixtures.

The total content of the additional anionic surfactant(s), when they are present in the anhydrous solid composition of the invention, preferably ranges from 1 to 30% by weight, relative to the total weight of the composition.

The total content of the anionic surfactant(s), that is to say in particular the total content of sulfate-type anionic surfactants and of additional anionic surfactants, present in the anhydrous solid composition of the invention, preferably ranges from 10 to 80% by weight, more preferably from 15 to 75% by weight, and better still from 30 to 70% by weight, relative to the total weight of the composition.

Amphoteric or zwitterionic surfactants

The anhydrous solid composition according to the present invention also comprises one or more amphoteric or zwitterionic surfactants.

In particular, the amphoteric or zwitterionic, preferably non-silicone, surfactant(s) used in the anhydrous solid composition according to the present invention may in particular be derivatives of secondary or tertiary aliphatic amines, optionally quaternized, in which the aliphatic group is a linear or branched chain comprising from 8 to 22 carbon atoms, the said amine derivatives containing at least one anionic group such as, for example, a carboxylate, sulphonate, sulphate, phosphate or phosphonate group.

Mention may be made in particular of (C ₈ -C ₂₀ )alkyl betaines, (C ₈ -C ₂₀ )alkyl sulfobetaines, (C ₈ -C ₂₀ )alkylamido(C ₁ -C ₆ )alkyl betaines, (C 8 -C 6 )alkyl betaines, (C 8 -C 20 )alkyl betaines, ₈ -C ₂₀ )-amid(C ₁ -C ₆ )alkylsulfobetaines, and mixtures thereof.

Among the optionally quaternized secondary or tertiary aliphatic amine derivatives that can be used, as defined above, mention may also be made of the compounds of the following structures (I) and (II) respectively:

R _a -CONHCH ₂ CH ₂ -N ⁺ (R _b )(R _c )-CH ₂ COO ^- , M ⁺ , X ^- (I)
formula (I), in which:
- R _a represents a C ₁₀ to C ₃₀ alkyl or alkenyl group derived from an acid R _a COOH, preferably present in hydrolyzed coconut oil, preferably R _a represents a heptyl, nonyl or undecyl group;
- R _b represents a beta-hydroxyethyl group;
- R _c represents a carboxymethyl group;
- M ⁺ represents a cationic counter ion derived from an alkali metal, alkaline earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine; And
- X ^- represents an organic or inorganic anionic counter ion, such as that chosen from halides, acetates, phosphates, nitrates, alkyl (C ₁ -C ₄ )sulfates, alkyl (C ₁ -C ₄ )- or alkyl (C ₁ -C ₄ )aryl-sulphonates, in particular methyl sulphate and ethyl sulphate; or else M ⁺ and X ^- are absent;

R _a '-CONHCH ₂ CH ₂ -N(B)(B') (II)
formula (II), in which:
- B represents the -CH ₂ CH ₂ OX'group;
- B' represents the group -(CH ₂ ) _z Y', with z=1 or 2;
- X' represents the group -CH ₂ COOH, -CH ₂ -COOZ', -CH ₂ CH ₂ COOH, CH ₂ CH ₂ -COOZ', or a hydrogen atom;
- Y' represents the group –COOH, -COOZ', -CH ₂ CH(OH)SO ₃ H or the group CH ₂ CH(OH)SO ₃ -Z';
- Z′ represents a cationic counter ion derived from an alkali metal or alkaline earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;
- R _a 'represents a C ₁₀ to C ₃₀ alkyl or alkenyl group of an acid R _a '-COOH preferably present in coconut oil or in hydrolyzed linseed oil, preferably R _a ' a group alkyl, in particular C ₁₇ and its iso form, an unsaturated C ₁₇ group.

These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate, disodium capryloamphodipropionate, acid lauroamphodipropionic acid, cocoamphodipropionic acid.

By way of example, mention may be made of the cocoamphodiacetate marketed by the company RHODIA under the trade name ^MIRANOL® C2M concentrate.

It is also possible to use compounds of formula (III):
R _a ''-NHCH(Y'')-(CH ₂ ) _n CONH(CH ₂ ) _n' -N(R _d )(R _e ) (III)
formula (III), in which:
- Y'' represents the group –COOH, -COOZ'', -CH ₂ -CH(OH)SO ₃ H or the group CH ₂ CH(OH)SO ₃ -Z'';
- R _d and R _e , independently of one another, represent a C ₁ to C ₄ alkyl or hydroxyalkyl radical;
- Z'' represents a cationic counter ion derived from an alkali metal or alkaline earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;
- R _a '' represents a C ₁₀ to C ₃₀ alkyl or alkenyl group of an acid R _a ''-COOH preferably present in coconut oil or in hydrolyzed linseed oil; And
- n and n', independently of each other, denote an integer ranging from 1 to 3.

Among the compounds of formula (III), mention may be made of the compound classified in the CTFA dictionary under the name sodium diethylaminopropyl cocoaspartamide and marketed by the company CHIMEX under the name CHIMEXANE HB.

These compounds can be used alone or in mixtures.

Among the amphoteric or zwitterionic surfactants mentioned above, alkyl (C ₈ -C ₂₀ ) betaines are advantageously used, such as cocobetaine, alkyl (C ₈ -C ₂₀ ) amidoalkyl (C ₃ -C ₈ ) betaines, such as cocamidopropylbetaine, (C ₈ -C ₂₀ )alkylamphoacetates, (C ₈ -C ₂₀ )alkylamphodiacetates and mixtures thereof; and preferably (C ₈ -C ₂₀ )alkyl betaines, (C ₈ -C ₂₀ )alkylamido(C ₃ -C ₈ )alkyl betaines and mixtures thereof.

Preferably, the amphoteric or zwitterionic surfactant(s) are chosen from (C ₈ -C ₂₀ )alkyl betaines, (C ₈ -C ₂₀ )alkylamido(C ₃ -C ₈ )alkyl betaines and mixtures thereof, and better still from (C ₈ -C ₂₀ )alkylamido(C ₃ -C ₈ )alkyl betaines and mixtures thereof.

The total content of the amphoteric or zwitterionic surfactant(s), present in the anhydrous solid composition according to the invention, preferably ranges from 1 to 30% by weight, more preferably from 2 to 20% by weight, and better still from 3 to 15 % by weight, relative to the total weight of the composition.

The weight ratio (R) between the total content of anionic surfactant(s) of sulfate type (i) and the total content of amphoteric or zwitterionic surfactant(s) (ii), present in the anhydrous solid composition of the invention, is greater than or equal to 3. Advantageously, this weight ratio (R) is greater than or equal to 4, preferably greater than or equal to 5, and more preferably greater than or equal to 6.

The total content of anionic surfactants of sulfate type (i) and of amphoteric or zwitterionic surfactants (ii), present in the anhydrous solid composition of the invention, is preferably less than or equal to 90% by weight, and more preferably less than or equal to 75% by weight, relative to the total weight of the composition.

Cationic polymers

The anhydrous solid composition according to the present invention may optionally also comprise one or more cationic polymers.

By “cationic polymer”, is meant within the meaning of the present invention, any polymer comprising cationic groups and/or groups which can be ionized into cationic groups. Preferably, the cationic polymer(s) are hydrophilic or amphiphilic.

The cationic polymers are preferably not siliconized (do not include an Si—O unit).

The preferred cationic polymers are chosen from those which contain units comprising primary, secondary, tertiary and/or quaternary amine groups which can either form part of the main polymer chain, or be carried by a side substituent directly linked to it.

Preferably, the cationic polymers according to the invention do not comprise any anionic group or any group which can be ionized into anionic groups.

The cationic polymers which can be used preferably have a weight-average molar mass (Mw) of between 500 and 5×10 ⁶ approximately, preferably between 10 ³ and 3×10 ⁶ approximately.

Among the cationic polymers, mention may be made more particularly of:

(1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of the following formula:


formulas in which:
- R ₃ , identical or different, denote a hydrogen atom or a CH ₃ radical;
- A, identical or different, represent a divalent alkyl group, linear or branched, of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms or a hydroxyalkyl group of 1 to 4 carbon atoms;
- R ₄ , R ₅ and R ₆ , identical or different, represent an alkyl group having from 1 to 18 carbon atoms or a benzyl radical; preferably an alkyl group having 1 to 6 carbon atoms;
- R ₁ and R ₂ , identical or different, represent a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms, preferably methyl or ethyl; And
- X denotes an anion derived from a mineral or organic acid such as a methosulfate anion or a halide such as chloride or bromide.

The copolymers of family (1) can also contain one or more units deriving from comonomers which can be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen by lower alkyls (C ₁ -C ₄ ), acrylic or methacrylic acids or their esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters.

Among these copolymers of family (1), mention may be made of:
- copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulphate or with a dimethyl halide, such as that sold under the name HERCOFLOC by the company HERCULES,
- copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride, such as those sold under the name BINA QUAT P 100 by the company CIBA GEIGY,
- the copolymer of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate, such as that sold under the name RETEN by the company HERCULES,
- vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers, quaternized or not, such as the products sold under the name "GAFQUAT" by the company ISP, such as for example "GAFQUAT 734" or "GAFQUAT 755" or else the products called "COPOLYMER 845 , 958 and 937". These polymers are described in detail in French patents 2,077,143 and 2,393,573,
- dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers, such as the product sold under the name GAFFIX VC 713 by the company ISP,
- vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers, such as those marketed under the name STYLEZE CC 10 by ISP;
- quaternized dimethylaminopropyl methacrylamide/vinylpyrrolidone copolymers, such as the product sold under the name "GAFQUAT HS 100" by the company ISP,
- polymers, preferably crosslinked, of methacryloyloxyalkyl (C ₁ -C ₄ ) trialkyl (C ₁ -C ₄ ) ammonium salts such as the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homo- or copolymerization being followed by cross-linking with an olefinically unsaturated compound, in particular methylene bis acrylamide. It is more particularly possible to use a crosslinked acrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion comprising 50% by weight of the said copolymer in mineral oil. This dispersion is marketed under the name " ^SALCARE® SC 92" by the company CIBA. It is also possible to use a crosslinked homopolymer of methacryloyloxyethyl trimethylammonium chloride comprising approximately 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are marketed under the names " ^SALCARE® SC 95" and " ^SALCARE® SC 96" by the company CIBA.

(2) Cationic polysaccharides, in particular celluloses and gums of cationic galactomannans. Among the cationic polysaccharides, mention may more particularly be made of cellulose ether derivatives comprising quaternary ammonium groups, cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and cationic galactomannan gums.

Cellulose ether derivatives comprising quaternary ammonium groups are described in particular in FR1492597, and mention may be made of the polymers marketed under the name "UCARE POLYMER JR" (JR 400 LT, JR 125, JR 30M) or "LR" (LR 400, LR 30M) by the AMERCHOL company. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose having reacted with an epoxide substituted by a trimethylammonium group.

Cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer are described in particular in patent US4131576, and mention may be made of hydroxyalkylcelluloses, such as hydroxymethyl-, hydroxyethyl- or hydroxypropyl celluloses grafted in particular with a salt methacryloylethyl trimethylammonium, methacrylamidopropyl trimethylammonium, dimethyl-diallylammonium. The marketed products corresponding to this definition are more particularly the products sold under the name "Celquat L 200" and "Celquat H 100" by the National Starch Company.

Among the cationic cellulose derivatives, it is also possible to use cationic associative celluloses, which can be chosen from quaternized cellulose derivatives, and in particular quaternized celluloses modified by groups comprising at least one fatty chain, such as linear alkyl groups or branched, linear or branched arylalkyl, linear or branched alkylaryl, preferably linear or branched alkyl, these groups comprising at least 8 carbon atoms, in particular from 8 to 30 carbon atoms, better still from 10 to 24, or even from 10 to 14 , carbon atoms; or mixtures thereof.

Preferably, mention may be made of quaternized hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as linear or branched alkyl, linear or branched arylalkyl, linear or branched alkylaryl, preferably linear or branched alkyl, these groups comprising at less than 8 carbon atoms, in particular from 8 to 30 carbon atoms, better still from 10 to 24, or even from 10 to 14, carbon atoms; or mixtures thereof.

Preferably, mention may be made of the hydroxyethylcelluloses of formula (IV):

in which :
- R represents an ammonium group R _a R _b R _c N ⁺ –, Q ^- in which R _a , R _b , and R _c , identical or different, represent a hydrogen atom or an alkyl, linear or branched, in C ₁ to C ₃₀ , preferably an alkyl, and Q ⁻ represents an anionic counterion such as a halide such as a chloride or bromide;
- R' represents an ammonium group R' _a R' _b R' _c N ⁺ -, Q' ^- in which R' _a , R' _b , and R' _c , identical or different, represent a hydrogen atom or a alkyl, linear or branched, C ₁ to C ₃₀ , preferably an alkyl, and Q' ^- represents an anionic counterion such as a halide such as a chloride or bromide;
it being understood that at least one of the radicals R _a , R _b , R _c , R′ _a , R′ _b , R′ _c represents a linear or branched C ₈ to C ₃₀ alkyl;
- n, x and y, identical or different, represent an integer between 1 and 10,000.

Preferably, in formula (IV), at least one of the radicals R _a , R _b , R _c , R′ _a , R′ _b , R′ _c represents an alkyl, linear or branched, C ₈ to C ₃₀ ; better in C ₁₀ to C ₂₄ , or even in C ₁₀ to C ₁₄ ; mention may in particular be made of the dodecyl radical (C ₁₂ ). Preferably, the other radical or radicals represent a linear or branched C ₁ to C ₄ alkyl, in particular methyl.

Preferably, in formula (IV), only one of the radicals R _a , R _b , R _c , R′ _a , R′ _b , R′ _c represents a linear or branched C ₈ to C ₃₀ alkyl; better in C ₁₀ to C ₂₄ , or even in C ₁₀ to C ₁₄ ; mention may in particular be made of the dodecyl radical (C ₁₂ ). Preferably, the other radicals represent a linear or branched C ₁ to C ₄ alkyl, in particular methyl.

Even better, R can be a group chosen from –N ⁺ (CH ₃ ) ₃ , Q' ^- and
–N ⁺ (C ₁₂ H ₂₅ )(CH ₃ ) ₂ , Q' ^- , preferably a –N ⁺ (CH ₃ ) ₃ , Q' ^- group.

Even better, R' can be a group –N ⁺ (C ₁₂ H ₂₅ )(CH ₃ ) ₂ , Q' ^- .

The aryl radicals preferably designate the phenyl, benzyl, naphthyl or anthryl groups.

Mention may in particular be made of polymers with the INCI name:
- Polyquaternium-24, such as the product QUATRISOFT LM ^200® , marketed by the company AMERCHOL/DOW CHEMICAL;
- PG-Hydroxyethylcellulose Cocodimonium Chloride, such as the product CRODACEL ^QM® ;
- PG-Hydroxyethylcellulose Lauryldimonium Chloride (C ₁₂ alkyl), such as the product CRODACEL QL ^® and
- PG-Hydroxyethylcellulose Stearyldimonium Chloride (C ₁₈ alkyl) such as the product CRODACEL QS ^® , marketed by the company CRODA.

Mention may also be made of the hydroxyethylcelluloses of formula (IV) in which R represents trimethylammonium halide and R' represents dimethyldodecylammonium halide, preferably R represents trimethylammonium chloride Cl ^- ,(CH ₃ ) ₃ N ⁺ - and R 'represents dimethyldodecylammonium chloride Cl ^- ,(CH ₃ ) ₂ (C ₁₂ H ₂₅ )N ⁺ -. This type of polymer is known under the INCI name Polyquaternium-67; as commercial products, mention may be made of SOFTCAT POLYMER ^SL® polymers such as SL-100, SL-60, SL-30 and SL-5 from AMERCHOL/DOW CHEMICAL.

More particularly, the polymers of formula (IV) are, for example, those whose viscosity is inclusively between 2000 and 3000 cPs (between 2 and 3 Pa.s), preferably between 2700 and 2800 cPs (between 2.7 and 2.8 Pa. .s). Typically SOFTCAT POLYMER SL-5 has a viscosity of 2500 cPs (2.5 Pa.s), SOFTCAT POLYMER SL-30 has a viscosity of 2700 cPs, SOFTCAT POLYMER SL-60 has a viscosity of 2700 cPs (2, 7 Pa.s) and SOFTCAT POLYMER SL-100 has a viscosity of 2800 cPs (2.8 Pa.s). It is also possible to use SOFTCAT POLYMER SX-1300X with a viscosity of between 1000 and 2000 cPs (between 1 and 2 Pa.s).

Cationic galactomannan gums are described more particularly in patents US3589578 and US4031307, and mention may be made of guar gums comprising cationic trialkylammonium groups. For example, guar gums modified with a salt (for example a chloride) of 2,3-epoxypropyl trimethylammonium are used. Such products are marketed in particular under the names JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 or JAGUAR C162 by the company RHODIA.

(3) polymers consisting of piperazinyl units and divalent alkylene or hydroxyalkylene radicals with straight or branched chains, optionally interrupted by oxygen, sulfur or nitrogen atoms or by aromatic or heterocyclic rings, as well as the products of oxidation and/or quaternization of these polymers.

(4) water-soluble polyaminoamides, prepared in particular by polycondensation of an acid compound with a polyamine; these polyaminoamides can be cross-linked with an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide or else by an oligomer resulting from the reaction of a bifunctional compound reactive with a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide, d an epilhalohydrin, a diepoxide or a bis-unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mole per amine group of the polyaminoamide; these polyaminoamides can be alkylated or if they contain one or more tertiary amine functions, quaternized.

(5) derivatives of polyaminoamides resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation by bifunctional agents. Mention may be made, for example, of adipic acid-diacoylaminohydroxyalcoyldialoylene triamine polymers in which the alkyl radical contains from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl. Among these derivatives, mention may more particularly be made of the adipic acid/dimethylaminohydroxypropyl/diethylene triamine polymers sold under the name “Cartaretine F, F4 or F8” by the company Sandoz.

(6) polymers obtained by reaction of a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic acids having from 3 to 8 carbon atoms; the molar ratio between the polyalkylene polyamine and the dicarboxylic acid preferably being between 0.8:1 and 1.4:1; the resulting polyaminoamide being reacted with epichlorohydrin in a molar ratio of epichlorohydrin to secondary amine group of the polyaminoamide preferably between 0.5:1 and 1.8:1. Polymers of this type are in particular marketed under the name "Hercosett 57" by the company Hercules Inc. or else under the name "PD 170" or "Delsette 101" by the company Hercules in the case of the adipic acid copolymer /epoxypropyl/diethylene-triamine.

(7) alkyl diallyl amine or dialkyl diallyl ammonium cyclopolymers such as homopolymers or copolymers comprising, as main constituent of the chain, units corresponding to formulas (V) or (VI):

formulas (V) and (VI), in which:
- k and t are equal to 0 or 1, the sum k + t being equal to 1;
- R ₁₂ denotes a hydrogen atom or a methyl radical;
- R ₁₀ and R ₁₁ , independently of one another, denote an alkyl group having from 1 to 6 carbon atoms, a hydroxyalkyl group in which the alkyl group has 1 to 5 carbon atoms, an amidoalkyl group in C ₁ to C ₄ ; or alternatively R ₁₀ and R ₁₁ can denote, together with the nitrogen atom to which they are attached, heterocyclic groups, such as piperidinyl or morpholinyl; R ₁₀ and R ₁₁ , independently of one another, preferably denote an alkyl group having from 1 to 4 carbon atoms; And
- Y ^- is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, phosphate.

Mention may be made more particularly of the homopolymer of salts (for example chloride) of dimethyldiallylammonium, for example sold under the name "MERQUAT 100" by the company NALCO (and their counterparts of low average molar masses by weight) and the copolymers of salts (for example chloride) of diallyldimethylammonium and of acrylamide marketed in particular under the name “MERQUAT 550” or “MERQUAT 7SPR”.

(8) diquaternary ammonium polymers comprising recurring units of formula:

formula (VII), in which:
- R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ , identical or different, represent aliphatic, alicyclic or arylaliphatic radicals comprising from 1 to 20 carbon atoms or lower hydroxyalkylaliphatic radicals, or alternatively R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ , together or separately, constitute with the nitrogen atoms to which they are attached heterocycles optionally comprising a second heteroatom other than nitrogen or alternatively R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ represent a C alkyl radical ₁ to C ₆ linear or branched substituted by a nitrile, ester, acyl, amide or -CO-OR ₁₇ -D or -CO-NH-R ₁₇ -D group where R ₁₇ is an alkylene and D a quaternary ammonium group;
- A ₁ and B ₁ represent divalent polymethylene groups comprising from 2 to 20 carbon atoms which may be linear or branched, saturated or unsaturated, and which may contain, linked to or intercalated in the main chain, one or more aromatic rings, or a or more atoms of oxygen, sulfur or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and
- X ^- denotes an anion derived from a mineral or organic acid;
it being understood that A ₁ , R ₁₃ and R ₁₅ can form with the two nitrogen atoms to which they are attached a piperazine ring;
in addition, if A ₁ denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B ₁ can also denote a (CH ₂ ) _n -CO-D-OC-(CH ₂ ) _n - group in which D denotes:
a) a glycol residue of formula -OZO-, where Z denotes a linear or branched hydrocarbon radical or a group corresponding to one of the following formulas: -(CH ₂ -CH ₂ -O) _x -CH ₂ -CH ₂ - and -[CH ₂ -CH(CH ₃ )-O] _y -CH ₂ -CH(CH ₃ )- where x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or a number any of 1 to 4 representing an average degree of polymerization;
b) a bis-secondary diamine residue such as a piperazine derivative;
c) a bis-primary diamine residue of formula: -NH-Y-NH-, where Y denotes a linear or branched hydrocarbon radical, or else the divalent radical -CH ₂ -CH ₂ -SS-CH ₂ -CH ₂ - ; Or
d) a ureylene group of formula: -NH-CO-NH-.

Preferably, X ^- is an anion such as chloride or bromide. These polymers have a number average molar mass (Mn) generally between 1000 and 100000.

Mention may more particularly be made of polymers which consist of recurring units corresponding to the formula:

formula (VIII) in which R ₁ , R ₂ , R ₃ and R ₄ , which are identical or different, denote an alkyl or hydroxyalkyl radical having from 1 to 4 carbon atoms approximately, n and p are integers ranging from 2 to 20 about and, X ^- is an anion derived from a mineral or organic acid.

A particularly preferred compound of formula (VIII) is that for which R ₁ , R ₂ , R ₃ and R ₄ represent a methyl radical, n=3, p=6 and X=Cl, called Hexadimethrine chloride according to the INCI nomenclature (CTFA ).

(9) polyquaternary ammonium polymers comprising units of formula (IX):

formula (IX), in which:
- R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ , which are identical or different, represent a hydrogen atom or a methyl, ethyl, propyl, β-hydroxyethyl, β-hydroxypropyl or -CH ₂ CH ₂ (OCH ₂ CH ₂ ) _p OH, where p is equal to 0 or to an integer between 1 and 6, provided that R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ do not simultaneously represent a hydrogen atom,
- r and s, identical or different, are whole numbers between 1 and 6,
- q is equal to 0 or an integer between 1 and 34,
- X ^- denotes an anion such as a halide, and
- A denotes a radical of a dihalide or preferably represents -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -.

Mention may be made, for example, of the products “ ^Mirapol® A 15”, “ ^Mirapol® AD1”, “ ^Mirapol® AZ1” and “ ^Mirapol® 175” sold by the company Miranol.

(10) quaternary polymers of vinylpyrrolidone and vinylimidazole such as, for example, the products marketed under the names Luviquat ^® FC 905, FC 550 and FC 370 by the company BASF

(11) polyamines such as ^Polyquart® H sold by Cognis, referenced under the name "POLYETHYLENEGLYCOL (15) TALLOW POLYAMINE" in the CTFA dictionary.

(12) polymers comprising in their structure:
(a) one or more grounds corresponding to the following formula (A):

(b) optionally one or more units corresponding to the following formula (B):

In other words, these polymers can be chosen in particular from homo- or copolymers comprising one or more units derived from vinylamine and optionally one or more units derived from vinylformamide.

Preferably, these cationic polymers are chosen from polymers comprising, in their structure, from 5 to 100% by moles of units corresponding to formula (A) and from 0 to 95% by moles of units corresponding to formula (B) , preferably from 10 to 100% by moles of units corresponding to formula (A) and from 0 to 90% by moles of units corresponding to formula (B).

These polymers can be obtained for example by partial hydrolysis of polyvinylformamide. This hydrolysis can take place in an acidic or basic medium.

The weight-average molecular mass of said polymer, measured by light diffraction, can vary from 1000 to 3,000,000 g/mole, preferably from 10,000 to 1,000,000 and more particularly from 100,000 to 500,000 g/mole.

The cationic charge density of these polymers can vary from 2 meq/g to 20 meq/g, preferably from 2.5 to 15 and more particularly from 3.5 to 10 meq/g.

The polymers comprising units of formula (A) and optionally units of formula (B) are in particular sold under the name LUPAMIN by the company BASF, such as for example, and in a non-limiting manner, the products offered under the name LUPAMIN 9095 , LUPAMIN 5095, LUPAMIN 1095, LUPAMIN 9030 (or LUVIQUAT 9030) and LUPAMIN 9010.

Preferably, the cationic polymer(s) are chosen from cationic polysaccharides (family (2)) and mixtures thereof, more preferably from cationic galactomannan gums and mixtures thereof, and better still from cationic guar gums and mixtures thereof.

The total content of the cationic polymer(s), when they are present in the anhydrous solid composition according to the invention, is preferably greater than or equal to 0.05% by weight, more preferably this total content ranges from 0.05 to 5 % by weight, better still from 0.1 to 2% by weight, and even more preferentially from 0.2 to 1.5% by weight, relative to the total weight of the composition.

In a preferred variant of the invention, the anhydrous solid composition further comprises one or more cationic polymers chosen from cationic polysaccharides (family (2)) and mixtures thereof, and the total content of the cationic polysaccharide(s) is preferably greater than or equal to 0.05% by weight, more preferably this total content ranges from 0.05 to 5% by weight, better still from 0.1 to 2% by weight, and even more preferably from 0.2 to 1.5% by weight, relative to the total weight of the composition.

The charges

The anhydrous solid composition according to the present invention may optionally also comprise one or more fillers, different from the cationic polymers defined above.

By "filler" is meant within the meaning of the present invention, inorganic or organic, polymeric or non-polymeric solid particles.

The fillers according to the invention participate in the solubilization or in the disintegration of the anhydrous solid composition of the invention, in particular in the presence of water. They can also contribute to improving the cosmetic performance due to the other compounds present in the composition.

Some fillers may also have “anti-caking” properties.

The mineral fillers can be chosen from solid salts of alkali metals or alkaline earth metals, in particular sodium or calcium salts, in particular sodium or calcium halides, such as sodium chloride and calcium chloride; or alternatively carbonates, in particular sodium or calcium, such as, for example, calcium carbonate and sodium bicarbonate. Mention may also be made of silicates, such as for example mica or clays, in particular kaolin.

The non-polymeric organic fillers can be chosen from monosaccharides, such as for example trehalose, sorbitol and mannitol.

The polymeric organic fillers, different from the cationic polymers described above, can be chosen from polysaccharides and mixtures thereof. Mention may in particular be made of cyclodextrins, starches, alginates, gellans, guar gums, celluloses, such as hydroxypropyl methyl cellulose, and wood flours. Among the polymeric organic fillers, mention may also be made of crosslinked polyvinyl pyrrolidones and polyacrylates (aquakeep for example).

Preferably, the fillers according to the invention are chosen from starches, celluloses, mica, clays and mixtures thereof, and more preferably from starches, celluloses and mixtures thereof . Better still, the anhydrous solid composition comprises a mixture of starch and at least one cellulose, in particular hydroxypropyl methyl cellulose.

The total content of the filler(s), when they are present in the anhydrous solid composition according to the invention, is preferably greater than or equal to 10% by weight, more preferably greater than or equal to 15% by weight, and better still greater than or equal to 20% by weight, relative to the total weight of the composition. Advantageously, the total content of the filler(s), when they are present in the anhydrous solid composition according to the invention, ranges from 10 to 80% by weight, preferably from 15 to 70% by weight, and more preferably from 20 at 70% by weight, relative to the total weight of the composition.

Nonionic surfactants

The anhydrous solid composition according to the present invention may optionally also comprise one or more nonionic surfactants.

Examples of nonionic surfactants that can be used in the compositions of the present invention are described, for example, in "Handbook of Surfactants" by MR PORTER, Blackie & Son editions (Glasgow and London), 1991, pp 116-178. They are chosen in particular from alcohols, alpha-diols, (C ₁ -C ₂₀ )alkylphenols or fatty acids, these compounds being polyethoxylated, polypropoxylated or polyglycerolated, and having at least one fatty chain comprising, for example, 8 to 18 carbon atoms, the number of ethylene oxide or propylene oxide groups possibly ranging in particular from 1 to 100 and the number of glycerol groups possibly ranging in particular from 1 to 30.

Mention may also be made of condensates of ethylene oxide and of propylene oxide with fatty alcohols; polyethoxylated fatty amides preferably having from 1 to 30 ethylene oxide units, polyglycerolated fatty amides comprising on average from 1 to 5 glycerol groups and in particular from 1.5 to 4, fatty acid esters of sorbitan containing from 2 to 30 ethylene oxide units, sucrose fatty acid esters, polyethylene glycol fatty acid esters, (C ₆ to C ₂₄ alkyl)polyglycosides, derivatives of N-( C ₆ to C ₂₄ alkyl)glucamine, amine oxides such as (C ₁₀ to C ₁₄ alkyl)amine oxides or N-(C ₁₀ to C ₁₄ acyl)-aminopropylmorpholine oxides.

Among the nonionic surfactants, it is more particularly preferred to use alkyl(poly)glycoside nonionic surfactants.

The term "alky(poly)glycoside" denotes an alkylpolyglycoside or an alkylmonoglycoside also called alkylglycoside in the present application, which can be alkoxylated by one or more alkylene oxide groups, preferably C ₂ to C ₄ .

The nonionic alkyl(poly)glycoside surfactant(s) used, alone(s) or as a mixture(s), in accordance with the present invention may be represented by the following formula (X):
R ₁ O-(R ₂ O) _t (G) _v (X)
formula (X), in which:
- R ₁ represents a saturated or unsaturated, linear or branched alkyl group containing from 8 to 24 carbon atoms, an alkylphenyl group whose linear or branched alkyl group contains from 8 to 24 carbon atoms,
- R ₂ represents an alkylene group comprising approximately 2 to 4 carbon atoms,
- G represents a saccharide unit comprising 5 to 6 carbon atoms,
- t denotes a value ranging from 0 to 10, preferably 0 to 4, and
-v designates a value ranging from 1 to 15.

Preferably, the nonionic alkyl(poly)glycoside surfactant(s) correspond to formula (X) in which:
- R ₁ denotes a saturated or unsaturated, linear or branched alkyl group, comprising from 8 to 18 carbon atoms,
- G denotes glucose, fructose or galactose, and preferably glucose,
- t denotes a value ranging from 0 to 3, and is preferably equal to 0, and
- R ₂ and v are as defined previously.

The degree of polymerization of the nonionic alkyl(poly)glycoside surfactant(s), as represented for example by the subscript v in formula (X) above, varies on average from 1 to 15, and preferably from 1 to 4. This degree of polymerization varies more particularly from 1 to 2, and better still from 1.1 to 1.5, on average.

The glycosidic bonds between the saccharide units are 1,6 or 1,4; and preferably in 1,4.

The nonionic alkyl(poly)glycoside surfactants which can be used in the present invention are preferably alkyl(poly)glucosides represented in particular by the products sold by the company COGNIS under the names ^PLANTAREN® (600 CS/U, 1200 and 2000) or PLANTACARE ^® (818, 1200 and 2000). It is also possible to use the products sold by the company SEPPIC under the names TRITON CG 110 (or ORAMIX CG 110) and TRITON CG 312 (or ORAMIX ^® NS 10), the products sold by the company BASF under the name LUTENSOL GD 70 or else those sold by the company CHEM Y under the name AG10 LK, or the products sold by the company EVONIK GOLDSCHMIDT under the trade names TEGO CARE CG 90 or TEGO CARE CG 90 MB.

As nonionic surfactant, the compounds with the INCI name caprylyl/capryl glucoside, decyl glucoside, coco glucoside, lauryl glucoside, myristyl glucoside, cetearyl glucoside and/or arachidyl glucoside can preferably be used. The compound with the INCI name cetearyl glucoside is particularly preferred.

The total content of the nonionic surfactant(s), when they are present in the anhydrous solid composition according to the invention, preferably ranges from 0.1 to 10% by weight, and more preferably from 0.2 to 5% by weight. , relative to the total weight of the composition.

In one embodiment, the anhydrous solid composition according to the invention comprises one or more nonionic surfactants, preferably one or more nonionic surfactants chosen from alkyl(poly)glycosides and mixtures thereof, and more preferably one or more nonionic surfactants ions chosen from alkyl(poly)glucosides and mixtures thereof. According to this embodiment, the total content of the alkyl(poly)glycoside(s), preferably of the alkyl(poly)glucoside(s), preferably ranges from 0.1 to 10% by weight, and more preferably from 0.2 to 5% by weight, relative to the total weight of the composition.

Cationic surfactants

The anhydrous solid composition according to the present invention may optionally also comprise one or more cationic surfactants.

The term "cationic surfactant" means a positively charged surfactant when it is contained in the compositions according to the invention. This surfactant can bear one or more permanent positive charges or contain one or more cationizable functions within the compositions according to the invention.

The cationic surfactants are advantageously chosen from salts of primary, secondary or tertiary fatty amines, optionally polyoxyalkylenated; quaternary ammonium salts, and mixtures thereof.

As quaternary ammonium salts, mention may in particular be made of:
- quaternary ammonium salts of formula (XI):

in which :
the groups R ₈ to R ₁₁ , which are identical or different, represent a linear or branched aliphatic group, comprising from 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, at least one of the groups R ₈ to R ₁₁ having 8 to 30 carbon atoms, preferably 12 to 24 carbon atoms; the aliphatic groups which may contain heteroatoms such as in particular oxygen, nitrogen, sulfur and halogens; And
X ^- is an anion chosen in particular from the group of halides, phosphates, acetates, lactates, alkyl (C ₁ -C ₄ )sulphates, alkyl (C ₁ -C ₄ )sulphonates or alkyl (C ₁ -C ₄ )aryl-sulphonates .

The aliphatic groups R ₈ to R ₁₁ can be chosen from C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, polyoxyalkylene (C ₂ -C ₆ ), C ₁ -C ₃₀ alkylamide, alkyl (C ₁₂ -C ₂₂ )amido(C ₂ -C ₆ )alkyl, (C ₁₂ -C ₂₂ )alkylacetate and C ₁ -C ₃₀ hydroxyalkyl.

Mention may in particular be made of tetraalkylammonium halides, in particular chlorides, such as dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl group contains from 12 to 22 carbon atoms, in particular behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium, benzyldimethylstearylammonium.

Mention may also be made of the halides, and in particular the chlorides, of palmitylamidopropyltrimethylammonium or of stearamidopropyldimethyl-(myristyl acetate)-ammonium; in particular the product marketed under the name CERAPHYL® 70 by the company VAN DYK.

- the quaternary ammonium salts of the imidazoline of formula (XII)

in which :
- R ₁₂ represents an alkenyl or alkyl group containing from 8 to 30 carbon atoms, for example derived from tallow fatty acids,
- R ₁₃ represents a hydrogen atom, a C ₁ to C ₄ alkyl group or an alkenyl or alkyl group containing from 8 to 30 carbon atoms,
- R ₁₄ represents a C ₁ to C ₄ alkyl group,
- R ₁₅ represents a hydrogen atom or a C ₁ to C ₄ alkyl group, and
- X ^- is an anion, chosen in particular from the group of halides, phosphates, acetates, lactates, alkyl (C1-C4) sulphates, alkyl (C1-C4) sulphonates or alkyl (C1-C4) aryl-sulphonates.

Preferably, R ₁₂ and R ₁₃ denote a mixture of alkenyl or alkyl groups containing from 12 to 21 carbon atoms, for example derived from tallow fatty acids, R ₁₄ denotes a methyl group, R ₁₅ denotes a hydrogen atom. Such a product is for example marketed under the name ^REWOQUAT® W75 or W90 by the company Evonik.

- di- or tri-quaternary ammonium salts of formula (XIII):

in which :
- R ₁₆ denotes an alkyl group comprising from 16 to 30 carbon atoms optionally hydroxylated and/or optionally interrupted by one or more oxygen atoms,
- R ₁₇ denotes hydrogen, an alkyl group containing from 1 to 4 carbon atoms or a group - (CH ₂ ) ₃ -N ⁺ (R _16a )(R _17a )(R _18a ), R _16a , R _17a , R _18a , identical or different, denoting hydrogen or an alkyl group containing from 1 to 4 carbon atoms,
- R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ , which are identical or different, denote hydrogen or an alkyl group comprising from 1 to 4 carbon atoms, and
- X ^- is an anion chosen in particular from the group of halides, acetates, phosphates, nitrates, alkyl (C ₁ -C ₄ )sulphates, alkyl (C ₁ -C ₄ )sulphonates and alkyl (C ₁ -C ₄ )aryl- sulfonates, in particular methyl sulfate and ethyl sulfate.

Such compounds are for example Finquat CT-P (Quaternium 89) and Finquat CT (Quaternium 75) offered by the company FINETEX.

- quaternary ammonium salts containing one or more ester functions of formula (XIV) below:

in which :
- R ₂₂ is chosen from C ₁ to C ₆ alkyl groups and C ₁ to C ₆ hydroxyalkyl or dihydroxyalkyl groups,
- R ₂₃ is chosen from the group R ₂₆ -C(=O)-; C ₁ to C ₂₂ hydrocarbon R ₂₇ groups, linear or branched, saturated or unsaturated; and the hydrogen atom,
- R ₂₅ is chosen from the group R ₂₈ -C(=O)-; C ₁ to C ₆ hydrocarbon R ₂₉ groups, linear or branched, saturated or unsaturated; and the hydrogen atom,
- R ₂₄ , R ₂₆ and R ₂₈ , identical or different, are chosen from C ₇ to C ₂₁ hydrocarbon groups, linear or branched, saturated or unsaturated,
- r, s and t, identical or different, are integers ranging from 2 to 6,
- r1 and t1, identical or different, are 0 or 1,
- y is an integer from 1 to 10,
- x and z, identical or different, are integers ranging from 0 to 10,
- X- is an anion,
it being understood that r2 + r1 = 2r and t1 + t2 = 2t, and that the sum x + y + z is from 1 to 15,
provided that when x = 0 then R ₂₃ denotes R ₂₇ and that when z = 0 then R ₂₅ denotes R ₂₉ .

The R ₂₂ alkyl groups can be linear or branched, preferably linear. Preferably, R ₂₂ denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl group, and more particularly a methyl or ethyl group.

Advantageously, the sum x + y + z is from 1 to 10.

When R ₂₃ is a hydrocarbon group R ₂₇ , it may comprise from 12 to 22 carbon atoms, or alternatively comprise from 1 to 3 carbon atoms.

Advantageously, R ₂₄ , R ₂₆ and R ₂₈ , identical or different, are chosen from C ₁₁ to C ₂₁ hydrocarbon groups, linear or branched, saturated or unsaturated, and more particularly from C 11 to C ₁₁ alkyl and alkenyl groups. ₂₁ , linear or branched.

Preferably, x and z, identical or different, are worth 0 or 1.

Advantageously, y is equal to 1.

Preferably, r, s and t, which are identical or different, are equal to 2 or 3, and even more particularly are equal to 2.

The anion X ^- is preferably a halide, preferably chloride, bromide or iodide, an alkyl (C1-C4) sulphate, an alkyl (C1-C4) sulphonate or an alkyl (C1-C4) aryl-sulphonate, a methanesulphonate , a phosphate, a nitrate, a tosylate, an anion derived from an organic acid such as an acetate or a lactate or any other anion compatible with the ammonium with an ester function. The anion X ⁻ is more particularly a chloride, a methyl sulphate or an ethyl sulphate.

More particularly, in the composition according to the invention, the ammonium salts of formula (XIV) in which:
- R ₂₂ denotes a methyl or ethyl group,
- x and y are equal to 1,
- z is equal to 0 or 1,
- r, s and t are equal to 2,
- R ₂₃ is chosen from the group R ₂₆ -C(=O)-; methyl, ethyl or C ₁₄ to C ₂₂ hydrocarbon groups, the hydrogen atom,
- R ₂₅ is chosen from the group R ₂₈ -C(=O)-; the hydrogen atom,
- R ₂₄ , R ₂₆ and R ₂₈ , identical or different, are chosen from C ₁₃ to C ₁₇ hydrocarbon groups, linear or branched, saturated or unsaturated, and preferably from C ₁₃ to C ₁₇ alkyl and alkenyl groups , linear or branched, saturated or unsaturated.

Advantageously, the hydrocarbon groups are linear.

Mention may be made, among the compounds of formula (XIV), of the salts, in particular the chloride or the methyl sulphate of diacyloxyethyldimethylammonium, of diacyloxyethyl-hydroxyethylmethylammonium, of monoacyloxyethyldihydroxyethyl methylammonium, of triacyloxyethylmethylammonium, of monoacyloxyethylhydroxyethyldimethylammonium, and mixtures thereof. The acyl groups preferably have 14 to 18 carbon atoms and come more particularly from a vegetable oil such as palm or sunflower oil. When the compound contains several acyl groups, the latter may be the same or different.

These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, alkyldiethanolamine or alkyldiisopropanol-amine optionally oxyalkylenated on fatty acids, or on mixtures of fatty acids in particular of vegetable or animal origin. , or by transesterification of their methyl esters. This esterification can be followed by a quaternization using an alkylating agent such as an alkyl halide, preferably methyl or ethyl, a dialkyl sulphate, preferably methyl or ethyl, methyl methanesulfonate, methyl para-toluenesulfonate, glycol or glycerol chlorohydrin. Such compounds are for example marketed under the names ^DEHYQUART® by the company HENKEL, ^STEPANQUAT® by the company STEPAN, ^NOXAMIUM® by the company CECA, ^REWOQUAT® WE 18 by the company Evonik.

The composition according to the invention may contain, for example, a mixture of mono-, di- and triester quaternary ammonium salts with a majority by weight of diester salts. It is also possible to use the ammonium salts containing at least one ester function described in patents US-A-4874554 and US-A-4137180. It is also possible to use behenoylhydroxypropyltrimethylammonium chloride, for example, offered by the company KAO under the name Quartamin BTC 131.

Preferably, the ammonium salts containing at least one ester function contain two ester functions.

Advantageously, when they are present in the anhydrous solid composition according to the invention, the content of the cationic surfactant(s) ranges from 0.01 to 5% by weight, preferably from 0.05 to 3% by weight, and more preferably from 0.1 to 2% by weight relative to the total weight of the composition.

The total content of surfactants, present in the anhydrous solid composition according to the invention, is preferably less than or equal to 85% by weight, more preferably this total content ranges from 20 to 80% by weight, and better still from 30 to 75 % by weight, relative to the total weight of the composition.

Organic solvents

The anhydrous solid composition according to the present invention may optionally also comprise one or more organic solvents.

Preferably, the organic solvent(s) are chosen from linear or branched monoalcohols having from 1 to 8 carbon atoms, and more preferably from 1 to 4 carbon atoms, polyols, polyethylene glycols, aromatic alcohols and mixtures thereof.

By way of examples of organic solvents that can be used according to the invention, mention may in particular be made of ethanol, propanol, butanol, isopropanol, isobutanol, propylene glycol, dipropylene glycol, isoprene glycol, butylene glycol, glycerol, benzyl alcohol, phenoxyethanol and mixtures thereof.

The organic solvent(s) which can be used according to the invention can be chosen from linear or branched monoalcohols having from 1 to 4 carbon atoms, and mixtures thereof, preferably from ethanol, propane, butane, isopropane, isobutane, and mixtures thereof.

Preferably, the organic solvent(s) are chosen from polyols and mixtures thereof, and more preferably from glycerol, propylene glycol, and mixtures thereof.

In a preferred embodiment of the invention, the anhydrous solid composition comprises one or more organic solvents, preferentially one or more polyols.

The total content of the organic solvent(s), when they are present in the anhydrous solid composition according to the invention, is preferably less than or equal to 20% by weight, more preferably less than or equal to 15% by weight, and better still ranges from 0.5 to 12% by weight, relative to the total weight of the composition.

The anhydrous solid composition according to the present invention may optionally also comprise one or more additional compounds different from the compounds defined above, preferably chosen from anionic and nonionic polymers, and mixtures thereof, antioxidants, penetrating agents , sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile, modified or unmodified silicones, film-forming agents, ceramides, preservatives, opacifying agents, lubricants (or anti-caking agents) and their mixtures.

According to a particular embodiment, the anhydrous solid composition of the invention may optionally comprise one or more lubricants. Such a lubricant can in particular act as an anti-caking agent, also called an anti-caking agent.

The lubricant(s) that can be used are different from the fillers and from the cationic polymers defined above.

Among the lubricants which can be used in the anhydrous solid composition of the invention, mention may in particular be made of silica, in particular colloidal anhydrous silica, sericite, polyamide ( ^Nylon® ), poly-p-alanine and polyethylene powders, tetrafluoroethylene (Teflon ^® ) polymer powders, acrylate and dimethicone copolymers, stearic acid, metallic soaps derived from organic carboxylic acids having 8 to 22 carbon atoms, preferably 12 to 18 atoms carbon, such as for example zinc, magnesium or lithium stearates, zinc laurate and magnesium myristate, alkali or alkaline-earth metal carbonates, such as for example magnesium, sodium carbonates, and calcium, fatty acids such as stearic acid, especially crystalline celluloses, and mixtures thereof.

According to one embodiment, the lubricant or lubricants are advantageously chosen from metal soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, and mixtures thereof, better still from zinc stearate, magnesium stearate, lithium stearate, zinc laurate, magnesium myristate and mixtures thereof. More preferably, the lubricant is magnesium stearate.

According to another embodiment, the lubricant or lubricants are advantageously chosen from alkali or alkaline-earth metal carbonates and their mixtures, preferably from magnesium carbonate, sodium carbonate, calcium carbonate and their mixtures; and more preferably magnesium carbonate.

Preferably, when the additional compound(s) above are present in the anhydrous solid composition according to the invention, the additional compound(s) are generally present in an amount comprised for each of them between 0.01 and 20% by weight relative to the weight of the composition.

Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the anhydrous solid composition of the invention are not, or substantially not, altered by the planned additions.

A subject of the present invention is also a method for the cosmetic treatment, and in particular a method for washing and/or conditioning, keratin fibres, in particular human keratin fibers such as the hair, comprising the application to said keratin fibers of an anhydrous solid composition as defined previously; the anhydrous solid composition being applied directly to said keratinous fibers or after having been previously moistened with water.

The anhydrous solid composition according to the invention can be applied to dry or wet keratin fibers, and preferably to wet keratin fibers.

The anhydrous solid composition, thus applied, can optionally be rinsed out or not, after a possible exposure time which can range from 1 to 15 minutes, preferably from 2 to 10 minutes.

Preferably, the anhydrous solid composition is rinsed off after application.

According to a first embodiment of the invention, the anhydrous solid composition is applied directly to the keratin fibers, that is to say without being moistened and/or disintegrated in water beforehand.

When, according to this first embodiment, the anhydrous solid composition of the invention is applied directly (that is to say without prior moistening or disintegration) to the dry keratin fibers, water can optionally be added to said fibers to then rub/massage in order to solubilize/pre-emulsify said composition and form an abundant and immediate foam. The foam thus obtained can then be rinsed after a possible exposure time.

Conversely, it is also possible to apply the anhydrous solid composition of the invention directly (that is to say without prior moistening or disintegration) to the wet keratin fibres, then massage/rub to disintegrate the particles and obtain a immediate and abundant foam. The foam thus obtained can then be rinsed after a possible exposure time.

According to another embodiment of the invention, the anhydrous solid composition is moistened and/or disintegrated beforehand in water before being applied to the keratin fibres. According to this embodiment, a small quantity (preferably ranging from 1 to 3 g) of anhydrous solid composition is advantageously taken and dissolved with water, for example in the hand, so as to form an abundant and immediate foam. The foam thus obtained can then be applied to the keratin fibres, dry or wet, before possibly being rinsed off with water after a possible exposure time.

A subject of the present invention is also the use of an anhydrous solid composition as defined above for washing and/or conditioning keratin fibres, in particular human keratin fibers such as the hair.

The present invention also relates to a packaging article, preferably cosmetic, comprising:
- an envelope defining at least one cavity, the envelope comprising one or more water-soluble and/or fat-soluble compounds,
- an anhydrous solid composition as defined above;
it being understood that the anhydrous solid composition is in one of the cavities defined by the envelope.

By “cosmetic packaging article” is meant an article suitable for cosmetic use; in particular for use of the conditioning article on keratin fibres, in particular the hair and/or on the scalp. In particular, the conditioning article makes it possible to wash and/or condition keratin fibres, in particular human keratin fibers such as the hair.

Preferably, the packaging article according to the invention is water-soluble or fat-soluble at a temperature less than or equal to 35°C.

Preferably, the envelope of the packaging article according to the invention is water-soluble at a temperature less than or equal to 35°C.

By “water-soluble”, is meant soluble in water, in particular at a rate of at least 10 grams per liter of water, preferably at least 20 g/l, better still at least 50 g/l, at a lower temperature or equal to 35°C. Thus, when water preferably having a temperature below 35°C is added to the packaging article, the envelope will dissolve and release the anhydrous solid composition present in one of the cavities of the envelope.

The term “liposoluble” is understood to mean soluble in a liquid fatty substance as defined below, in particular at the rate of at least 10 grams per liter of liquid fatty substance, in particular in a vegetable or mineral oil such as coconut oil. 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 less than or equal to 35°C.

The term “temperature less than or equal to 35° C.” is understood to mean a temperature not exceeding 35° C. but greater than or equal to 0° C., for example ranging from more than 1 to 35° C., preferably from 5 to 30° C. C, more preferably from 10 to 30°C, and even more preferably from 15 to 25°C. It is understood that all temperatures are given at atmospheric pressure (1 atm).

The packaging article may comprise one or more cavities, at least one of which contains the anhydrous solid composition as defined previously. Preferably, the packaging article only comprises a single cavity in which the anhydrous solid composition is contained.

Advantageously, the envelope represents from 0.5 to 20% by weight, preferably from 1 to 15% by weight, more preferably from 2 to 10% by weight, and better still from 4 to 8% by weight, with respect to the total weight of the packaging item.

Advantageously, the anhydrous solid composition as defined above represents from 80 to 99.5% by weight, preferably from 85 to 99% by weight, more preferably from 90 to 98% by weight, and better still from 92 to 96% by weight. weight, relative to the total weight of the packaging item.

The weight ratio between the total weight of the anhydrous solid composition of the invention and the total weight of the casing advantageously ranges from 80/20 to 99/1, preferably from 85/15 to 98/2, and more preferably from 90/10 to 97/3.

The envelope of the packaging article comprises one or more water-soluble and/or fat-soluble compounds, preferably one or more water-soluble compounds advantageously chosen from water-soluble polymers and mixtures thereof.

The water-soluble polymer(s) which can be used according to the present invention contain water-soluble units in their backbones. The water-soluble units are obtained from one or more water-soluble monomers.

By “water-soluble monomer”, is meant a monomer whose solubility in water is greater than or equal to 1%, preferably greater than or equal to 5% at 25° C. and at atmospheric pressure (760 mm Hg).

The said water-soluble polymer(s) capable of forming the envelope are advantageously obtained from water-soluble monomers comprising at least one double bond. The latter can be chosen from cationic, anionic, nonionic monomers and their mixtures.

As water-soluble monomers capable of being used as precursors of water-soluble units, alone or as a mixture, mention may be made, by way of examples, of the following monomers which may be in free or salified form:
- (meth)acrylic acid,
- styrene sulfonic acid,
- vinylsulfonic acid and (meth)allylsulfonic acid,
- vinyl phosphonic acid,
- N-vinylacetamide and N-methyl N-vinylacetamide,
- N-vinylformamide and N-methyl N-vinylformamide,
- N-vinyllactams comprising a cyclic alkyl group having from 4 to 9 carbon atoms, such as N-vinylpyrrolidone, N-butyrolactam and N-vinylcaprolactam,
- maleic anhydride,
- itaconic acid,
- vinyl alcohol of formula CH ₂ =CHOH,
- vinyl acetate of formula CH ₂ =CHOC(O)CH ₃ ,
- vinyl ethers of formula CH ₂ =CHOR in which R is a hydrocarbon radical, linear or branched, saturated or unsaturated, having from 1 to 6 carbon atoms,
- halides (chloride) of dimethyldiallyl ammonium,
- quaternized dimethylaminoethyl methacrylate (MADAME),
- (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 the following formula: H ₂ C=C(R)-C(O)-X, in which:
- R is chosen from H, (C ₁ -C ₆ )alkyl such as methyl, ethyl and propyl, and
- X is chosen from:
- alkoxy of -OR' type where R' is a hydrocarbon radical, linear or branched, saturated or unsaturated, having 1 to 6 carbons, optionally substituted by at least one halogen atom (iodine, bromine, chlorine, fluorine) ; a sulphonic (-SO ₃ ^- ), sulphate (SO ₄ ^- ), phosphate (-PO ₄ H ₂ ) group; hydroxy (-OH); primary amine (-NH ₂ ); secondary (NHR ₆ ), tertiary (-NR ₆ R ₇ ) or quaternary (-N ⁺ R ₆ R ₇ R ₈ ) amine with R ₆ , R ₇ and R ₈ being, independently of each other, a radical hydrocarbon, linear or branched, saturated or unsaturated, having 1 to 6 carbon atoms, provided that the sum of the carbon atoms of R' + R ₆ + R ₇ + R ₈ does not exceed 6;
- the groups -NH ₂ , -NHR' and -NR'R" in which R' and R" are independently of each other hydrocarbon radicals, linear or branched, saturated or unsaturated having 1 to 6 carbon atoms , provided that the total number of carbon atoms of R′ + R″ does not exceed 6, said R′ and R″ being optionally substituted by a halogen atom (iodine, bromine, chlorine, fluorine); a hydroxy group (-OH); sulfonic (-SO ₃ ^- ); sulphate (SO ₄ ^- ); phosphate (-PO ₄ H ₂ ); primary amine (-NH ₂ ); secondary (-NHR ₆ ), tertiary (NR ₆ R ₇ ) and/or quaternary (-N ⁺ R ₆ R ₇ R ₈ ) amine with R ₆ , R ₇ and R ₈ being, independently of each other, a hydrocarbon radical, linear or branched, saturated or unsaturated, having 1 to 6 carbon atoms, provided that the sum of the carbon atoms of R' + R'' + R ₆ + R ₇ + R ₈ does not exceed 6. As compounds corresponding to this formula, mention may be made, for example, of N,N-dimethylacrylamide and N,N-diethylacrylamide; And
- and mixtures thereof.

As anionic monomers, mention may in particular be made of (meth)acrylic acid, acrylamido-2-methylpropanesulfonic acid, itaconic acid and their salts of an alkali metal, alkaline earth metal or ammonium or those derived of an organic amine such as alkanolamine.

As non-ionic monomers, mention may in particular be made of (meth)acrylamide, N-vinylformamide, N-vinylacetoamide and hydroxypropyl (meth)acrylate, vinyl alcohol of formula CH ₂ =CHOH, and l vinyl acetate of formula CH ₂ =CHOC(O)CH ₃ .

The cationic monomers are preferably chosen from quaternary ammonium salts derived from a diallylamine, and those corresponding to the following formula:
H ₂ C=C(R ₁ )-DN ⁺ R ₂ R ₃ R ₄ , X ^-
in which :
• R ₁ represents a hydrogen atom or a methyl group,
• R ₂ and R ₃ , identical or different, represent a hydrogen atom or a linear or branched C ₁ to C ₄ alkyl group,
• R ₄ represents a hydrogen atom, a linear or branched C ₁ to C ₄ alkyl group or an aryl group,
• D represents the following divalent unit: -(Y) _n -(A)- in which:
- Y represents an amide function, an ester (OC(O) or C(O)-O), a urethane or a urea,
- A represents a linear or branched, cyclic or acyclic C ₁ to C ₁₀ alkylene group, which may be substituted or interrupted by a divalent aromatic or heteroaromatic group. The alkylene groups can be interrupted by an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom; the alkylene possibly being interrupted by a ketone function, an amide, an ester (OC(O) or C(O)-O), a urethane, or a urea,
- n is an integer ranging from 0 to 1,
• X ^- represents an anionic counterion, such as for example a chloride or a sulphate.

As examples of water-soluble cationic monomers, mention may in particular be made of the following compounds as well as their salts: (meth)acrylate of dimethylaminoethyl, (meth)acrylate of (meth)acryloyl-oxyethyltrimethylammonium, (meth)acrylate of (meth)acryloyloxyethyl -dimethylbenzyl-ammonium, N-[dimethylaminopropyl](meth)-acrylamide (meth)acrylate, (meth)acryl-amidopropyltrimethylammonium (meth)acrylate, (meth)acrylamido-propyldimethylbenzylammonium (meth)acrylate, dimethylaminohydroxypropryl, (meth)acryloyloxyhydroxypropyl-trimethylammonium (meth)acrylate, (meth)acryloyloxyhydroxypropyl-dimethylbenzylammonium (meth)acrylate and dimethyldiallylammonium (meth)acrylate.

Among the water-soluble polymers that can be used according to the present invention, mention may also be made of polyhydroxyalcohol (PHA).

Preferably, the water-soluble polymers are polymerized from one or more monomers chosen from vinyl alcohol of formula CH ₂ =CHOH, vinyl acetate of formula CH ₂ =CHOC(O)CH ₃ and mixtures thereof.

The water-soluble polymers capable of forming the envelope of the packaging article can also be chosen from water-soluble polymers derived from natural products, such as polysaccharides, i.e. polymers with sugar units. These water-soluble polymers are different from the cationic polysaccharide(s) (v) present in the anhydrous solid composition.

By “ sugar unit ”, is meant a unit derived from a carbohydrate of formula C _n (H ₂ O) _n-1 or (CH ₂ O) _n which can optionally be modified by substitution and/or by oxidation and/or by dehydration . The sugar units likely to enter into 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 sulphate, anhydrogalactose sulphate.

The polymers with sugar(s) unit(s) according to the invention can be of natural or synthetic origin. They can be nonionic, anionic, amphoteric or cationic. The basic units of the sugar unit polymers of the invention can be mono- or disaccharides.

Mention may in particular be made, as polymers capable of being used, of the following native gums, as well as their derivatives:
(a) exudates from trees or shrubs 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);
- tragacanth (or tragacanth) gum (polymer of galacturonic acid, galactose, fucose, xylose and arabinose);
b) gums derived from seaweed including:
- agar (polymer derived from galactose and anhydrogalactose);
- alginates (polymers of mannuronic acid and glucuronic acid);
- carrageenans and furcelleranes (polymers of galactose sulphate and anhydrogalactose sulphate);
c) gums from seeds or tubers of which:
- 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) whose main constituent is glucomannan is a high molecular weight polysaccharide (500,000 < M _glucomannan < 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 (polymer of glucose);
- biosaccharide gum (polymer of galacturonic acid, fucose and D-galactose),
e) plant extracts including:
- cellulose (polymer of glucose);
- starch (polymer of glucose);
- inulin (polymer of fructose and glucose).

These polymers can be modified physically or chemically. By way of physical treatment, mention may be made in particular of the temperature. Examples of chemical treatments include esterification, etherification, amidification and oxidation reactions. These treatments lead to polymers which may be nonionic, anionic, cationic or amphoteric.

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

The nonionic guar gums that can be used according to the invention can be modified with C ₁ to C ₆ hydroxylakyl groups. Among the hydroxyalkyl groups, mention may be made of hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.

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

The degree of hydroxyalkylation preferably varies from 0.4 to 1.2 and corresponds to the number of molecules of alkylene oxide consumed by the number of free hydroxyl functions present on the guar gum.

Such nonionic guar gums optionally modified with hydroxyalkyl groups are, for example, sold under the trade names JAGUAR HP8, JAGUAR HP60 and JAGUAR HP120 by the company RHODIA CHIMIE.

The guar gums modified with cationic groups which can more particularly be used according to the invention are guar gums comprising cationic trialkylammonium groups. Preferably, 2 to 30% by number of the hydroxyl functions of these guar gums carry cationic trialkyammonium groups. Even more preferentially, 5 to 20% of the number of hydroxyl functions of these guar gums are connected by cationic trialkyammonium groups. Among these trialkylammonium groups, mention may very particularly be made of trimethylammonium and triethylammonium groups. Even more preferentially, these groups represent from 5 to 20% by weight relative to the total weight of the modified guar gum.

According to the invention, it is possible to use guar gums modified with 2,3-epoxypropyl trimethylammonium chloride.

These guar gums modified with cationic groups are products already known per se and are for example described in US Pat. Nos. 3,589,578 and US Pat. C13 S, JAGUAR C 15, JAGUAR C 17 by RHODIA CHIMIE.

As modified locust bean gum, it is possible to use cationic locust bean gum containing hydroxypropyltrimmonium groups such as Catinal CLB 200 offered by the company TOHO.

The starch molecules used in the present invention may originate from all plant sources of starch, in particular cereals and tubers; more particularly, it may be corn, rice, cassava, barley, potato, wheat, sorghum, pea, oat or tapioca starches. It is also possible to use the hydrolysates of the starches mentioned above. The starch is preferably derived from potato.

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

More specifically, these reactions can be carried out as follows:
- pre-gelatinization by breaking up the starch granules (eg drying and cooking in a drying drum);
- oxidation by strong oxidants leading to the introduction of carboxyl groups into the starch molecule and to the depolymerization of the starch molecule (for example by treating an aqueous solution of starch with sodium hypochlorite);
- cross-linking by 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 acyl in C ₁ to C ₆ (acetyl), hydroxyalkylated in C ₁ to C ₆ (hydroxyethyl, hydroxypropyl), carboxymethyl, octenylsuccinic.

It is possible in particular to obtain, by crosslinking with phosphorus compounds, monostarch phosphates (of the Am-O-PO-(OX) ₂ type), distarch phosphates (of the Am-O-PO-(OX)-O-Am type) or even tristarch (of the Am-O-PO-(O-Am) ₂ type) or mixtures thereof; with Am signifying starch and X denoting in particular alkali metals (for example sodium or potassium), alkaline earth metals (for example calcium, magnesium), ammonia salts, amine salts such as those of monoethanolamine, diethanolamine, triethanolamine, 3-amino-1,2-propanediol, ammonium salts derived from basic amino acids such as lysine, arginine, sarcosine, ornithine, citrulline.

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

Mention may in particular be made of distarch phosphates or compounds rich in distarch phosphate such as the product offered under the references PREJEL VA-70-T AGGL (gelatinized hydroxypropylated cassava distarch phosphate) or PREJEL TK1 (gelatinized cassava distarch phosphate) or PREJEL 200 (gelatinized acetylated cassava distarch phosphate) from AVEBE or STRUCTURE ZEA from NATIONAL STARCH (gelatinized maize distarch phosphate).

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

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

The amphoteric starches are chosen in particular from the compounds of the following formulas:

formulas (XV) to (XVIII), in which:
- St-O represents a starch molecule;
- R, identical or different, represents a hydrogen atom or a methyl radical;
- R′, identical or different, represents a hydrogen atom, a methyl radical or a –C(O)-OH group;
- n is an integer equal to 2 or 3;
- M, identical or different, denotes a hydrogen atom, an alkali or alkaline earth metal such as Na, K, Li, a quaternary ammonium NH ₄ , or an organic amine; And
- R" represents a hydrogen atom or a C ₁ -C ₁₈ alkyl radical.

These compounds are in particular described in US5455340 and US4017460.

The starches of formulas (XVI) or (XVII) are particularly used; and preferably starches modified with 2-chloroethylaminodipropionic acid, that is to say the starches of formula (XVI) or (XVII) in which R, R', R" and M represent a hydrogen atom and n is equal to 2. Preferably, the amphoteric starch is a starch chloroethylamido dipropionate.

Cellulose and cellulose derivatives can be anionic, cationic, amphoteric or nonionic.

Among these derivatives, a distinction is made between cellulose ethers, cellulose esters and cellulose ether esters.

Among the cellulose esters, mention may be made of inorganic cellulose esters (nitrates, sulphates or phosphates of cellulose), organic cellulose esters (monoacetates, triacetates, amidopropionates, acetatebutyrates, acetatepropionates or acetatetrimellitates of cellulose) and mixed organic/ inorganic cellulose such as cellulose acetatebutyratesulfates and cellulose acetatepropionatesulfates.

Among the cellulose ether esters, mention may be made of hydroxypropyl methylcellulose phthalates and ethylcellulose sulphates.

Among the nonionic cellulose ethers, mention may be made of alkylcelluloses such as methylcelluloses and ethylcelluloses (for example Ethocel standard 100 Premium from DOW CHEMICAL); hydroxyalkylcelluloses such as hydroxymethylcelluloses, hydroxyethylcelluloses (for example Natrosol 250 HHR offered by AQUALON) and hydroxypropylcelluloses (for example Klucel EF from AQUALON); mixed hydroxyalkyl-alkylcelluloses such as hydroxypropyl-methylcelluloses (for example Methocel E4M from DOW CHEMICAL), hydroxyethyl-methylcelluloses, hydroxyethyl-ethylcelluloses (for example Bermocoll E 481 FQ from AKZO NOBEL) and hydroxybutyl-methylcelluloses.

Among the anionic cellulose ethers, mention may be made of carboxyalkylcelluloses and their salts. As an example, mention may be made of carboxymethylcelluloses, carboxymethylmethylcelluloses (for example Blanose 7M from the company AQUALON) and carboxymethylhydroxyethylcelluloses, as well as their sodium salts.

Among the cationic cellulose ethers, mention may be made of crosslinked or non-crosslinked quaternized hydroxyethyl celluloses. The quaternizing agent may in particular be diallyldimethylammonium chloride (for example Celquat L200 from NATIONAL STARCH). As another cationic cellulose ether, mention may be made of hydroxyethyl cellulose hydroxypropyltrimethylammonium (for example Ucare polymer JR 400 from AMERCHOL).

Among the associative polymers with sugar(s) unit(s), mention may be made of celluloses or their derivatives, modified by groups comprising at least one fatty chain such as alkyl, arylalkyl, alkylaryl groups or their mixtures where the alkyl groups are C8-C22; nonionic alkylhydroxyethylcelluloses such as the products NATROSOL PLUS GRADE 330 CS and POLYSURF 67 (C ₁₆ alkyl) sold by the company AQUALON; quaternized (cationic) alkylhydroxyethylcelluloses such as the products QUATRISOFT LM 200, QUATRISOFT LM-X 529-18-A, QUATRISOFT LM-X 529-18-B (C12 alkyl) and QUATRISOFT LM-X 529-8 (C12 alkyl) ₁₈ ) sold by the company AMERCHOL, the products CRODACEL QM, CRODACEL QL (C ₁₂ alkyl) and CRODACEL QS (C ₁₈ alkyl) sold by the company CRODA and the product SOFTCAT SL 100 sold by the company AMERCHOL; nonionic nonoxynylhydroxyethylcelluloses such as the product AMERCELL HM-1500 sold by the company AMERCHOL; nonionic alkylcelluloses such as the product BERMOCOLL EHM 100 sold by the company BEROL NOBEL.

As polymers with sugar(s) pattern(s) derived from associative guar, mention may be made of hydroxypropylguars modified with a fatty chain such as the product ESAFLOR HM 22 (modified with a C ₂₂ alkyl chain) sold by the company LAMBERTI; the product MIRACARE XC 95-3 (modified by a C ₁₄ alkyl chain) and the product RE 205-146 (modified by a C ₂₀ alkyl chain) sold by RHODIA CHIMIE.

The water-soluble polymer(s) with sugar(s) unit(s) that can be used to form the envelope of the packaging article are preferably chosen from guar gums, locust bean gums, xanthan gums, starches and celluloses, in their modified (derived) or unmodified form.

Preferably, the polymer(s) containing sugar unit(s) are nonionic.

The water-soluble polymers described above more particularly have a weight-average molecular weight (Mw) 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 Viscocity) method. as defined in "Principles of Polymer Chemistry" Cornell University Press, Ithaca, NY 1953 Chapter VII "Determination of molecular Weight" pp 266-316.

The water-soluble or fat-soluble compound(s) capable of forming the envelope of the packaging article according to the invention can be in the form of fibers or in film.

According to a first embodiment, the water-soluble or fat-soluble compound or compounds are in the form of fibres. By "fiber" is meant any object whose length is greater than its section. In other words, we must understand an object of length L and diameter D such that L is greater and preferably much greater (i.e. at least 3 times more) than D, D being the diameter of the circle in which is inscribed the section of the fiber. In particular, the L/D ratio (or aspect ratio) is chosen in the range going from 3.5 to 2500, preferably from 5 to 500, and better still from 5 to 150. The section of a fiber can be any shape, round, serrated or fluted, or even bean-shaped, but also multi-lobed, in particular tri-lobed or five-lobed, X-shaped, ribbon-shaped, square, triangular, elliptical, or other. The fibers of the invention can be hollow or non-hollow.

According to this embodiment, the fibers can be spun, carded or twisted. Advantageously, the fibers used in the context of the present invention are spun. The average diameter of the fibers implemented according to the present invention, identical or different, is less than 500 μm. Advantageously, such a diameter is less than 200 μm, preferably less than 100 μm, or even less than 50 μm.

Mention may more particularly be made of water-soluble fibers which include fibers based on PVA (polyvinylalcohol), polysaccharide fibers such as glucomannans, starches, celluloses such as carboxymethylcelluloses, polyalginic acid fibers, acid fibers polylactic, and polyalkyleneoxide fibers, as well as mixtures thereof. More preferably, the water-soluble fibre(s) used in the invention are chosen from fibers based on PVA.

The husk fibers are usually tangled. The term "casing comprising water-soluble fibers" means a casing which may be entirely made up of water-soluble fibers which may comprise both water-soluble fibers and water-insoluble fibers at a temperature less than or equal to 35°C, the soluble fibers having to be in greater quantity than the insoluble fibres. The fiber casing must comprise at least 60% by weight of soluble fibers, preferably at least 70% and better still at least 80% by weight relative to the total weight of the fibers. 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 fibers relative to the total weight of the fibers of the envelope.

When the envelope contains insoluble fibers, these can be made of any material usually used as insoluble fibers; this may be, for example, fibers of silk, cotton, wool, linen, polyamide (Nylon ^® ), polylactic acid, modified cellulose (rayon, viscose, rayon acetate), poly-p -phenylene terephthalamide, in particular Kevlar ^® , polyolefin and in particular polyethylene or polypropylene, glass, silica, aramid, carbon in particular in the form of graphite, Teflon ^® , insoluble collagen, polyesters, polyvinyl chloride or vinylidene, polyethylene terephthalate, fibers formed from a mixture of the compounds mentioned above, such as polyamide/polyester or viscose/polyester fibers.

In addition, when the envelope contains fibers, it can be woven or non-woven.

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

Such a woven material results from an operation aimed at assembling the fibers in an organized manner such as weaving itself, but can also result from knitting.

According to another variant of the invention, the envelope is non-woven.

By "nonwoven" is meant in the sense of the present invention a substrate comprising fibers, in particular polymeric water-soluble fibers, in which the individual fibers are arranged in a disordered manner in a structure in the form of a sheet and which are neither woven , nor knitted. The fibers of the nonwoven are generally bonded together, either under the effect of a mechanical action (for example needling, air jet, water jet), or under the effect of a thermal action, or by adding a binder.

Such a nonwoven is, for example, defined by the ISO 9092 standard as a veil or sheet of directionally or randomly oriented fibers, linked by friction and/or cohesion and/or adhesion, excluding paper and products obtained by weaving, knitting, tufting or sewing incorporating yarns or binding filaments.

A nonwoven differs from a paper by the length of the fibers used. In paper, the fibers are shorter. However, there are nonwovens based on cellulosic fiber which are wet-laid and have short fibers like in paper. The difference between a nonwoven and a paper is generally the absence of hydrogen bonding between the fibers in a nonwoven.

Very preferably, the fibers used in the context of the present invention are chosen from synthetic fibers such as PVA fibers. In particular, the envelope is non-woven, and preferably made of non-woven PVA fibers.

To produce the nonwoven envelope of the packaging article, PVA fibers which are soluble in water at a temperature less than or equal to 35° C. are preferably used, such as for example the fibers sold by the Japanese company Kuraray under the name KURALON K-II, and particularly the WN2 grade soluble from 20°C. These fibers are described in document EP-A-636716 which teaches the manufacture of water-soluble PVA fibers at temperatures not exceeding 100° C., by spinning and stretching the polyvinyl alcohol polymer in the dry state. or wet in the presence of solvents involved in the solubilization and solidification of the fiber. The fiber thus obtained can lead to the production of woven or non-woven substrates.

These fibers can also be prepared from a dope, 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 the wet drawing of the filaments from which the first solvent is removed and then dried and subjected to heat treatment. The section of these fibers can be substantially circular. These fibers have a tensile strength of at least 2.7 g/dtex (3 g/d). Application EP-A-0 636 716 describes such water-soluble fibers based on PVA and their method of manufacture. For example, the fibers can also be formed by extrusion and deposited on a conveyor to form a sheet of fibers which is then consolidated by a conventional fiber bonding technique, such as for example needling, hot bonding, calendering or bonding by hot air jets (in English air through bonding), a technique in which the water-soluble web passes through a tunnel where hot air is blown, or hydrobonding aimed at binding the fibers under the action of fine jets of water under very high pressure, which cannot be applied to fibers whose dissolution temperature is too low pressure.

As we have seen previously, the invention is not limited to the use of PVA, and it is also possible to use fibers made of other water-soluble materials provided that these materials dissolve in water having the desired temperature, for example polysaccharide fibers marketed under the name LYSORB by the company LYSAC TECHNOLOGIES, INC or other fibers based on polysaccharide polymers such as glucomannans or starch.

The casing can comprise a mixture of different fibers that are soluble in water at different temperatures (up to 35°C).

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

According to a particular embodiment of the invention, the envelope is a nonwoven, comprising water-soluble fibers, alone or mixed with insoluble fibers as indicated above, with at most 40% by weight of insoluble fibers per relative to the total weight of the fibers constituting the sheet. Preferably, the nonwoven consists essentially of water-soluble fibers, that is to say it does not contain insoluble fibers.

According to another embodiment of the invention, the envelope of the packaging article can consist of one or more films, which each comprise one or more water-soluble and/or fat-soluble compounds, in particular as defined above. . When the envelope consists of several films, said films can be assembled, for example glued together, in order to form a single unitary film.

The thickness of the "overall" film (that is to say the thickness of the single film when the envelope contains only one or of the unitary film when the envelope contains several films) is advantageously included between 10 and 1000 microns, preferably between 10 and 800 microns, and more preferably between 15-500 microns.

By film is meant in particular a continuous layer preferably formed of one or more water-soluble and/or fat-soluble compounds as defined above, in particular of polymer(s).

The main industrial methods of producing polymeric films are the extrusion of a molten polymer, the casting of a solution of a polymer on a polished metal surface (in some cases, the solution of the polymer is introduced into a precipitation tank ), casting a dispersion of the polymer onto a polished surface and calendering.

The films that can be used according to the present invention can be chosen from multilayer film-film, film-paper (coating) and film-coating.

When applied by spraying, brushing or various industrial processes, surface coatings undergo what is known as film formation, and in particular film-coating. In most film forming processes, a liquid coating of relatively low viscosity is applied to a solid substrate and is cured into a strong, adherent high molecular weight polymer film having the properties desired by the user.

The films which can be used according to the present invention are in particular PVA films which can be manufactured from any industrial method of production, such as a method of casting a polymeric solution based on PVA, an extrusion method in the presence or not water, a dry extrusion molding method or a biaxial orientation method.

The packaging article, as well as the envelope, can have any suitable shape for the intended use, for example a rectangular, round or oval shape. Preferably, it has a rounded geometry, for example in the form of a sphere, disc, or oval, or else square or parallelepipedal, preferably with rounded corners. The envelope preferably has dimensions allowing it to be gripped between at least two fingers. Thus, it may for example have an ovoid shape about 2 to 10 cm long and about 0.5 to 4 cm wide, or a circular disc shape about 2 to 10 cm in diameter, or a square shape with a side of approximately 2 to 15 cm, or a rectangle shape with a length of approximately 2 to 25 cm, it being understood that it may have any other shape and size appropriate for the desired use.

Preferably, the envelope can be round in shape with an internal diameter ranging from 3 to 7 cm, more preferably from 4 to 5 cm; to which can be added the dimension of the edges (sealed part) which can range from 1 to 5mm, better from 2 to 4mm; and a height ranging from 2 to 7mm, preferably from 3 to 5mm.

The envelope can also be square or rectangular in shape with a length preferably ranging from 2 to 6 cm, more preferably from 3 to 5 cm, and a width preferably ranging from 2 to 5 cm, more preferably 2.5 to 4 cm; to which can be added the dimension of the edges (sealed part) which can preferably range from 1 to 5mm, and more preferably from 2 to 4mm.

Advantageously, the envelope has a small thickness, and can be made up of several layers of different materials. Preferably the thickness of the envelope ranges from 3 to 99.9% of its other dimensions. The envelope is thus substantially flat, with thin slices.

The surface delimiting the cavity or cavities has an extent that is advantageously less than 625 cm ² , preferably between 0.025 cm ² and 400 cm ² , more preferably between 1 and 200 cm ² , better still between 2 and 50 cm ² , and better still between 4 and 25 cm ² , in order to have an optimized compaction of the composition. It has been observed that when the surface of the article is in the above ranges, the compaction of the anhydrous solid powder composition is lower and the transformation of the powder into the fluid composition in the hands is easier, without formation of agglomerates.

Preferably, the height of the envelope is greater than or equal to 2mm, more preferably ranges from 2 to 10mm, and better still from 3 to 7mm.

Preferably, the film(s) used in the context of the present invention are chosen from synthetic films, such as PVA or PVOH films, as well as mixtures thereof.

Preferably, the envelope consists of several layers, for example, 2 or 3 layers, of films each made, preferably, of different materials. Advantageously, at least one of these films is a film comprising or consisting of PVA and/or PVOH.

Preferably, the film or films are sealed in order to form one or more cavities which will include the anhydrous solid composition of the invention and prevent it from escaping.

Advantageously, the packaging article comprises from 1 to 5 g, preferably from 2 to 4.5 g of anhydrous solid composition; and 0.1 to 0.8g, preferably 0.2 to 0.5g of envelope.

The present invention further relates to a method for the cosmetic treatment of keratin fibres, in particular human keratin fibers such as the hair, comprising a step of implementing a conditioning article as defined above, preferably said cosmetic treatment process comprises the following steps:
i) mixing the packaging article in a composition capable of dissolving, in whole or in part, the envelope of the said packaging article,
ii) applying the composition obtained in step i) to the keratin fibres,
iii) possibly allow a pause,
iv) rinsing said keratinous fibres, and
v) optionally drying said keratinous fibers.

It is understood that the composition capable of dissolving the envelope depends on the nature of the envelope. In other words, the composition capable of dissolving the envelope is water or an aqueous composition, when the packaging article mainly or solely contains a hydrophilic envelope. And, the composition capable of solubilizing the envelope is an organic anhydrous composition or an aqueous composition comprising at least one liquid fatty substance or at least one organic solvent different from the liquid fatty substances such as lower monoalcohols, for example ethanol, or as polyols, for example propylene glycol or glycerin, when the packaging article mainly or solely contains a lipophilic envelope.

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

By way of example, mention may more particularly be made of alkanols such as ethyl alcohol, isopropyl alcohol, aromatic alcohols such as benzyl alcohol, and phenylethyl alcohol, or even polyols or polyol ethers such as , for example, ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol or its ethers such as, for example, propylene glycol monomethyl ether, butylene glycol, dipropylene glycol as well as diethylene glycol alkyl ethers such as, for example, monoethyl ether or diethylene glycol monobutyl ether.

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

The dilution ratio (expressed by weight) between one or more packaging items, as defined above, and the composition capable of solubilizing the packaging item(s) is preferably between 10/90 and 90/10, and more preferably between 10/90 and 50/50. Even better, this dilution ratio is 20/80.

In particular, the composition obtained at the end of the mixing (step i) of the process) can be applied to dry or wet keratin fibres. It is advantageously left to rest on the keratin fibers for a period ranging from 1 to 15 minutes, preferably from 2 to 10 minutes.

Then, the keratin fibers are rinsed with water. They can optionally be washed with shampoo, followed by rinsing with water, before being dried or left to dry.

A subject of the present invention is also the use of a conditioning article, as defined above, for washing and/or conditioning keratin fibres, and in particular human keratin fibers such as the hair.

The following examples serve to illustrate the invention without, however, being of a limiting nature.

Examples

Example 1
The following anhydrous solid compositions A1 to A4 according to the invention were prepared from the ingredients whose contents are indicated in the tables below (% in g of active material).
R corresponds to the weight ratio between the content of sulphate anionic surfactant and the content of amphoteric surfactant.

Layout A1 Layout A2 Layout A3 Layout A4 Cocamidopropyl betaine 5.1 5.1 10.4 6.9 Sodium lauryl sulphate 19.5 19.5 64.6 43.1 Propylene glycol 5 5 1.5 1.5 Hydroxypropyl guar chloride, hydroxypropyl trimonium 1 1 0.8 0.8 Hydroxypropyl methyl cellulose - 0.2 1.4 1.4 sodium chloride - - 1.9 1.25 Scent 0.5 0.5 - - Corn starch Qsp 100 Qsp 100 Qsp 100 Qsp 100 R 3.8 3.8 6.2 6.2

The solid anhydrous compositions A1-A4 (they all contain less than 0.2% water by weight, relative to the total weight of each of the compositions) thus obtained have good foam properties, in particular in terms of foam height.

The presence of hydroxypropyl methylcellulose in composition A2 also makes the foam obtained even more resistant to sebum and confers better disentangling properties on the hair, compared to composition A1 (evaluation of disentangling by 2 testers on SA20 locks, application of 0.2g of composition per g of locks, lather, leave on for 5 min and rinse 15 times).

Furthermore, compositions A1-A4 are packaged in powder form in a water-soluble sachet based on PVOH. The conditioning article thus obtained can then be used as a washing composition: it is placed in the palm of the hand, water is added thereto in order to dissolve it and possibly form a foam, then it is applied to the hair, preferably previously moistened.

Claims (17)

Anhydrous solid composition comprising:
(i) one or more sulfate-type anionic surfactants, and
(ii) one or more amphoteric or zwitterionic surfactants;
the weight ratio between the total content of anionic surfactant(s) of sulfate type (i) and the total content of amphoteric or zwitterionic surfactant(s) (ii) being greater than or equal to 3. Composition according to Claim 1, characterized in that the anionic surfactant(s) of sulphate type are chosen from alkyl sulphates, alkyl ether sulphates, alkylamidosulphates, alkylamidoether sulphates, alkylaryl-polyether sulphates, monoglyceride-sulphates; as well as their salts and their mixtures; the alkyl groups of these compounds comprising in particular from 8 to 30 carbon atoms; the aryl group preferably denoting a phenyl or benzyl group; these compounds possibly being polyoxyalkylenated, and then preferably comprising from 1 to 50 ethylene oxide units. Composition according to any one of the preceding claims, characterized in that the anionic surfactant(s) of sulphate type are chosen from:
- alkyl sulphates, in particular C ₈ to C ₂₆ , and preferably C ₁₀ to C ₂₂ ,
- alkyl ether sulphates, in particular C ₈ to C ₂₆ , and preferably C ₁₀ to C ₂₂ , preferably comprising from 2 to 10 ethylene oxide units;
in particular in the form of alkali or alkaline-earth metal, ammonium or aminoalcohol salts, and
their mixtures. Composition according to any one of the preceding claims, characterized in that the total content of the anionic surfactant(s) of sulphate type ranges from 1 to 80% by weight, preferably from 10 to 75% by weight, more preferably from 30 to 70% by weight, and better still from 35 to 70% by weight, relative to the total weight of the composition. Composition according to any one of the preceding claims, characterized in that the amphoteric or zwitterionic surfactant(s) are chosen from (C ₈ -C ₂₀ )alkyl betaines, (C ₈ -C ₂₀ )alkyl amido(C ₃ -C ₈ ) betaines, and mixtures thereof; and preferably from (C ₈ -C ₂₀ )alkylamido(C ₃ -C ₈ )alkyl betaines and mixtures thereof. Composition according to any one of the preceding claims, characterized in that the total content of the amphoteric or zwitterionic surfactant(s) ranges from 1 to 30% by weight, preferably from 2 to 20% by weight, and more preferably from 3 to 15 % by weight, relative to the total weight of the composition. Composition according to any one of the preceding claims, characterized in that the total content of anionic surfactants of sulphate type (i) and of amphoteric or zwitterionic surfactants (ii) is less than or equal to 90% by weight, and preferably less than or equal to 75% by weight, relative to the total weight of the composition. Composition according to any one of the preceding claims, characterized in that the weight ratio between the total content of anionic surfactant(s) of sulphate type (i) and the total content of amphoteric or zwitterionic surfactant(s) (ii ) is greater than or equal to 4, preferably greater than or equal to 5, and more preferably greater than or equal to 6. Composition according to any one of the preceding claims, characterized in that it also comprises one or more cationic polymers, and preferably chosen from:
(1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of the following formula:

formulas in which:
- R ₃ , identical or different, denote a hydrogen atom or a CH ₃ radical;
- A, identical or different, represent a divalent alkyl group, linear or branched, of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms or a hydroxyalkyl group of 1 to 4 carbon atoms;
- R ₄ , R ₅ and R ₆ , identical or different, represent an alkyl group having from 1 to 18 carbon atoms or a benzyl radical;
- R ₁ and R ₂ , identical or different, represent a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms, and
- X denotes an anion derived from a mineral or organic acid such as a methosulfate anion or a halide such as chloride or bromide;
(2) cationic polysaccharides;
(3) polymers consisting of piperazinyl units and divalent alkylene or hydroxyalkylene radicals with straight or branched chains, optionally interrupted by oxygen, sulfur or nitrogen atoms or by aromatic or heterocyclic rings, as well as the products of oxidation and/or quaternization of these polymers;
(4) water-soluble polyaminoamides, prepared in particular by polycondensation of an acid compound with a polyamine;
(5) derivatives of polyaminoamides resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation by bifunctional agents;
(6) polymers obtained by reaction of a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic acids having from 3 to 8 carbon atoms;
(7) alkyl diallyl amine or dialkyl diallyl ammonium cyclopolymers;
(8) diquaternary ammonium polymers comprising recurring units of formula (VII):

formula (VII), in which:
- R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ , identical or different, represent aliphatic, alicyclic or arylaliphatic radicals comprising from 1 to 20 carbon atoms or lower hydroxyalkylaliphatic radicals, or alternatively R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ , together or separately, constitute with the nitrogen atoms to which they are attached heterocycles optionally comprising a second heteroatom other than nitrogen or alternatively R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ represent a C alkyl radical ₁ to C ₆ linear or branched substituted by a nitrile, ester, acyl, amide or -CO-OR ₁₇ -D or -CO-NH-R ₁₇ -D group where R ₁₇ is an alkylene and D a quaternary ammonium group;
- A ₁ and B ₁ represent divalent polymethylene groups comprising from 2 to 20 carbon atoms which may be linear or branched, saturated or unsaturated, and which may contain, linked to or intercalated in the main chain, one or more aromatic rings, or a or more atoms of oxygen, sulfur or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and
- X ^- denotes an anion derived from a mineral or organic acid;
it being understood that A ₁ , R ₁₃ and R ₁₅ can form with the two nitrogen atoms to which they are attached a piperazine ring;
in addition, if A ₁ denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B ₁ can also denote a (CH ₂ ) _n -CO-D-OC-(CH ₂ ) _n - group in which D denotes:
a) a glycol residue of formula -OZO-, where Z denotes a linear or branched hydrocarbon radical or a group corresponding to one of the following formulas: -(CH ₂ -CH ₂ -O) _x -CH ₂ -CH ₂ - and -[CH ₂ -CH(CH ₃ )-O] _y -CH ₂ -CH(CH ₃ )- where x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or a number any of 1 to 4 representing an average degree of polymerization;
b) a bis-secondary diamine residue such as a piperazine derivative;
c) a bis-primary diamine residue of formula: -NH-Y-NH-, where Y denotes a linear or branched hydrocarbon radical, or else the divalent radical -CH ₂ -CH ₂ -SS-CH ₂ -CH ₂ - ; Or
d) a ureylene group of formula: -NH-CO-NH-;
(9) polyquaternary ammonium polymers comprising units of formula (IX):

formula (IX), in which:
- R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ , identical or different, represent a hydrogen atom or a methyl, ethyl, propyl, β-hydroxyethyl, β-hydroxypropyl or -CH ₂ CH ₂ (OCH ₂ CH ₂ ) _p OH, where p is equal to 0 or to an integer between 1 and 6, provided that R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ do not simultaneously represent a hydrogen atom,
- r and s, identical or different, are whole numbers between 1 and 6,
- q is equal to 0 or an integer between 1 and 34,
- X ^- denotes an anion such as a halide, and
- A denotes a radical of a dihalide or preferably represents -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -;
(10) quaternary polymers of vinylpyrrolidone and vinylimidazole;
(11) polyamines; And
(12) polymers comprising in their structure:
(a) one or more grounds corresponding to the following formula (A):

(b) optionally one or more units corresponding to the following formula (B):
. Composition according to the preceding claim, characterized in that the cationic polymer or polymers are chosen from cationic polysaccharides and mixtures thereof, preferably from cationic galactomannan gums and mixtures thereof, and more preferably from cationic guar gums and mixtures thereof. Composition according to any one of Claims 9 or 10, characterized in that the total content of the cationic polymer or polymers is greater than or equal to 0.05% by weight, preferably this total content ranges from 0.05 to 5% by weight, more preferably from 0.1 to 2% by weight, and better still from 0.2 to 1.5% by weight relative to the total weight of the composition. Composition according to any one of the preceding claims, characterized in that it additionally comprises one or more fillers, preferably chosen from starches, celluloses, mica, clays and mixtures thereof, and more preferably from starches, celluloses and mixtures thereof. Composition according to the preceding claim, characterized in that the total content of the filler(s) is greater than or equal to 10% by weight, preferably greater than or equal to 15% by weight, and more preferably greater than or equal to 20% by weight , relative to the total weight of the composition. Process for the cosmetic treatment of keratin fibers, in particular human keratin fibers such as the hair, comprising the application to the said keratin fibers of an anhydrous solid composition as defined in any one of the preceding claims; the anhydrous solid composition being applied directly to said keratinous fibers or after having been previously moistened with water. Packaging item comprising:
- an envelope defining at least one cavity, the envelope comprising one or more water-soluble and/or fat-soluble compounds;
- an anhydrous solid composition as defined in any one of claims 1 to 13;
it being understood that the anhydrous solid composition is in one of the cavities defined by the envelope. Process for the cosmetic treatment of keratin fibres, in particular human keratin fibers such as the hair, comprising a step of implementing a conditioning article as defined in claim 15, said cosmetic treatment process preferably comprises the following steps :
i) mixing the packaging article in a composition capable of dissolving, in whole or in part, the envelope of the said packaging article,
ii) applying the composition obtained in step i) to the keratin fibres,
iii) possibly allow a pause,
iv) rinsing said keratinous fibres, and
v) optionally drying said keratinous fibres. Use of an anhydrous solid composition as defined in any one of Claims 1 to 13 or of a conditioning article as defined in Claim 15 for washing and/or conditioning keratin fibers, in particular fibers human keratins such as hair.