FR3141339A1 - SOLID COMPOSITION COMPRISING A CATIONIC SURFACTANT, TWO STARCHES, A LIQUID FAT AND A SPECIFIC QUANTITY OF WATER - Google Patents

Abstract

The present invention relates to a solid composition intended in particular for the care of keratin fibers, in particular human keratin fibers such as hair, and which comprises at least one cationic surfactant, at least two starches, at least one liquid fatty substance and a specific quantity of water. The invention also relates to a packaging article containing said solid composition, as well as methods of cosmetic treatment of keratin fibers, in particular human keratin fibers such as hair using said solid composition or said conditioning article. The invention further relates to the use of said solid composition or of said conditioning article for the care of keratin fibers, in particular human keratin fibers such as hair.

Description

SOLID COMPOSITION COMPRISING A CATIONIC SURFACTANT, TWO STARCHES, A LIQUID FAT AND A SPECIFIC QUANTITY OF WATER

The present invention relates to a solid composition intended in particular for the cosmetic treatment, and more particularly for the care, of keratin fibers, in particular human keratin fibers such as hair, and which comprises at least one cationic surfactant, at least two starches, at least a liquid fatty substance and a specific amount of water.

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

The invention further relates to the use of said solid composition or of said conditioning article for the cosmetic treatment, preferably care, of keratin fibers, in particular human keratin fibers such as hair.

In the field of hair hygiene, care (or conditioning) products for keratin fibers are generally intended to condition said fibers to provide them with good cosmetic properties. Classic products, such as conditioners, are most often in more or less thickened liquid form. Due to their liquid texture, these products can, however, have various disadvantages, including being difficult to dose.

In fact, the more liquid they are, the more they tend to escape between the fingers, making their dosage difficult and leading to 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 traveling.

In order to modify the texture of these products, and in particular make it more compact, thickeners are generally used. The addition of these compounds, however, is often done to the detriment of the cosmetic effects of the compositions. The use of these thicker compositions also requires a lot of rinsing water in order to remove excess product from the fibers. However, in many countries where access to water is restricted, the rinsing time and therefore the quantity of water necessary to thoroughly rinse the product are key indicators of the usability of a composition.

To overcome some of these problems, new solid cosmetic formulations, including conditioners in solid granule or powder form, have been developed. Such formulations are described, for example, in US 2021/007960. 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. Those in the form of agglomerates, such as granules for example, may have a tendency to disintegrate or disintegrate with difficulty in the presence of water, adversely impacting their use and their spreading on the keratin fibers, and do not always allow obtain satisfactory care. They can also be difficult to remove when rinsing and sometimes even leave residues on the fibers that are unpleasant for the consumer.

Conditioners in powder or particle form can lose fluidity during storage due to the agglutination of solid unit particles together, which can negatively impact the qualities of use.

These formulations may also not be entirely satisfactory in terms of cosmetic performance, particularly in terms of suppleness, feel, softness, detangling, smoothing, and shine.

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 easily graspable and disintegrate easily, but it must also be quick to rinse without leaving residue on the keratin fibers. With regard to solid compositions in the form of powders or particles in particular, these must not clump together during storage so as not to deteriorate the qualities of use.

The composition must also confer good cosmetic properties, particularly in terms of flexibility, feel, softness, coating, shine and detangling.

It has now been discovered that a solid composition comprising at least one cationic surfactant, at least two starches, at least one liquid fatty substance and water in a particular content makes it possible to achieve the objectives set out above, and in particular to offer a composition in solid form combining good conditioning power, without requiring large quantities of water.

The subject of the present invention is therefore a solid composition comprising:
i) one or more cationic surfactants,
(ii) two or more starches,
iii) one or more liquid fatty substances and
iii) from 0.1 to 10% by weight of water _, relative to the total weight of the composition.

Said solid composition may more particularly be a cosmetic composition, in particular a hair composition, and advantageously, a hair conditioning composition.

The particular combination of the compounds of the invention makes it possible to obtain a solid composition that is easy to collect, handle and dose. Indeed, the composition thus obtained has a cohesion or granulation such that the gripping and dosing properties are improved, while avoiding unwanted agglomerates negatively impacting the qualities of use. The composition can then be packaged in single-dose form, a particularly interesting form for example when traveling or playing a sport (light bags, limitation of the risk of leakage, reduction of waste).

In addition, this composition disintegrates quickly on contact with water and makes it possible to easily and quickly obtain easy spreading and homogeneous distribution on the keratin fibers comparable to those of a classic liquid conditioner composition.

The composition according to the invention also makes it possible to obtain a good coating of the keratin fibers, with a homogeneous and slippery finish.

Furthermore, the composition of the invention rinses quickly without leaving unpleasant residues on the fibers and gives them a natural and clean feel after rinsing. The fibers treated with the composition of the invention have good cosmetic properties, particularly in terms of softness, flexibility and feel. They are also well individualized and therefore easier to untangle.

The present invention also relates to a method of cosmetic treatment, in particular care, of keratin fibers, in particular human keratin fibers such as hair, comprising the application to said keratin fibers of a solid composition as defined below. afterwards, the solid composition being applied directly to said keratin fibers or after having been previously moistened with water.

The present invention further relates to the use of a solid composition as defined below for cosmetic treatment, preferably the care of keratin fibers, in particular human keratin fibers such as 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;
- a solid composition as defined above;
it being understood that the solid composition is found in one of the cavities defined by the envelope.

This packaging article makes it possible in particular to resolve the problems of dosing the solid composition. It also facilitates its storage and transport. In particular, the packaging article of the invention offers better protection of the composition against humidity.

The packaging article can also make it possible to obtain a final composition for caring for keratin fibers that is thicker in the hand, which can be in the form of a cream, without lumps, without leaving residue on the hair after rinsing.

The packaging article can thus improve, in particular facilitate, the distribution of the composition on the keratin fibers.

The packaging article can make it possible to better control the dose of composition applied to the keratin fibers, thus reducing the risk of waste.

The packaging article also makes it possible to minimize the risks of disintegration of the composition.

The invention also relates to the use of the above conditioning article for cosmetic treatment, preferably for the care of keratin fibers, in particular human keratin fibers such as hair.

The invention also relates to a method of cosmetic treatment, in particular care, of keratin fibers, in particular human keratin fibers such as hair, comprising a step of implementing at least one conditioning article as defined below. -above.

Preferably, said cosmetic treatment method comprises the following steps:
a) mixing the packaging article in a composition capable of solubilizing, in whole or in part, the envelope of said packaging article,
b) apply the composition obtained in step a) to the keratin fibers,
c) possibly leave to pause,
d) rinsing said keratin fibers,
e) optionally drying said keratin fibers.

Other objects, characteristics, aspects and advantages of the invention will appear even more clearly on reading the description and examples 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 “between” and “ranging from… to…”.

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

Preferably, the solid composition according to the invention (final composition, after drying) has a water activity lower than 0.75, better still lower than 0.72, even better lower than 0.70. Water activity, Aw, represents the proportion of bound water relative to free water which is conducive to the development of microorganisms. The value varies between 0 and 1. The activity is 0 for a completely dry product and it is 1 for pure water.

The solid composition according to the invention may comprise water added during its preparation and/or water which may come from the raw materials used during the preparation of said composition.

The solid composition according to the invention can be in the form of powder, paste, particles (for example spherical particles such as small balls or granules), compressed tablet, stick or bread. Preferably, the composition according to the invention is in the form of powder or 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 is such that the weight ratio of particles which have a size less than or equal to 50 µm (fine content), preferably less than or equal to 45 µm (fine content) is advantageously less than or equal to at 5% by weight, preferably less than 3% by weight and more particularly less than 1% by weight, relative to the total weight of particles (particle size evaluated using a RETSCH AS 200 DIGIT particle size analyzer; Height of oscillation: 1.25 mm / sieving time: 5 minutes).

By “paste” is meant a composition having a viscosity greater than 0.5 Pa.s (5 poise) and preferably greater than 1 Pa.s (10 poise), measured at 25°C and at a shear rate of 1 s ^-1 ; this viscosity can be determined using a Coneplan rheometer.

By “particles” we mean small, split objects made up 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 (like granules, pellets, balls), square, rectangular, or elongated like sticks. Spherical particles are particularly preferred.

Advantageously, the solid composition is in powder form.

Advantageously, the size of the powders or particles is, in its largest dimension, between 30 µm and 5 mm, and more particularly between 45 µm and 2 mm, better between 50 µm and 1 mm, even better between 60 and 700 µm.

Advantageously, the solid composition is in powder form, the size of the powders being, in its largest dimension, between 30 µm and 5 mm, and more particularly between 45 µm and 2 mm, better still between 50 µm and 5 mm. 1 mm, even better between 60 and 700 µm.

When the solid composition according to the invention is not in the form of powder or particles, it advantageously has a penetration force at 25°C and under 1.013 x 10 ⁵ Pa (1 atm), greater than or equal to 200 g, preferably greater than or equal to 300 g, more preferably greater than or equal to 400 g, and better still greater than or equal to 500 g. The penetration force is determined by penetrometry. 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 fitted with a screwed tip, said tip being a 2 mm 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, to a height of 5 mm. The force exerted on the piston is recorded and the average force value is calculated.

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

The density of the 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 0.7. It is measured as follows:
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 tube and the density (d) is then determined according to the formula d=m/v.

Cationic surfactants i)
The solid composition according to the present invention comprises one or more cationic surfactants i).

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

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

As quaternary ammonium salts, we can cite in particular:

quaternary ammonium salts of formula (Ia):

in which :
the groups R ₈ to R ₁₁ , 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 comprising from 8 to 30 carbon atoms, preferably from 12 to 24 carbon atoms; aliphatic groups which may contain heteroatoms such as in particular oxygen, nitrogen, sulfur and halogens; And
^- _{​ ​ ​ ​ ​ ​} .

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

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

the quaternary ammonium salts of imidazoline of formula (IIa):

in which :
R ₁₂ represents an alkenyl or alkyl group containing 8 to 30 carbon atoms, for example derived from tallow fatty acids,
R ₁₃ represents a hydrogen atom, a C ₁ -C ₄ alkyl group or an alkenyl or alkyl group containing 8 to 30 carbon atoms,
R ₁₄ represents a C ₁ -C ₄ alkyl group,
R ₁₅ represents a hydrogen atom or a C ₁ -C ₄ alkyl group,
^- _{​ ​ ​ ​ ​ ​} sulfonates.

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

quaternary di- or triammonium salts of formula (IIIa):

in which :
- R ₁₆ designates an alkyl group comprising from 16 to 30 carbon atoms optionally hydroxylated and/or optionally interrupted by one or more oxygen atoms,
- R ₁₇ designates hydrogen, an alkyl group containing 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 designating hydrogen or an alkyl group comprising 1 to 4 carbon atoms,
- R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ , identical or different, designate hydrogen or an alkyl group comprising 1 to 4 carbon atoms, and
^- _{​ ​ ​ ​ ​ ​} 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 (IVa) following:

in which :
- R ₂₂ is chosen from C ₁ -C ₆ alkyl groups and C ₁ -C ₆ hydroxyalkyl or dihydroxyalkyl groups,
- R ₂₃ is chosen from the group R ₂₆ -C(=O)-; the R ₂₇ hydrocarbon groups in C ₁ -C ₂₂ , linear or branched, saturated or unsaturated; and the hydrogen atom,
- R ₂₅ is chosen from the group R ₂₈ -C(=O)-; the R ₂₉ hydrocarbon groups in C ₁ -C ₆ , 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 -C ₂₁ hydrocarbon groups, linear or branched, saturated or unsaturated,
- r, s and t, identical or different, are integers valued from 2 to 6,
- r1 and t1, identical or different, are 0 or 1,
- y is an integer valued from 1 to 10,
- x and z, identical or different, are integers valued 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 designates R ₂₇ and that when z = 0 then R ₂₅ designates 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 worth 1 to 10.

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

When R ₂₅ is a hydrocarbon R ₂₉ group, it preferably has 1 to 3 carbon atoms.

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

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

Advantageously, y is equal to 1.

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

_The ^anion _{​ ​ ​ ​ ​} aryl-sulfonate, a methanesulfonate, 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 ester-functional ammonium. The anion X- is more particularly a chloride, a methyl sulfate or an ethyl sulfate.

More particularly, ammonium salts of formula (IVa) are used in the composition according to the invention in which:
- R ₂₂ designates 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 -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 -C ₁₇ hydrocarbon groups, linear or branched, saturated or unsaturated, and preferably from C ₁₃ -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 (IVa) of salts, in particular chloride or methyl sulfate of diacyloxyethyldimethylammonium, diacyloxyethyl-hydroxyethylmethylammonium, monoacyloxyethyldihydroxyethyl methylammonium, triacyloxyethylmethylammonium, 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, they 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, particularly of plant or animal origin. , or by transesterification of their methyl esters. This esterification can be followed by quaternization using an alkylating agent such as an alkyl halide, preferably methyl or ethyl, a dialkyl sulfate, 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 quaternary ammonium mono-, di- and triester 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, ammonium salts containing at least one ester function contain two ester functions.

As fatty amines, we can cite amidoamines.
The amidoamines according to the invention can be chosen from fatty amidoamines, the fatty chain being able to be carried by the amine group or by the amido group.

Amidoamine means a compound comprising at least one amide function and at least one primary, secondary or tertiary amine function.

By fatty amidoamine is meant an amidoamine comprising, in general, at least one C ₆ -C ₃₀ hydrocarbon chain. Preferably, the fatty amidoamines useful according to the invention are not quaternized.

Preferably, the fatty amidoamines useful according to the invention are not (poly)oxyalkylenated.

Among the fatty amidoamines useful according to the invention, mention may be made of the following amidoamines of formula (Va):
RCONHR''N(R') ₂ (Va)
in which :
- R represents a linear or branched monovalent hydrocarbon radical, saturated or unsaturated and substituted or unsubstituted, having from 5 to 29 carbon atoms, preferably from 7 to 23 carbon atoms, and in particular a C ₅ -C alkyl radical ₂₉ , preferably C ₇ -C ₂₃ , linear or branched, or a C ₅ -C ₂₉ alkenyl radical, preferably C ₇ -C ₂₃ linear or branched;
- R'' represents a divalent hydrocarbon radical having less than 6 carbon atoms, preferably 2 to 4 carbon atoms, better still, 3 carbon atoms; And
- R', identical or different, represent a monovalent hydrocarbon radical having less than 6 carbon atoms, preferably 1 to 4 carbon atoms, linear or branched, saturated or unsaturated and substituted or unsubstituted, preferably a methyl radical .

The fatty amidoamines of formula (Va) are, for example, chosen from oleamidopropyl dimethylamine, stearamidopropyl dimethylamine marketed by the company INOLEX CHEMICAL COMPANY under the name LEXAMINE S13, isostearamidopropyl dimethylamine, stearamidoethyl dimethylamine, lauramidopropyl dimethylamine, myristamidopropyl dimethylamine, behenamidopropyl dimethylamine, dilinoleamidopropyl dimethylamine, palmitamidopropyl dimethylamine, ricinoleamindopropyl dimethylamine, soyamidopropyl dimethylamine, avocadoamidopropyl dimethylamine, cocamidopropyl dimethylamine, minkamidopropyl dimethylamine, oatamidopropyl dimethylamine, sesamidopropyl dimethylamine, tallamidopropyl dimethylamine, l olivamidopropyl dimethylamine, palmitamidopropyl dimethylamine, stearamidoethyldiethylamine, brassicamidopropyl dimethylamine and mixtures thereof.

Preferably, the fatty amidoamines are chosen from oleamidopropyl dimethylamine, stearamidopropyl dimethylamine, behenamidopropyl dimethylamine, brassicamidopropyl dimethylamine and mixtures thereof.

Preferably, the cationic surfactants i) are chosen from those of formula (Ia) or (IVa) or (Va), and better still from the salts of cetyltrimethylammonium, behenyltrimethylammonium, dipalmitoylethylhydroxyethylmethylammonium and their mixtures; and more particularly among behenyltrimethylammonium chloride or methosulfate, cetyltrimethylammonium chloride or methosulfate, dipalmitoylethylhydroxyethylmethylammonium chloride or methosulfate, oleamidopropyl dimethylamine, behenamidopropyl dimethylamine, stearamidopropyl dimethylamine, brassicamidopropyl dimethylamine and mixtures thereof and their mixtures.

The total content of the cationic surfactant(s) i) present in the solid composition according to the invention preferably ranges from 0.01 to 15% by weight, preferably from 0.1 to 10% by weight, better still from 0.5 to 8%. % by weight, and better still from 1 to 5% by weight relative to the total weight of the composition.

Starch(s) ii)
The solid composition according to the present invention comprises two or more than two starches ii).

Starches may or may not be modified.

The unmodified starches which can be used in the present invention can originate from all plant sources of starch, in particular cereals and tubers; more particularly it can be corn, rice, cassava, barley, potato, wheat, sorghum, pea, oat, tapioca starches. The hydrolysates of the starches mentioned above can also be used. The unmodified starch preferably comes from corn or potatoes.

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 particularly, these reactions can be carried out in the following way:
- pregelatinization by bursting the starch granules (for example drying and cooking in a drying drum);
- oxidation by strong oxidants leading to the introduction of carboxyl groups into the starch molecule and the depolymerization of the starch molecule (for example by treating an aqueous starch solution with sodium hypochlorite);
- crosslinking by functional agents capable of reacting with the hydroxyl groups of the starch molecules which will thus be linked together (for example with glyceryl and/or phosphate groups);
- esterification in an alkaline medium for the grafting of functional groups, in particular C ₁ to C ₆ acyl (acetyl), C ₁ to C ₆ hydroxyalkyl (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 their mixtures; with Am meaning starch and triethanolamine, 3-amino-1,2-propanediol, ammonium salts 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 such as the product offered under the references PREJEL VA-70-T AGGL (gelatinized hydroxypropyl cassava distarch phosphate) or PREJEL TK1 (gelatinized cassava distarch phosphate) or PREJEL 200 (gelatinized distarch phosphate). gelatinized acetylated cassava) by the AVEBE Company or STRUCTURE ZEA from NATIONAL STARCH (gelatinized corn distarch phosphate).

A preferred modified 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 sulfate type, and preferably carboxylic. The cationic groups can be of the primary, secondary, tertiary or quaternary amine type.

Amphoteric starches are chosen in particular from the compounds of the following formulas:
formulas (VIa) to (IXa), 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, designates 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 described in particular in US 5,455,340 and US 4,017,460.

Starches of formulas (VIIa) or (VIIIa) are particularly used, and preferably starches modified with 2-chloroethylaminodipropionic acid, that is to say starches of formula (VIIa) or (VIIIa) 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.

More particularly, the starches are chosen from corn starches, potato starches, rice starches and modified starches such as those mentioned above, in particular phosphated such as distarch phosphates such as those described above. .

More preferably, said starches comprise one or more unmodified starches, such as corn or potato starch, and one or more modified starches such as a phosphated starch, for example a distarch starch such as those described below. above.

The total content of the starch(s) ii), present in the solid composition according to the invention preferably ranges from 10 to 90% by weight, preferably from 20 to 85% by weight, better still from 30 to ? 80% by weight, and better still from 40 to 75% by weight relative to the total weight of the composition.

In particular, the total content of unmodified starch(s) present in the solid composition according to the invention preferably ranges from 10 to 85% by weight, preferably from 20 to 80% by weight, better still from 30 to 75% by weight. % by weight, relative to the total weight of the composition.

In particular, the total content of modified starch(s), in particular phosphate(s), present in the solid composition according to the invention preferably ranges from 0.1 to 30% by weight, preferably from 0.5 to 20%%. by weight, and better still from 2 to 15% by weight relative to the total weight of the composition.

Liquid fatty substances iii)
The solid composition according to the invention comprises one or more liquid fatty substances iii).

By “fatty substance” is meant an organic compound insoluble in water at 25°C and at atmospheric pressure (1.013.10 ⁵ Pa) (solubility less than 5% by weight, and preferably less than 1% by weight, again more preferably less than 0.1% by weight). They have in their structure at least one hydrocarbon chain comprising at least 6 carbon atoms and/or a chain of at least two siloxane groups. In addition, fatty substances are generally soluble in organic solvents under the same conditions of temperature and pressure, such as for example chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran ( THF), petroleum jelly or decamethylcyclopentasiloxane.

The fatty substances which can be used in the present invention are neither (poly)oxyalkylenated nor (poly)glycerolated.

Preferably, the useful fatty substances according to the invention are non-silicone.

By “non-silicone fatty substance” is meant a fatty substance not containing Si-O bonds and by “silicone fatty substance” a fatty substance containing at least one Si-O bond.

The useful fatty substances according to the invention are liquid fatty substances (or oils). Liquid fatty substance means a fatty substance having a melting point less than or equal to 25°C and at atmospheric pressure (1.013.10 ⁵ Pa).

For the purposes of the present invention, the melting point corresponds to the temperature of the most endothermic peak observed in thermal analysis (differential calorimetric analysis or DSC) as described in standard ISO 11357-3; 1999. The melting point can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name “MDSC 2920” by the company TA Instruments. In the present application, all melting points are determined at atmospheric pressure (1.013.10 ⁵ Pa).

More particularly, the liquid fatty substance(s) according to the invention may be chosen from liquid C ₆ to C ₁₆ hydrocarbons, liquid hydrocarbons comprising more than 16 carbon atoms, non-silicone oils of animal origin, oils of triglyceride type of vegetable or synthetic origin, fluorinated oils, liquid fatty alcohols, liquid esters of fatty acids and/or fatty alcohols other than triglycerides, silicone oils and their mixtures.

It is recalled that alcohols, esters and fatty acids more particularly present at least one hydrocarbon group, linear or branched, saturated or unsaturated, comprising from 6 to 40, better still from 8 to 30 carbon atoms, optionally substituted, in particular by a or several hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds can include one to three carbon-carbon double bonds, conjugated or not.

Concerning the liquid C ₆ to C ₁₆ hydrocarbons, the latter can be linear, branched, optionally cyclic, and are preferably chosen from alkanes. By way of example, mention may be made of hexane, cyclohexane, undecane, dodecane, isododecane, tridecane, isoparaffins such as isohexadecane, isodecane, and their mixtures.

Liquid hydrocarbons comprising more than 16 carbon atoms can be linear or branched, of mineral or synthetic origin, and are preferably chosen from paraffin or petroleum jelly oils, polydecenes, hydrogenated polyisobutene such as Parléam®, and their mixtures.

As hydrocarbon oils (or non-silicone oils) of animal origin, we can cite perhydrosqualene.

The triglyceride oils of vegetable or synthetic origin are preferably chosen from liquid triglycerides of fatty acids containing from 6 to 30 carbon atoms such as the triglycerides of heptanoic or octanoic acids or, for example, sunflower oils, corn oils, soy, squash, grape seeds, sesame, hazelnut, apricot, macadamia, arara, sunflower, castor, avocado, triglycerides from caprylic/capric acids such as those sold by the company Stearineries Dubois or those sold under the names Miglyol® 810, 812 and 818 by the company Dynamit Nobel, jojoba oil, shea butter oil, and their mixtures.

Concerning fluorinated oils, these can be chosen from perfluoromethylcyclopentane and 1,3-perfluorodimethylcyclohexane, sold under the names “FLUTEC® PC1” and “FLUTEC® PC3” by the Company BNFL Fluorochemicals; perfluoro-1,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names “PF 5050®” and “PF 5060®” by the 3M Company, or even bromoperfluorooctyl sold under the name “FORALKYL®” by the Atochem Company; nonafluoro-methoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives, such as 4-trifluoromethyl perfluoromorpholine sold under the name “PF 5052®” by the 3M Company.

The liquid fatty alcohols suitable for implementing the invention are more particularly chosen from saturated or unsaturated, linear or branched, preferably unsaturated or branched alcohols comprising from 6 to 40 carbon atoms, preferably from 8 to 30 atoms. of carbon. These fatty alcohols are neither oxyalkylenated nor glycerolated. Mention may be made, for example, of octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, isostearyl alcohol, oleic alcohol, linolenic alcohol, ricinoleic alcohol, undecylenic alcohol or linoleic alcohol, and mixtures thereof. Preferably we will use oleic alcohol.

With regard to liquid esters of fatty acids and/or fatty alcohols, different from the triglycerides mentioned above, mention may be made in particular of esters of saturated or unsaturated aliphatic mono or polyacids, linear at C ₁ to C ₂₆ or branched at C ₃ to C ₂₆ and saturated or unsaturated aliphatic mono or polyalcohols, linear at C ₁ to C ₂₆ or branched at C ₃ to C ₂₆ , the total carbon number of the esters being greater than or equal to 6, more preferably greater than or equal to at 10.

Preferably, for monoalcohol esters, at least one of the alcohol or acid is branched.

Among the monoesters, we can cite dihydroabietyl behenate; octyldodecyl behenate; isocetyl behenate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; isostearyl octanoate; isocetyl octanoate; octyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; acetyl methyl ricinoleate; octyl isononanoate; 2-ethylhexyl isonate; octyldodecyl erucate; oleyl erucate; ethyl and isopropyl palmitates, such as ethyl-2-hexyl palmitate, 2-octyldecyl palmitate; alkyl myristates such as isopropyl myristate; isobutyl stearate; 2-hexyldecyl laurate, and mixtures thereof.

Preferably among the monoesters of monoacids and monoalcohols, ethyl and isopropyl palmitates, alkyl myristates such as isopropyl or ethyl myristate, isocetyl stearate, isononanoate of ethyl-2-hexyl, isodecyl neopentanoate, isostearyl neopentanoate, and mixtures thereof.

Esters of C ₄ to C ₂₂ di or tricarboxylic acids and C ₁ to C ₂₂ alcohols and esters of mono-, di-, or tricarboxylic acids and di-, tri-alcohols can also be used. -, tetra- or pentahydroxy in C ₂ to C ₂₆ .

We can in particular cite: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di n-propyl adipate; dioctyl adipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate; octyldodecyl stearate; pentaerythrityl monoricinoleate; pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate; pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate; propylene glycol dicaprylate; propylene glycol dicaprate, tridecyl erucate; triisopropyl citrate; triisotearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate, propylene glycol dioctanoate; neopentyl glycol diheptanoate; diethylene glycol diisanonate; polyethylene glycol distearates, and mixtures thereof.

The composition may also comprise, as fatty ester, sugar esters and diesters of C ₆ to C ₃₀ fatty acids, preferably C ₁₂ to C ₂₂ . It is recalled that the term “sugar” means oxygenated hydrocarbon compounds which have several alcohol functions, with or without aldehyde or ketone functions, and which contain at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides or polysaccharides other than the anionic polysaccharides described below.

As suitable sugars, we can cite for example sucrose (or sucrose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose, and their derivatives. particularly alkylated, such as methylated derivatives such as methylglucose.

The esters of sugars and fatty acids can be chosen in particular from the group comprising the esters or mixtures of esters of sugars described above and of C ₆ to C ₃₀ , preferably C ₁₂ to C ₂₂ , linear fatty acids. or branched, saturated or unsaturated. If they are unsaturated, these compounds can include one to three carbon-carbon double bonds, conjugated or not.

The esters can also be chosen from mono-, di-, tri- and tetra-esters, polyesters and mixtures thereof.

These esters can be for example oleate, laurate, palmitate, myristate, behenate, cocoate, stearate, linoleate, linolenate, caprate, arachidonate, or their mixtures such as in particular mixed oleo-palmitate, oleo-stearate, palmito-stearate esters.

More particularly, mono- and diesters are used and in particular mono- or di-oleate, stearate, behenate, oleopalmitate, linoleate, linolenate, oleostearate, of sucrose, glucose or methylglucose, and their mixtures.

As an example, we can cite the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.

The silicone oils which can be used in the composition according to the present invention may be volatile or non-volatile, cyclic, linear or branched, modified or not by organic groups, and preferably have a viscosity of 5.10 ^-6 to 2.5 m ² / s at 25°C, and preferably 1.10 ^-5 to 1 m ² /s.

Preferably, the silicone oils are chosen from polydialkylsiloxanes, in particular polydimethylsiloxanes (PDMS), and liquid polyorganosiloxanes comprising at least one aryl group.

These silicone oils can also be organomodified. The organomodified silicone oils which can be used in accordance with the invention are preferably liquid silicones as defined above and comprising in their structure one or more organofunctional groups fixed via a hydrocarbon group, for example chosen from amino and alkoxy groups.

Organopolysiloxanes are defined in more detail in the work of Walter NOLL “Chemistry and Technology of Silicones” (1968), Academie Press. They can be volatile or non-volatile.

When they are volatile, silicone oils are more particularly chosen from those having a boiling point of between 60°C and 260°C, and more particularly still from:
(i) cyclic polydialkylsiloxanes comprising from 3 to 7, preferably from 4 to 5 silicon atoms. These are, for example, octamethylcyclotetrasiloxane marketed in particular under the name VOLATILE SILICONE® 7207 by UNION CARBIDE or SILBIONE® 70045 V2 by RHODIA, decamethylcyclopentasiloxane marketed under the name VOLATILE SILICONE® 7158 by UNION CARBIDE, and SILBIONE ® 70045 V5 by RHODIA, as well as their mixtures.
We can also cite cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type, such as SILICONE VOLATILE® FZ 3109 marketed by the company UNION CARBIDE.
Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organic compounds derived from silicon, such as the mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1,1'-(hexa -2,2,2',2',3,3'-trimethylsilyloxy) bis-neopentane;
(ii) linear volatile polydialkylsiloxanes having 2 to 9 silicon atoms and having a viscosity less than or equal to 5.10 ^-6 m²/s at 25°C. This is, for example, decamethyltetrasiloxane sold in particular under the name “SH 200” by the company TORAY SILICONE. Silicones falling into this class are also described in the article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, P. 27-32 - TODD & BYERS “Volatile Silicone fluids for cosmetics”.

Non-volatile polydialkylsiloxanes are preferably used.

These silicone oils are more particularly chosen from polydialkylsiloxanes, among which we can mainly cite polydimethylsiloxanes with terminal trimethylsilyl groups. The viscosity of silicones is measured at 25°C according to standard ASTM 445 Appendix C.

Among these polydialkylsiloxanes, the following commercial products may be cited without limitation:
- SILBIONE® oils of the 47 and 70 047 series or MIRASIL® oils marketed by RHODIA such as, for example, oil 70 047 V 500 000;
- oils from the MIRASIL® series marketed by the company RHODIA;
- 200 series oils from the company DOW CORNING such as DC200 having a viscosity of 60,000 mm ² /s;
- VISCASIL® oils from GENERAL ELECTRIC and certain SF series oils (SF 96, SF 18) from GENERAL ELECTRIC.

We can also cite polydimethylsiloxanes with terminal dimethylsilanol groups known under the name dimethiconol (CTFA), such as the 48 series oils from the company RHODIA.

The organomodified silicones which can be used in accordance with the invention are silicones as defined above and comprising in their structure one or more organofunctional groups fixed via a hydrocarbon group.

With regard to liquid polyorganosiloxanes comprising at least one aryl group, they may in particular be polydiphenylsiloxanes, and polyalkyl-arylsiloxanes functionalized by the organofunctional groups mentioned above.

The polyalkylarylsiloxanes are particularly chosen from polydimethyl/methylphenylsiloxanes, linear and/or branched polydimethyl/diphenylsiloxanes with viscosities ranging from 1.10 ^-5 to 5.10 ^-2 m²/s at 25°C.

Among these polyalkylarylsiloxanes, we can cite by way of example the products marketed under the following names:
- SILBIONE® oils from the 70 641 series from RHODIA;
- RHODORSIL® 70 633 and 763 series oils from RHODIA;
- DOW CORNING 556 COSMETIC GRAD FLUID oil from DOW CORNING;
- silicones from the PK series from BAYER such as the PK20 product;
- silicones from the PN, PH series from BAYER such as the PN1000 and PH1000 products;
- certain oils from the SF series from GENERAL ELECTRIC such as SF 1023, SF 1154, SF 1250, SF 1265.

Among the organomodified silicones, mention may be made of polyorganosiloxanes comprising:
- substituted or unsubstituted amino groups such as the products marketed under the name GP 4 Silicone Fluid and GP 7100 by the company GENESEE or the products marketed under the names Q2 8220 and DOW CORNING 929 or 939 by the company DOW CORNING. The substituted amino groups are in particular C ₁ to C ₄ aminoalkyl groups;
- alkoxylated groups,
- hydroxyl groups.

The silicones likely to be used are preferably amine silicones. By amine silicone we designate any silicone comprising at least one primary, secondary, tertiary amine or a quaternary ammonium group.

The weight average molecular masses of these aminated silicones can be measured by Gel Permeation Chromatography (GPC) at room temperature (25°C) in polystyrene equivalent. The columns used are µ styragel columns. The eluent is THF, the flow rate is 1ml/min. 200 μl of a 0.5% solution by weight of silicone in THF are injected. Detection is done by refractometry and UVmetry.

Preferably, the amino silicone(s) capable of being used in the context of the invention are chosen from:

a) polysiloxanes corresponding to formula (A):

in which x' and y' are integers such that the weight average molecular weight (Mw) is between approximately 5,000 and 500,000;

b) amino silicones corresponding to formula (B):
R' _a G _3-a -Si(OSiG ₂ ) _n -(OSiG _b R' _2-b ) _m -O-SiG _3-a -R' _a (B)
in which :
- G, identical or different, denotes a hydrogen atom, a phenyl group, OH, C ₁ -C ₈ alkyl, for example methyl, or C ₁ -C ₈ alkoxy, for example methoxy,
- a, identical or different, designates 0 or an integer from 1 to 3, in particular 0,
- b designates 0 or 1, in particular 1,
- m and n are numbers such that the sum (n + m) varies from 1 to 2000, in particular from 50 to 150, n can designate a number from 0 to 1999, and in particular from 49 to 149 and m can designate a number from 1 to 2000, and in particular from 1 to 10;
- R', identical or different, designates a monovalent radical of formula -C _q H _2q L in which q is a number ranging from 2 to 8, and L is an amine group optionally quaternized chosen from the groups:
-N(R") ₂ ; -N ⁺ (R") ₃ A ^- ; -NR"-QN(R") ₂ and -NR"-QN ⁺ (R") ₃ A ^- ,
in which R", identical or different, denotes hydrogen, phenyl, benzyl, or a monovalent saturated hydrocarbon radical, for example a C ₁ -C ₂₀ alkyl radical; Q denotes a group of formula C _r H _2r , linear or branched, r being an integer ranging from 2 to 6, preferably from 2 to 4; and A- represents a cosmetically acceptable anion, in particular a halide such as fluoride, chloride, bromide or iodide.

Preferably, the amino silicones are chosen from the amino silicones of formula (B). Preferably, the silicone amines of formula (B) are chosen from the silicone amines corresponding to the following formulas (C), (D), (E), (F), (G) and/or (K).

Thus, the amino silicones corresponding to formula (B) can be chosen from, alone or in mixture:

A/ silicones called “trimethylsilylamodimethicone” corresponding to formula (C):

in which m and n are numbers such that the sum (n + m) varies from 1 to 2000, in particular from 50 to 150, n can designate a number from 0 to 1999, and in particular from 49 to 149 and m can designate a number from 1 to 2000, and in particular from 1 to 10.

B/ silicones of formula (D) following:

in which :
- m and n are numbers such that the sum (n + m) varies from 1 to 1000, in particular from 50 to 250 and more particularly from 100 to 200; n being able to designate a number from 0 to 999 and in particular from 49 to 249 and more particularly from 125 to 175 and m being able to designate a number from 1 to 1000, in particular from 1 to 10, more particularly from 1 to 5;
- R ₁ , R ₂ , R ₃ , identical or different, represent a hydroxy or C ₁ -C ₄ alkoxy radical, at least one of the radicals R ₁ to R ₃ designating an alkoxy radical.

Preferably the alkoxy radical is a methoxy radical.

The hydroxy/alkoxy molar ratio preferably ranges from 0.2:1 to 0.4:1 and preferably from 0.25:1 to 0.35:1 and more particularly is equal to 0.3:1.

The weight average molecular mass (Mw) of these silicones preferably ranges from 2000 to 1,000,000, more particularly from 3500 to 200,000.

C/ the following silicones of formula (E):

in which :
- p and q are numbers such that the sum (p+q) varies from 1 to 1000, in particular from 50 to 350, and more particularly from 150 to 250; p can designate a number from 0 to 999 and in particular from 49 to 349 and more particularly from 159 to 239 and q can designate a number from 1 to 1000, in particular from 1 to 10 and more particularly from 1 to 5;
- R ₁ , R ₂ , different, represent a hydroxy or C ₁ -C ₄ alkoxy radical, at least one of the R ₁ or R ₂ radicals designating an alkoxy radical.

Preferably the alkoxy radical is a methoxy radical.

The hydroxy/alkoxy molar ratio generally ranges from 1:0.8 to 1:1.1 and preferably from 1:0.9 to 1:1 and more particularly is equal to 1:0.95.

The weight average molecular mass (Mw) of the silicone preferably ranges from 2000 to 200000 and even more particularly from 5000 to 100000 and more particularly from 10000 to 50000.

Commercial products comprising silicones of structure (D) or (E) may include in their composition one or more other amino silicones whose structure is different from formulas (D) or (E).

A product containing structural amino silicones (D) is offered by the company WACKER under the name BELSIL® ADM 652.

A product containing structural amino silicones (E) is offered by WACKER under the name Fluid WR 1300®.

When these amino silicones are used, a particularly interesting embodiment is their use in the form of an oil-in-water emulsion. The oil-in-water emulsion may include one or more surfactants. The surfactants can be of any nature but preferably cationic and/or non-ionic. The number average size of the silicone particles in the emulsion generally ranges from 3 nm to 500 nanometers. Preferably, in particular as amino silicones of formula (E), microemulsions are used whose average particle size ranges from 5 nm to 60 nanometers (limits included) and more particularly from 10 nm to 50 nanometers (limits included). Thus, according to the invention, it is possible to use the amino silicone microemulsions of formula (E) offered under the names FINISH CT 96 E® or SLM 28020® by the company WACKER.

D/ silicones of the following formula (F):

in which :
- m and n are numbers such that the sum (n + m) varies from 1 to 2000 and in particular from 50 to 150, n can designate a number from 0 to 1999 and in particular from 49 to 149 and m can designate a number from 1 to 2000, and in particular from 1 to 10;
- A designates a linear or branched alkylene radical having from 4 to 8 carbon atoms and preferably 4 carbon atoms. This radical is preferably linear.

The weight average molecular mass (Mw) of these aminated silicones preferably ranges from 2000 to 1000000 and even more particularly from 3500 to 200000.

A silicone meeting this formula is for example XIAMETER MEM 8299 EMULSION from DOW CORNING.

E/ silicones of the following formula (G):

in which :
- m and n are numbers such that the sum (n + m) varies from 1 to 2000 and in particular from 50 to 150, n can designate a number from 0 to 1,999 and in particular from 49 to 149 and m can designate a number from 1 to 2000, and in particular from 1 to 10;
- A designates a linear or branched alkylene radical having from 4 to 8 carbon atoms and preferably 4 carbon atoms. This radical is preferably branched.

The weight average molecular mass (Mw) of these aminated silicones preferably ranges from 500 to 1000000 and even more particularly from 1000 to 200,000.

A silicone meeting this formula is for example DC2-8566 Amino Fluid from DOW CORNING.

c) amino silicones corresponding to formula (H):

in which :
- R ₅ represents a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, and in particular a C ₁ -C ₁₈ alkyl radical, or C ₂ -C ₁₈ alkenyl, for example methyl;
- R ₆ represents a divalent hydrocarbon radical, in particular a C ₁ -C ₁₈ alkylene radical or a divalent C ₁ -C ₁₈ alkyleneoxy radical, for example C ₁ -C ₈ linked to Si by an SiC bond;
- Q ^- is an anion such as a halide ion, in particular chloride or an organic acid salt, in particular acetate;
- r represents an average statistical value ranging from 2 to 20, in particular from 2 to 8;
- s represents an average statistical value ranging from 20 to 200, in particular from 20 to 50.

Such amino silicones are described in particular in US patent 4,185,087.

- d) quaternary ammonium silicones of formula (I):

in which :
- R ₇ , identical or different, represent a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, and in particular a C ₁ -C ₁₈ alkyl radical, a C ₂ -C ₁₈ alkenyl radical or a cycle comprising 5 or 6 carbon atoms, for example methyl;
- R ₆ represents a divalent hydrocarbon radical, in particular a C ₁ -C ₁₈ alkylene radical or a divalent C ₁ -C ₁₈ alkyleneoxy radical, for example C ₁ -C ₈ linked to Si by an SiC bond;
- R ₈ , identical or different, represent a hydrogen atom, a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, and in particular a C ₁ -C ₁₈ alkyl radical, a C ₂ -C ₁₈ alkenyl radical , a radical -R ₆ -NHCOR ₇ ;
- X ^- is an anion such as a halide ion, in particular chloride or an organic acid salt, in particular acetate;
- r represents an average statistical value ranging from 2 to 200, in particular from 5 to 100.

These silicones are for example described in application EP-A-0530974.

e) amino silicones of formula (J):

in which :
- R ₁ , R ₂ , R ₃ and R ₄ , identical or different, denote a C ₁ -C ₄ alkyl radical or a phenyl group,
- R ₅ denotes a C ₁ -C ₄ alkyl radical or a hydroxyl group,
- n is an integer varying from 1 to 5,
- m is an integer varying from 1 to 5, and
- x is chosen such that the amine index varies from 0.01 to 1 meq/g.

f) multiblock polyoxyalkylenated amino silicones, of type (AB) _n , A being a polysiloxane block and B being a polyoxyalkylenated block comprising at least one amine group.

Said silicones are preferably made up of repeating units of the following general formulas:
[-(SiMe ₂ O) _x SiMe ₂ - R -N(R")- R'-O(C ₂ H ₄ O) _a (C ₃ H ₆ O) _b -R'-N(H)-R- ]
or
[-(SiMe ₂ O) _x SiMe ₂ - R -N(R")- R' - O(C ₂ H ₄ O) _a (C ₃ H ₆ O) _b -]
in which :
- a is an integer greater than or equal to 1, preferably ranging from 5 to 200, more particularly ranging from 10 to 100;
- b is an integer between 0 and 200, preferably ranging from 4 to 100, more particularly between 5 and 30;
- x is an integer ranging from 1 to 10000, more particularly from 10 to 5000;
- R" is a hydrogen atom or a methyl;
- R, identical or different, represent a divalent C ₂ -C ₁₂ hydrocarbon radical, linear or branched, optionally comprising one or more heteroatoms such as oxygen; preferably, R denotes an ethylene radical, a linear or branched propylene radical, a linear or branched butylene radical, or a CH ₂ CH ₂ CH ₂ OCH ₂ CH(OH)CH ₂ - radical; preferably R denotes a radical CH ₂ CH ₂ CH ₂ OCH ₂ CH(OH)CH ₂ -;
- R', identical or different, represent a divalent C ₂ -C ₁₂ hydrocarbon radical, linear or branched, optionally comprising one or more heteroatoms such as oxygen; preferably, R' denotes an ethylene radical, a linear or branched propylene radical, a linear or branched butylene radical, or a CH ₂ CH ₂ CH ₂ OCH ₂ CH(OH)CH ₂ - radical; preferably R' designates -CH(CH ₃ )-CH ₂ -.

The siloxane blocks preferably represent 50 and 95% by moles of the total weight of the silicone, more particularly 70 to 85% by moles.

The amine level is preferably between 0.02 and 0.5 meq/g of copolymer in a 30% solution in dipropylene glycol, more particularly between 0.05 and 0.2.

The weight average molecular mass (Mw) of the silicone is preferably between 5000 and 1000000, more particularly between 10000 and 200000.

We can in particular cite the silicones marketed under the names Silsoft A-843 or Silsoft A+ by Momentive.

g) alpha, omega-bis-amino silicones corresponding to the following formula (K):

in which :
- the R radicals, independently of each other, represent a hydrogen atom, an OH group or a linear or branched C ₁ -C ₄ alkyl group,
- the radicals R1, R2, R3 and R4, independently of each other, represent a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ aminoalkyl group;
- x is between 0 and 6; y is between 0 and 6, and
- n is such that the molecular mass by weight (Mw) of the aminated silicone is between 5,000 and 200,000 g/mol.

Preferably, the radicals R are identical and represent CH ₃ (methyl).

Preferably, R1, R2, R3 and R4, independently of each other, represent a hydrogen atom, an alkyl group, preferably saturated linear, C ₁ -C4, better still C ₂ -C ₄ , in particular ethyl; or a C ₂ -C ₄ aminoalkyl group, in particular of structure –(C _a H _2a )-NH ₂ with a = 2 to 4; in particular aminoethyl (-CH ₂ -CH ₂ -NH ₂ ).

Preferably, x is between 1 and 5, better between 2 and 4, even better x=3.

Preferably, y is between 1 and 5, better still between 2 and 4, even better y=3.

Preferably, x=y.

Preferably, n is such that the weight average molecular mass (Mw) of the silicone is between 10,000 and 150,000 g/mol, or even between 15,000 and 100,000 g/mol.

More preferably, the aminated silicone corresponds to formula (K) in which the radicals R represent a methyl group, x = y = 3 and R1, R2, R3 and R4 represent a hydrogen atom; it is then a bis-aminopropyl dimethicone (INCI name).

Preferably, the liquid fatty substance(s) are chosen from vegetable oils such as those defined above, liquid fatty esters such as those defined above, aminated silicones such as amodimethicone and bis-aminated silicones, and their mixtures.

More preferably, they are chosen from sunflower, corn, soy, squash, grape seed, sesame, hazelnut, apricot, macadamia, arara, castor and avocado oils, shea butter oil, isopropyl myristate, coco caprylate/caprate, amino silicones such as amodimethicones and bis-amino silicones and mixtures thereof.

The total content of the liquid fatty substance(s) preferably varies from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, more preferably from 1 to 15% by weight, better still from 2 to 10%, even more preferably from 3 to 9% relative to the total weight of the composition.

Water iv)
The solid composition according to the invention contains water in an amount ranging from 0.1 to 10% by weight relative to the total weight of the composition. Preferably, the water content ranges from 0.5 to 10% by weight, more preferably from 1 to 9% by weight, and better still from 2 to 8% by weight, relative to the total weight of the composition.

Amphoteric or zwitterionic surfactant(s)
The solid composition according to the invention may further comprise one or more amphoteric or zwitterionic surfactants.

In particular, the amphoteric or zwitterionic surfactant(s), preferably non-silicone, used in the 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 chain linear or branched comprising from 8 to 22 carbon atoms, said amine derivatives containing at least one anionic group such as, for example, a carboxylate, sulfonate, sulfate, phosphate or phosphonate group.

Mention may be made in particular of alkyl(C ₈ -C ₂₀ )betaines, alkyl(C ₈ -C ₂₀ )sulphobetaines, alkyl(C ₈ -C ₂₀ )amidoalkyl(C ₁ -C ₆ )betaines, alkyl(C 8 -C 20) ₈ -C ₂₀ )-amidalkyl(C ₁ -C ₆ )sulfobetaines, and mixtures thereof.

Among the derivatives of secondary or tertiary aliphatic amines, optionally quaternized, which can be used, as defined above, we can also cite the following compounds of respective structures (III) and (IV):

R _a -CONHCH ₂ CH ₂ -N ⁺ (R _b )(R _c )-CH ₂ COO ^- , M ⁺ , X ^- (III)
formula (III), 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 counterion from an alkali, alkaline earth metal, such as sodium, an ammonium ion or an ion from an organic amine; And
^- _{​ ​ ​ ​ ​} -C ₄ )aryl sulfonates, in particular methyl sulfate and ethyl sulfate; or M ⁺ and X ^- are absent;

R _a '-CONHCH ₂ CH ₂ -N(B)(B') (IV)
formula (IV), in which:
- B represents the group -CH ₂ CH ₂ OX';
- 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 counterion from an alkali or alkaline earth metal, such as sodium, an ammonium ion or an ion 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.

As an example, we can cite cocoamphodiacetate marketed by the company RHODIA under the trade name MIRANOL ^® C2M concentrate.

We can also use compounds of formula (V):
R _a ''-NHCH(Y'')-(CH ₂ ) _n CONH(CH ₂ ) _n' -N(R _d )(R _e ) (V)
formula (V), 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 each other, represent a C ₁ to C ₄ alkyl or hydroxyalkyl radical;
- Z'' represents a cationic counterion from an alkali or alkaline earth metal, such as sodium, an ammonium ion or an ion 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, designate an integer ranging from 1 to 3.

Among the compounds of formula (V) we can cite 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 cited above, alkyl(C ₈ -C ₂₀ )betaines, such as cocobetaine, alkyl(C ₈ -C ₂₀ )amidoalkyl(C ₃ -C ₈ )betaines, such as as cocamidopropylbetaine, alkyl(C ₈ -C ₂₀ )amphoacetates, alkyl(C ₈ -C ₂₀ )amphodiacetates and their mixtures; and preferably alkyl(C ₈ -C ₂₀ )betaines, alkyl(C ₈ -C ₂₀ )amidoalkyl(C ₃ -C ₈ )betaines and mixtures thereof.

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

Preferably, the solid composition according to the invention comprises one or more amphoteric or zwitterionic surfactants, more preferably chosen from alkyl(C ₈ -C ₂₀ )betaines, alkyl(C ₈ -C ₂₀ )amidoalkyl(C ₃ -C ₈ ) )betaines and their mixtures, and better still among alkyl (C ₈ -C ₂₀ )amidoalkyl (C ₃ -C ₈ )betaines and their mixtures

When one or more amphoteric or zwitterionic surfactants are present in the solid composition according to the invention, their total content preferably ranges from 0.01 to 10% by weight, more preferably from 0.05 to 5% by weight, and better still another 0.1 to 1% by weight, relative to the total weight of the composition.

Cationic polymer(s)
The solid composition according to the invention may further comprise one or more cationic polymers.

For the purposes of the present invention, the term “cationic polymer” means any polymer comprising cationic groups and/or groups that can be ionized into cationic groups. Preferably, the cationic polymer(s) are hydrophilic or amphiphilic.

The cationic polymers are preferably not siliconed (do not include a 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 lateral substituent directly connected thereto.

Preferably the cationic polymers according to the invention do not comprise an anionic group nor a group that can be ionized into anionic groups.

The cationic polymers capable of being used preferably have a weight average molar mass (Mw) of between approximately 500 and 5.10 ⁶ , preferably between approximately 10 ³ and 3.10 ⁶ .

Among the cationic polymers, we can cite more particularly:

(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, designate 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 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 1 to 6 carbon atoms, preferably methyl or ethyl; And
- X designates an anion derived from a mineral or organic acid such as a methosulfate anion or a halide such as chloride or bromide.

The copolymers of family (1) may also contain one or more units deriving from comonomers which may 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, vinyl lactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters.

Among these copolymers of family (1), we can cite:
- copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with a dimethyl halide, such as that sold under the name HERCOFLOC by the company HERCULES,
- copolymers of acrylamide and 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 products sold under the name "GAFQUAT" by the company ISP such as for example "GAFQUAT 734" or "GAFQUAT 755" or 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 vinylpyrrolidone/dimethylaminopropyl methacrylamide 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 dimethylaminoethylmethacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethylmethacrylate quaternized with methyl chloride, the homo- or copolymerization being followed by crosslinking with an olefinically unsaturated compound, in particular methylene bis acrylamide. It is more particularly possible to use a crosslinked acrylamide/methacryloyloxyethyl trimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion comprising 50% by weight of said copolymer in mineral oil. This dispersion is 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, notably inulins, celluloses and cationic galactomannan gums. Among the cationic polysaccharides, mention may be made more particularly of cellulose ether derivatives comprising quaternary ammonium groups, cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and cationic galactomannan gums.

Cellulose ether derivatives comprising quaternary ammonium groups are described in particular in FR 1 492 597, and we can cite 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 ammonium hydroxyethylcellulose reacted with an epoxide substituted with a trimethylammonium group.

Cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer are described in particular in US patent 4,131,576, and mention may be made of hydroxyalkyl celluloses, such as hydroxymethyl-, hydroxyethyl- or hydroxypropyl celluloses grafted in particular. with a salt of methacryloylethyl trimethylammonium, methacrylamidopropyl trimethylammonium, dimethyl-diallylammonium. The products marketed meeting 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 by groups comprising at least one fatty chain, such as linear or branched alkyl groups, linear or branched arylalkyls, linear or branched alkylaryls, preferably linear or branched alkyls, 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, we can cite hydroxyethylcelluloses of formula (VI):

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 (VI), at least one of the radicals R _a , R _b , R _c , R' _a , R' _b , R' _c represents an alkyl, linear or branched, in C ₈ to C ₃₀ ; better in C ₁₀ to C ₂₄ , or even in C ₁₀ to C ₁₄ ; we can in particular cite the dodecyl radical (C ₁₂ ). Preferably, the other radical(s) represent a linear or branched C ₁ to C ₄ alkyl, in particular methyl.

Preferably, in formula (VI), 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 ; we can in particular cite 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 group –N ⁺ (CH ₃ ) ₃ , Q' ^- .

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

Aryl radicals preferably designate phenyl, benzyl, naphthyl or anthryl groups.

We can in particular cite the 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 hydroxyethylcelluloses of formula (VI) 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, we can cite SOFTCAT POLYMER SL ^® polymers such as SL-100, SL-60, SL-30 and SL-5 from the company AMERCHOL /DOW CHEMICAL.

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

Cationic galactomannan gums are described more particularly in patents US 3,589,578 and US 4,031,307, and we can cite 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 linear or branched chains, optionally interrupted by atoms of oxygen, sulfur, nitrogen 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 acidic compound with a polyamine; these polyaminoamides can be crosslinked by 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 even 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, 'an epihalohydrin, 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) polyaminoamide derivatives 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-diacoylaminohydroxyalkyldialoylene triamine polymers in which the alkyl radical contains from 1 to 4 carbon atoms and preferably denotes methyl, ethyl, propyl. Among these derivatives, mention may be made more particularly of the adipic acid/dimethylaminohydroxypropyl/diethylene triamine polymers sold under the name "Cartaretine F, F4 or F8" by the company Sandoz.

(6) the 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 the epichlorohydrin in a molar ratio of epichlorohydrin to the 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 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 (VII) or (VIII):

formulas (VII) and (VIII), 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 each other, designate an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group in which the alkyl group has 1 to 5 carbon atoms, a C amidoalkyl group ₁ to C ₄ ; or R ₁₀ and R ₁₁ can designate, jointly with the nitrogen atom to which they are attached, heterocyclic groups, such as piperidinyl or morpholinyl; R ₁₀ and R ₁₁ , independently of each other, preferably designate an alkyl group having 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 with low weight average molar masses) and the copolymers of salts (for example example chloride) of diallyldimethylammonium and acrylamide sold in particular under the name "MERQUAT 550" or "MERQUAT 7SPR".

(8) quaternary diammonium polymers comprising recurring units of formula (IX):

formula (IX), 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 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 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 several 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 piperazin ring;
furthermore if A ₁ designates a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B ₁ can also designate a group (CH ₂ ) _n -CO-D-OC-(CH ₂ ) _n - in which D designates:
a) a glycol residue of formula -OZO-, where Z designates 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 designate an integer from 1 to 4, representing a defined and unique degree of polymerization or a number any one from 1 to 4 representing an average degree of polymerization;
b) a bis-secondary diamine residue such as a piperazine derivative;
c) a bis-primary diamine residue of formula: -NH-Y-NH-, where Y designates a linear or branched hydrocarbon radical, or 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 100,000.

We can cite more particularly polymers which are made up of recurring units corresponding to formula (X):

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

A particularly preferred compound of formula (X) is that for which R ₁ , R ₂ , R ₃ and R ₄ represent a methyl radical, n=3, p=6 and ).

(9) quaternary polyammonium polymers comprising units of formula (XI):

formula (XI), 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 radical (OCH ₂ CH ₂ ) _p OH, where p is equal to 0 or 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 integers 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 designates a radical of a dihalide or preferably represents -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -.

We can for example cite 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 reasons corresponding to the following formula (A'):

(b) optionally one or more reasons 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 mol% of units corresponding to formula (A') and from 0 to 95 mol% of units corresponding to formula (B '), preferably from 10 to 100 mole % of units corresponding to formula (A') and from 0 to 90 mole % 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 environment.

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.

Polymers comprising units of formula (A) and possibly units of formula (B) are sold in particular under the name LUPAMIN by the company BASF, such as for example, and without limitation, 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 their mixtures, more preferably from cationic galactomannan gums and their mixtures, and better still from cationic guar gums and their mixtures.

Preferably, the solid composition according to the invention comprises one or more cationic polymers.

More preferably, the solid composition according to the invention comprises one or more cationic polymers chosen from cationic polysaccharides (family (2)) and their mixtures, more preferably from cationic galactomannan gums and their mixtures, and better still from guar gums. cationics and their mixtures.

Even more preferably, the solid composition according to the invention comprises one or more cationic polymers chosen from cationic polysaccharides (family (2)), cyclopolymers of alkyl diallyl amine or dialkyl diallyl ammonium (family 7) and their mixtures, even more preferably chosen from mixtures of cationic galactomannan gums and cyclopolymers of alkyl diallyl amine or dialkyl diallyl ammonium, better still chosen from mixtures of cationic guar gums and copolymers of salts (for example chloride) of diallyldimethylammonium and acrylamide.

The total content of the cationic polymer(s), when present in the solid composition according to the invention, is preferably greater than or equal to 0.05% by weight, more preferably 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.

According to a preferred embodiment, the cationic polymer(s) are chosen from cationic polysaccharides (family (2)) and their mixtures, and the total content of the cationic polysaccharide(s), present in the solid composition according to the invention, is preferably greater than or equal to 0.05% by weight, more preferably ranges from 0.05 to 5% by weight, and better still from 0.1 to 2% by weight, or even from 0.2 to 1.5% by weight relative to the total weight of the composition.

Polyol(s)
The solid composition according to the invention may further comprise one or more polyols.

The polyol(s) present in the solid composition of the invention are preferably chosen from the following polyols of formula (XIII):

(XIII)
formula (XIII) in which:
- R' ₁ , R' ₂ , R' ₃ and R' ₄ , identical or different, independently designate a hydrogen atom, an alkyl radical, linear or branched, in C ₁ to C ₆ or a mono or polyhydroxyalkyl radical from C ₁ to C ₆ ,
- A designates an alkyl radical, saturated or unsaturated, linear or branched containing from 1 to 18 carbon atoms, this radical comprises from 0 to 9 oxygen atoms, but no hydroxyl group, and
- m designates 0 or 1.

According to a first embodiment of the invention, the polyol(s) are preferably chosen from polyols of formula (XIII), in which m is 0, and mixtures thereof, and more preferably from propylene glycol (propane-1, 2-diol), 1,2,3-propanetriol, pinacol (2,3-dimethyl 2,3-butanediol), 1,2,3-butanetriol, 2,3-butanediol, glycerin, sorbitol and their mixtures.

According to another embodiment of the invention, the polyol(s) are preferably chosen from polyols of formula (XIII), in which m is 1 and R' ₁ , R' ₂ , R' ₃ , and R' ₄ , identical or different, designate, independently of one another, a hydrogen atom or a C ₁ to C ₆ alkyl radical, and their mixtures. According to this embodiment, the polyol(s) are advantageously chosen from polyethylene glycols and their mixtures, and more particularly the product named PEG-6 or PEG-8 in the work CTFA (International Cosmetic Ingredient Dictionary, Seventh Edition).

According to yet another embodiment of the invention, the polyol(s) are preferably chosen from polyols of formula (XIII), in which m is 1 and R' ₁ , R' ₂ , R' ₃ , and R' ₄ , identical or different, designate, independently of one another, a hydrogen atom or a C ₁ to C ₆ alkyl radical, and whose molecular weight is less than 200, and their mixtures. According to this particular embodiment, the polyol(s) are preferably chosen from 3-methyl-1,3,5-pentanetriol, 1,2,4-butanetriol, 1,5-pentanediol, 2-methyl- 1,3 propanediol, 1,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol (2,2-dimethyl-1,3-propanediol), isoprene glycol (3-methyl-1, 3-butanediol), hexylene glycol (2-methyl-2,4-pentanediol) and their mixtures, and more preferably among hexylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol and their mixtures.

Preferably, the molecular weight (MW) of said polyol(s) present in the solid composition of the invention is between 50 and 350, more preferably between 60 and 200, and better still between 70 and 150.

Preferably, the polyol(s) are chosen from diols, glycerin, and mixtures thereof, more preferably from the compounds of formula (XIII) in which, R' ₁ , R' ₂ , R' ₃ and R' ₄ , identical or different, designate independently of one another a hydrogen atom or a C ₁ to C ₆ alkyl radical, glycerin and their mixtures.

Advantageously, the polyol(s) are chosen from glycerin, propylene glycol (propane-1,2-diol), pinacol (2,3-dimethyl 2,3-butanediol), 2,3-butanediol, polyethylene glycols, 1,5-pentanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, 3-methyl-1,5-pentanediol, neopentylglycol (2,2-dimethyl-1,3-propanediol ), isoprene glycol (3-methyl-1,3-butanediol), hexylene glycol (2-methyl-2,4-pentanediol), dipropylene glycol, and mixtures thereof. Preferably, the polyol is glycerin or propylene glycol.

Preferably the solid composition according to the invention comprises one or more polyols.

The total content of the polyol(s), present in the solid composition according to the invention, preferably ranges from 0.1 to 15% by weight, more preferably from 0.5 to 10% by weight, and better still from 1 to 5%. by weight, relative to the total weight of the composition.

Anti-caking agent(s)
The solid composition according to the invention may further comprise one or more anti-caking agents.

By “anti-caking agent” is meant within the meaning of the present invention a lubricant acting as an anti-caking agent.

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

Among the lubricants which can be used in the solid composition of the invention, mention may in particular be made of silica, in particular anhydrous colloidal silica, sericite, polyamide ( ^Nylon® ), poly-p-alanine and polyethylene powders, powders of tetrafluoroethylene polymers (Teflon ^® ), copolymers of acrylate and dimethicone, stearic acid, metal soaps derived from organic carboxylic acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon 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, and calcium carbonates , fatty acids such as stearic acid, celluloses, particularly crystalline celluloses, and their mixtures.

According to one embodiment, the anti-caking agent(s) 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 their mixtures, 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 anti-caking agent(s) 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 the composition according to the invention comprises one or more anti-caking agents.

The total content of the anti-caking agent(s), when present in the solid composition according to the invention, preferably ranges from 0.1 to 20% by weight, more preferably from 1 to 15% by weight, and better still from 5 at 10% by weight, relative to the total weight of the composition.

Carboxylic acid(s)
The solid composition according to the present invention may further comprise one or more C _1-6 carboxylic acids.

The carboxylic acid(s) preferably correspond(s) to the following formula (XIV):
(XIV)
in which :
A represents a monovalent group when n is 0, or a polyvalent group when n is greater than or equal to 1; A represents a saturated or unsaturated, cyclic or non-cyclic, aromatic or non-aromatic hydrocarbon group, comprising from 1 to 6 carbon atoms, optionally interrupted by one or more heteroatoms, and/or substituted by one or more hydroxy groups and/or or amino; preferably A represents a monovalent C ₁ -C ₆ alkyl or phenyl group, or a polyvalent C ₁ -C ₆ alkylene or phenylene group optionally substituted by one or more hydroxy groups;
n represents an integer ranging from 0 to 10, preferably from 0 to 5, better still from 0 to 2.

More particularly, the carboxylic acid or acids of formula (XIV) are chosen from a-hydroxyacids, in which A represents either a phenyl group, or a C ₁ -C ₆ alkylene group, in particular C ₂ -C ₄ , substituted by one or more hydroxy groups; preferably by an OH group; and n goes from 0 to 2.

More particularly, the C _1-6 carboxylic acid or acids is or are chosen from those of formula (XIV) in which:
n=0 and A represents a C ₁ -C ₆ alkyl group, in particular a C ₂ -C ₄ alkyl group, or a C ₁ -C ₆ alkyl group, in particular a C ₂ -C ₄ alkyl group, substituted by an OH group ; Or
n=0 and A represents a phenyl group, or a phenyl group substituted by an OH group; Or
n = 1 or 2, and A represents a C ₁ -C ₆ alkyl group, in particular C ₂ -C ₄ , di- or trivalent, or a C ₁ -C ₆ alkyl group, in particular C ₂ - C ₄ , di- or trivalent substituted by an OH group.

Even more preferably, the C _1-6 carboxylic acid or acids is or are chosen from salicylic acid, citric acid, glutaric acid and lactic acid, and better still it is citric acid.

Preferably the composition according to the invention comprises one or more C _1-6 carboxylic acids.

When one or more C ₁ -C ₆ carboxylic acids is or are present, their total content ranges from 10 to 30% by weight, preferably from 11 to 25% by weight, and better still from 12 to 20% by weight per relative to the total weight of the composition.

The solid composition according to the invention may also comprise sodium chloride. Its content can range from 0.01 to 5% by weight, more preferably from 0.1 to 3% by weight, and better still from 0.2 to 2% by weight, relative to the total weight of the composition.

The present invention also relates to a method of cosmetic treatment, in particular care, of keratin fibers, in particular human keratin fibers such as hair, comprising the application to said keratin fibers of a solid composition as defined below. Before ; the solid composition being applied directly to said keratin fibers or after having been previously moistened with water.

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

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

Preferably, the solid composition is rinsed after application.

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

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

Conversely, the solid composition of the invention can also be applied directly (that is to say without prior humidification or disintegration) to the damp keratin fibers, then massage/rubbed to disintegrate the particles and obtain a composition liquid. The liquid composition thus obtained can then be rinsed after a possible exposure time.

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

The present invention further relates to the use of a solid composition as defined above for the cosmetic treatment, preferably care, of keratin fibers, in particular human keratin fibers such as 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,
- a solid composition as defined above;
it being understood that the solid composition is found 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 fibers, in particular the hair and/or the scalp. In particular, the conditioning article makes it possible to condition keratin fibers, in particular human keratin fibers such as 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 less than or equal to 35°C is added to the packaging article, the envelope will dissolve and release the solid composition present in one of the cavities of the packaging. 'envelope.

By "lipid-soluble" is meant soluble in a liquid fatty substance as defined below, in particular at a 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.

“Temperature less than or equal to 35°C” means 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 better still 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 solid composition as defined above. Preferably, the packaging article comprises only a single cavity in which the solid composition is contained.

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

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

The weight ratio between the total weight of the solid composition of the invention and the total weight of the envelope 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 their mixtures.

The water-soluble polymer(s) which can be used according to the present invention contain water-soluble units in their skeletons. 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, non-ionic monomers and mixtures thereof.

As water-soluble monomers capable of being used as precursors of water-soluble units, alone or in mixture, the following monomers may be cited by way of example, 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 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,
- dimethyldiallyl ammonium halides (chloride),
- 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 type -OR' where R' is a hydrocarbon radical, linear or branched, saturated or unsaturated, having from 1 to 6 carbons, optionally substituted by at least one halogen atom (iodine, bromine, chlorine, fluorine) ; a sulfonic group (-SO ₃ ^- ), sulfate (SO ₄ ^- ), phosphate (-PO ₄ H ₂ ); hydroxy (-OH); primary amine (-NH ₂ ); secondary amine (NHR ₆ ), tertiary (-NR ₆ R ₇ ) or quaternary (-N ⁺ R ₆ R ₇ R ₈ ) 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 ^- ); sulfate (SO ₄ ^- ); phosphate (-PO ₄ H ₂ ); primary amine (-NH ₂ ); secondary amine (-NHR ₆ ), tertiary (NR ₆ R ₇ ) and/or quaternary (-N ⁺ R ₆ R ₇ R ₈ ) 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, we can cite for example N,N-dimethylacrylamide, and N,N-diethylacrylamide; And
- and their mixtures.

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 or ammonium or those derived from 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 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 ^,
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 pattern: -(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 being able to be interrupted by a ketone function, an amide, an ester (OC(O) or C(O)-O), a urethane, or a urea,
- n is an integer varying from 0 to 1,
• X ^- represents an anionic counterion, such as a chloride or sulfate.

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

Among the water-soluble polymers which can be used according to the present invention, mention may also be made of polyhydroxyalkanoates (PHA), poly(hydroxybutyrate)(PHB), poly(hydroxyvalerate) (PHV), biodegradable polyesters and mixtures thereof.

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 their mixtures.

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) that may be present in the 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 be optionally modified by substitution and/or by oxidation and/or by dehydration . The sugar units capable of entering 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 sulfate, anhydrogalactose sulfate.

The polymers with sugar motif(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 may be mono- or disaccharides.

We can in particular cite as polymers likely to be used, 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 from arabinose, galactose, mannose, xylose and glucuronic acid);
- karaya gum (polymer from galacturonic acid, galactose, rhamnose and glucuronic acid);
- tragacanth (or tragacanth) gum (polymer of galacturonic acid, galactose, fucose, xylose and arabinose);
b) gums from algae including:
- agar (polymer derived from galactose and anhydrogalactose);
- alginates (polymers of mannuronic acid and glucuronic acid);
- carrageenans and furcelleranes (polymers of galactose sulfate and anhydrogalactose sulfate);
c) gums from seeds or tubers including:
- guar gum (mannose and galactose polymer);
- locust bean gum (mannose and galactose polymer);
- fenugreek gum (mannose and galactose polymer);
- tamarind gum (polymer of galactose, xylose and glucose);
- konjac gum (glucose and mannose polymer) 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 branching approximately every 50 or 60 units;
d) microbial gums including:
- xanthan gum (polymer of glucose, mannose acetate, mannose/pyruvic acid and glucuronic acid);
- gellan gum (polymer of partially acylated glucose, rhamnose and glucuronic acid);
- scleroglucan gum (glucose polymer);
- biosaccharide gum (polymer of galacturonic acid, fucose and D-galactose),
e) plant extracts including:
- cellulose (glucose polymer);
- natural or modified starch (glucose polymer) (aluminum starch octenylsuccinate, hydroxypropyl starch phosphates);
- inulin (polymer of fructose and glucose).

These polymers can be modified physically or chemically. As a physical treatment, we can cite in particular temperature. As chemical treatments, we can cite esterification, etherification, amidification and oxidation reactions. These treatments lead to polymers which can 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 which can be used according to the invention can be modified by C ₁ to C ₆ hydroxyl alkyl groups. Among the hydroxyalkyl groups, mention may be made of hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.

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

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

Such nonionic guar gums possibly modified by 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 by cationic groups which can be used more particularly 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 preferably, 5 to 20% of the number of hydroxyl functions of these guar gums are connected by cationic trialkyammonium groups. Among these trialkylammonium groups, we can particularly cite the trimethylammonium and triethylammonium groups. Even more preferably, these groups represent 5 to 20% by weight relative to the total weight of the modified guar gum.

According to the invention, guar gums modified with 2,3-epoxypropyl trimethylammonium chloride can be used.

These guar gums modified by cationic groups are products already known in themselves and are for example described in patents US 3,589,578 and US 4,0131,307. Such products are also sold in particular under the trade names of JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 by the company 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 that can be used in the envelope of the packaging article according to the present invention are the same as that described above for the solid composition.

Preferably, starches of formulas (VIIa) or (VIIIa) will be used in particular; and preferably starches modified with 2-chloroethylaminodipropionic acid, that is to say starches of formula (VIIa) or (VIIIa) 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.

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

Among these derivatives, we distinguish cellulose ethers, cellulose esters and cellulose ether esters.

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

Among the ether esters of cellulose, we can cite hydroxypropyl methylcellulose phthalates and ethylcellulose sulfates.

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 quaternized hydroxyethylcelluloses, crosslinked or not. 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 motif(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; non-ionic 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; non-ionic nonoxynylhydroxyethylcelluloses such as the product AMERCELL HM-1500 sold by the company AMERCHOL; non-ionic alkylcelluloses such as the product BERMOCOLL EHM 100 sold by the company BEROL NOBEL.

As polymers with sugar motif(s) derived from associative guar, mention may be made of hydroxypropyl guars modified by a fatty chain such as the product ESAFLOR HM 22 (modified by a C ₂₂ alkyl chain) sold by the company LAMBERTI; _the product _MIRACARE

The water-soluble polymer(s) with sugar motif(s) which 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 (derivatives) or unmodified form.

Preferably, the said polymer(s) with sugar unit(s) are non-ionic.

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 may be in the form of fibers or in film.

According to a first embodiment, the water-soluble or fat-soluble compound(s) are in the form of fibers. By “fiber” we mean 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 form factor) 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 from 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 used 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.

We can more particularly cite water-soluble fibers which include fibers based on poly(vinyl alcohol) (= PVA), polysaccharide fibers such as glucomannans, starches, celluloses such as carboxymethylcelluloses, polyalginic acid fibers, polylactic acid fibers, and polyalkyleneoxide fibers, as well as mixtures thereof. More preferably the water-soluble fiber(s) used in the invention are chosen from PVA-based fibers.

The fibers of the covering are generally tangled. The term "envelope comprising water-soluble fibers" means an envelope 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, soluble fibers must be in greater quantity than insoluble fibers. The fiber casing must contain at least 60% by weight of soluble fiber, preferably at least 70% and better still at least 80% by weight relative to the total weight of the fibers. It can thus contain, 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 in the envelope.

When the envelope contains insoluble fibers, these can be made of any material usually used as insoluble fibers; it can 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 graphite form, 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 water-soluble polymeric fibers, and more particularly from an interweaving, 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 bond 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 “non-woven” is meant for the purposes of the present invention a substrate comprising fibers, in particular water-soluble polymeric fibers, in which the individual fibers are arranged in a disorderly manner in a sheet-like structure 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 a 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 binding threads or 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 manufactured by wet process 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 non-woven envelope of the packaging article, PVA fibers 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 spinning solution, by dissolving a water-soluble PVA-based polymer in a first organic solvent, spinning the solution in a second organic solvent to obtain solidified filaments and wet drawing of the filaments from which the first solvent is removed 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 manufacturing process. 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 binding technique, such as for example needling, hot binding, calendering. or bonding by hot air jets (in English air through bonding), a technique in which the water-soluble sheet passes through a tunnel into which hot air is blown, or hydrobonding aimed at bonding 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 fibers made from other water-soluble materials can also be used 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 include a mixture of different fibers soluble in water at different temperatures (up to 35°C).

The fibers can be composite, and they can include, for example, a core and a sheath that are not of the same nature, for example made 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 web. 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 may 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 is made up of several films, said films can be assembled, for example glued together, in order to form only one 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 unit 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 for producing polymer films are extrusion of a molten polymer, pouring a solution of a polymer onto 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 which 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 film based on a high molecular weight polymer 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 using any industrial production method, such as a method of casting a polymeric solution based on PVA, a method of extrusion in the presence or absence water, a dry extrusion molding method or a biaxial orientation method.

The packaging item, as well as the envelope, can have any shape appropriate 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, disk, or oval, or square or parallelepiped preferably with rounded corners. The envelope preferably has dimensions allowing it to be gripped between at least two fingers. Thus, it can have for example an ovoid shape of approximately 2 to 10 cm long and approximately 0.5 to 4 cm wide, or a circular disc shape of approximately 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 can have any other shape and dimension appropriate for the intended 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 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 low 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(ies) has an extent 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 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 solid composition into powder is weaker and the transformation of the powder into fluid composition in the hands is done more easily, without formation of agglomerates.

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

Preferably, the film(s) used in the context of the present invention are chosen from synthetic films, such as poly(vinyl alcohol) (=PVA) films, as well as their mixtures.

Preferably, the envelope is made up 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.

Preferably, the film(s) are sealed to form one or more cavities which will include the solid composition of the invention and prevent it from escaping.

Advantageously, the envelope represents 0.5 to 20% by weight, preferably 1 to 15% by weight, more preferably 2 to 10% by weight, better still 4 to 10% by weight, and better still 4 at 8% by weight, relative to the total weight of the packaging article.

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

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

Advantageously, the packaging article comprises from 1 to 8 g, preferably from 2 to 6 g of solid composition; and from 0.1 to 1 g, preferably from 0.2 to 0.7 g of envelope.

The present invention further relates to a method of cosmetic treatment of keratin fibers, in particular human keratin fibers such as hair, comprising a step of implementing a conditioning article as defined above, preferably said cosmetic treatment process includes the following steps:
i) mixing the packaging article in a composition capable of solubilizing, in whole or in part, the envelope of said packaging article,
ii) apply the composition obtained in step i) to the keratin fibers,
iii) possibly leave to stand,
iv) rinsing said keratin fibers, and
v) optionally drying said keratin 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 solubilizing the envelope is water or an aqueous composition, when the packaging article contains mainly or only 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 liquid fatty substances such as lower monoalcohols, for example ethanol, or as polyols, for example propylene glycol or glycerin, when the packaging article contains mainly or only a lipophilic envelope.

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

By way of example, mention may be made more particularly of alcohols 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 articles, as defined above, and the composition capable of solubilizing the packaging article(s) is preferably between 10/90 and 90/10, and more preferably between 10/90 and 50/50. Better yet, this dilution ratio is 20/80.

In particular, the composition obtained at the end of the mixture (step i) of the process) can be applied to dry or wet keratin fibers. It is advantageously left to sit 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 possibly be washed with shampoo, followed by rinsing with water, before being dried or left to dry.

The present invention further relates to the use of a packaging article as defined above for the cosmetic treatment, more particularly the care, of keratin fibers, in particular human keratin fibers such as hair.

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

Examples
In the examples which follow, all quantities are indicated, unless otherwise indicated, as a percentage by weight of active ingredient relative to the total weight of the composition.

Example 1
A composition according to the invention was prepared from the ingredients indicated in Table 1 below:

Composition 1 Behentrimonium chloride 2.4 Corn starch (Zea mays (corn) starch) 43.3 Distarch Phosphate 10 Citric acid 14.8 Soya oil 1 Isopropyl myristate 2 Sunflower oil 0.5 Shea butter (Butyrospermium Parkii Butter) 3 Coco caprylate/caprate 0.5 Cocamidopropyl betaine 0.2 Sodium chloride 0.5 Magnesium carbonate 7 Isopropylic alcohol 0.5 Hydroxypropyl guar hydroxypropyltrimonium chloride 0.8 Water 7 Glycerin 3 Scent 3.5

The powdered ingredients (corn starch, starch phosphate, citric acid, guar) were mixed with stirring in a tank. The liquid ingredients (except the perfume) are heated to a temperature of 40°C. These ingredients are added as a binder to the tank by spraying and mixed. Finally, we add the perfume by spraying and mix. Everything is then dried in an oven at 45°C for 20 hours. After cooling to room temperature, the mixture is ground using a grinder to obtain a powder. We obtain a powder formula with free flow (slope angle = 30°, <35° for excellent flow) and a density of 0.48 and water activity 0.628 (after drying). Particle size before grinding X50%=286µm and after grinding X50%=216µm.

According to the present invention, the slope angle represents the characteristic angle of a pile of powder obtained by mechanically pouring the powder from a funnel and is an indication of the flowability of a powder. As an indication, a sealing powder with difficult flow has a slope angle greater than 55°.

The composition thus prepared was packaged in powder form in a water-soluble PVA-based sachet. The packaging article thus obtained can then be used as a care composition: put it in the palm of the hand, add water to solubilize it and form a cream, then apply to the hair, preferably previously moistened.

The composition is easily distributed over the hair, promotes softening and improves detangling.

Example 2
Compositions A (according to the invention) and B (comparative) were prepared from the ingredients indicated in Table 2 below:

Composition A
(invention) Composition B
(comparative) Water 7 7 Behentrimonium chloride 2.4 2.4 Cocamidopropyl betaine 0.2 0.2 Glycerin 3.0 3.0 Soya oil 1.0 1.0 Isopropyl myristate 2.0 2.0 Sunflower oil 0.5 0.5 Coco caprylate/caprate 0.5 0.5 Shea butter oil 3.0 3.0 Sodium chloride 0.5 0.5 Scent 3.5 3.5 Isopropylic alcohol 0.5 0.5 Hydroxypropyl guar hydroxypropyltrimonium chloride 0.8 0.8 Distarch Phosphate 10 - Corn starch (Zea mays (corn) starch) Qs 100 Qs 100 Magnesium carbonate 7 7 Citric acid 14.8 14.8

The powdered ingredients (corn starch, starch phosphate, citric acid, guar) were mixed with stirring in a tank. The liquid ingredients (except the perfume) are heated to 40°C. These ingredients are added as a binder to the tank by spraying and mixed. Finally, we add the perfume by spraying and mix. Everything is then dried in an oven at 45°C for 20 hours. After cooling to room temperature, the mixture is ground using a grinder to obtain a powder.

Each of compositions A and B was applied directly to strands of moderately sensitized hair (SA20 strands) weighing 2.7 g and moistened. The quantity deposited was 0.35 g per wick. We gently kneaded the lock between the fingers along its entire length.

After an exposure time of 2 minutes, the locks are rinsed.

A panel of people evaluated the disintegration and cosmetic properties of compositions A and B.

Composition A according to the invention disintegrated better than comparative composition B. No lumps were observed on the hair with composition A.

The cosmetic properties in terms of detangling, straightening and suppleness were evaluated sensory, blind, on damp and dried hair.

To assess detangling, the expert assesses the ease of passing a fine comb through the hair, sliding it from root to tip.

The evaluation of smoothness is tactile. The expert grasps the strand between thumb and index finger and slides his fingers along the strand from the upper part to the ends; he assesses if the hair has any rough edges, if it does not catch the fingers.

The strands of hair treated with composition A according to the invention present a better transformation upon application, upon rinsing, detangling, smooth and supple when wet.

Compositions A and B were each packaged in an envelope composed of two layers (1) and (2) forming a unit film, at a rate of 0.35g of powder and 0.02g (94% of powder + 6% of paper).

Layer (1) comprises wood pulp and carboxymethyl cellulose. Layer (2) comprises a vinyl alcohol polymer (PVA).

Disintegration was assessed in the same way as previously.

Composition A packaged in the envelope disintegrated better, in the presence of water, than the comparative composition B packaged in the envelope. No lumps were observed on the hair with composition A packaged in the envelope.

Example 3
Compositions C (according to the invention) and D (comparative) were prepared from the ingredients indicated in Table 3 below:

Composition C
(invention) Composition D
(comparative) Water 7 18.4 Behentrimonium chloride 2.4 2.4 Cocamidopropyl betaine 0.2 0.2 Glycerin 3.0 3.0 Soya oil 1.0 1.0 Isopropyl myristate 2.0 2.0 Sunflower oil 0.5 0.5 Coco caprylate/caprate 0.5 0.5 Shea Butter Oil 3.0 3.0 Sodium chloride 0.5 0.5 Scent 3.5 3.5 Isopropylic alcohol 0.5 0.5 Hydroxypropyl guar hydroxypropyltrimonium chloride 0.8 0.8 Distarch Phosphate 10 10 Corn starch (Zea mays (corn) starch) Qs 100 Qs 100 Magnesium carbonate 7 7 Citric acid 14.8 14.8

The powdered ingredients (corn starch, starch phosphate, citric acid, guar) were mixed with stirring in a tank. The liquid ingredients (except the perfume) are heated to 40°C. These ingredients are added as a binder to the tank by spraying and mixed. Finally, we add the perfume by spraying and mix. Everything is then dried in an oven at 45°C for 20 hours. After cooling to room temperature, the mixture is ground using a grinder to obtain a powder.

Composition C is in the form of a powder, the granules being well separated from each other. The composition according to the invention gives a fairly free powder formula (with a slope angle of 30°), i.e. with excellent flow, with a particle size before grinding X50%=286µm and after grinding X50%=216µm , a density of 0.48 and water activity 0.628 (after drying).

Composition D is amalgamated and is not in powder form (without flow), rather in the form of a paste. This composition is very difficult to leave on the hair even after adding water, because it remains in the form of a block.

Each of compositions C and D was applied directly to moderately sensitized locks (SA20 locks) weighing 2.7 g and moistened. The quantity deposited was 0.35 g per wick. We gently kneaded the lock between the fingers along its entire length.

After an exposure time of 2 minutes, the locks are rinsed.

A panel of people evaluated the disintegration and the cosmetic properties conferred by compositions C and D.

Composition C according to the invention disintegrated better than comparative composition D. No lumps were observed on the hair with composition C.

The cosmetic properties in terms of detangling, straightening and suppleness were evaluated sensory, blind, on damp and dried hair.

To assess detangling, the expert assesses the ease of passing a fine comb through the hair, sliding it from root to tip.

The evaluation of smoothness is tactile. The expert grasps the strand between thumb and index finger and slides his fingers along the strand from the upper part to the ends; he assesses if the hair has any rough edges, if it does not catch the fingers.

The strands of hair treated with composition C according to the invention have improved detangling, smooth feel and flexibility.

Composition C was packaged in an envelope composed of two layers (1) and (2) forming a unit film, at a rate of 0.35g of powder and 0.02g (94% of powder + 6% of paper). Layer (1) comprises wood pulp and carboxymethyl cellulose. Layer (2) comprises a vinyl alcohol polymer (PVA).

Disintegration was assessed in the same way as previously.

Composition C packaged in the envelope disintegrated well and no lumps were observed on the hair with composition C packaged in the envelope.

Claims (18)

Solid composition comprising:
i) one or more cationic surfactants,
(ii) two or more starches,
iii) one or more liquid fatty substances,
iii) from 0.1 to 10% by weight of water relative to the total weight of the composition. Solid composition according to claim 1, characterized in that the cationic surfactant(s) i) is or are chosen from:
quaternary ammonium salts of formula (Ia):

in which :
the groups R ₈ to R ₁₁ , 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 comprising from 8 to 30 carbon atoms, preferably from 12 to 24 carbon atoms; aliphatic groups which may contain heteroatoms such as in particular oxygen, nitrogen, sulfur and halogens; And
X ^- is an anion;
the quaternary ammonium salts of imidazoline of formula (IIa):

in which :
R ₁₂ represents an alkenyl or alkyl group containing 8 to 30 carbon atoms,
R ₁₃ represents a hydrogen atom, a C ₁ -C ₄ alkyl group or an alkenyl or alkyl group containing 8 to 30 carbon atoms,
R ₁₄ represents a C ₁ -C ₄ alkyl group,
R ₁₅ represents a hydrogen atom or a C ₁ -C ₄ alkyl group,
X ^- is an anion;
quaternary di- or triammonium salts of formula (IIIa):

in which :
- R ₁₆ designates an alkyl group comprising from 16 to 30 carbon atoms optionally hydroxylated and/or optionally interrupted by one or more oxygen atoms,
- R ₁₇ designates hydrogen, an alkyl group containing 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 designating hydrogen or an alkyl group comprising 1 to 4 carbon atoms,
- R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ , identical or different, designate hydrogen or an alkyl group comprising 1 to 4 carbon atoms, and
- X ^- is an anion;
quaternary ammonium salts containing one or more ester functions of formula (IVa) following:

in which :
- R ₂₂ is chosen from C ₁ -C ₆ alkyl groups and C ₁ -C ₆ hydroxyalkyl or dihydroxyalkyl groups,
- R ₂₃ is chosen from the group R ₂₆ -C(=O)-; the R ₂₇ hydrocarbon groups in C ₁ -C ₂₂ , linear or branched, saturated or unsaturated; and the hydrogen atom,
- R ₂₅ is chosen from the group R ₂₈ -C(=O)-; the R ₂₉ hydrocarbon groups in C ₁ -C ₆ , 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 -C ₂₁ hydrocarbon groups, linear or branched, saturated or unsaturated,
- r, s and t, identical or different, are integers valued from 2 to 6,
- r1 and t1, identical or different, are 0 or 1,
- y is an integer valued from 1 to 10,
- x and z, identical or different, are integers valued 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 designates R ₂₇ and that when z = 0 then R ₂₅ designates R _29,
amidoamines comprising at least one C6-C30 hydrocarbon chain, preferably corresponding to the following formula (Va):
RCONHR''N(R') ₂ (Va)
in which :
- R represents a linear or branched monovalent hydrocarbon radical, saturated or unsaturated and substituted or unsubstituted, having from 5 to 29 carbon atoms, preferably from 7 to 23 carbon atoms, and in particular a C ₅ -C alkyl radical ₂₉ , preferably C ₇ -C ₂₃ , linear or branched, or a C ₅ -C ₂₉ alkenyl radical, preferably C ₇ -C ₂₃ linear or branched;
- R'' represents a divalent hydrocarbon radical having less than 6 carbon atoms, preferably 2 to 4 carbon atoms, better still, 3 carbon atoms; And
- R', identical or different, represent a monovalent hydrocarbon radical having less than 6 carbon atoms, preferably 1 to 4 carbon atoms, linear or branched, saturated or unsaturated and substituted or unsubstituted, preferably a methyl radical . Solid composition according to claim 1 or 2, characterized in that the cationic surfactant(s) i) is or are chosen from the salts of cetyltrimethylammonium, behenyltrimethylammonium, dipalmitoylethylhydroxyethylmethylammonium and their mixtures; and more particularly among behenyltrimethylammonium chloride or methosulfate, cetyltrimethylammonium chloride or methosulfate, dipalmitoylethylhydroxyethylmethylammonium chloride or methosulfate, oleamidopropyl dimethylamine, stearamidopropyl dimethylamine, behenamidopropyl dimethylamine, brassicamidopropyl dimethylamine, and mixtures thereof. Solid composition according to any one of the preceding claims, characterized in that the total content of the cationic surfactant(s) i) preferably ranges from 0.01 to 15% by weight, preferably from 0.1 to 10% by weight, better still from 0.5 to 8% by weight, and better still from 1 to 5% by weight relative to the total weight of the composition. Solid composition according to any one of the preceding claims, characterized in that the starches ii) comprise one or more unmodified starches and one or more modified starches. Solid composition according to claim 5, characterized in that the unmodified starch is chosen from corn starches, rice starches and potato starches, and the modified starches are chosen from phosphate starches, such as distarch phosphates. Solid composition according to any one of the preceding claims, characterized in that the total content of starches ii) ranges from 10 to 90% by weight, preferably from 20 to 85% by weight, better still from 30 to 80% by weight, and better still from 40 to 75% by weight, relative to the total weight of the composition. Solid composition according to any one of the preceding claims, characterized in that the liquid fatty substance(s) are chosen from vegetable oils, liquid fatty esters of fatty acid and/or fatty alcohol, and their blends, best among sunflower, corn, soybean, squash, grapeseed, sesame, hazelnut, apricot, macadamia, arara, castor and avocado oils, oil shea butter, isopropyl myristate, coco caprylate/caprate, amino silicones such as amodimethicones and bis-amino silicones, and mixtures thereof. Solid composition according to any one of the preceding claims, characterized in that the total content of the liquid fatty substance(s) varies from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, plus preferably from 1 to 15% by weight, better still from 2 to 10%, even more preferably from 3 to 8% by weight relative to the total weight of the composition. Solid composition according to any one of the preceding claims, characterized in that the water content varies from 0.5 to 10% by weight, more preferably from 1 to 9% by weight, and better still from 2 to 8% by weight. relative to the total weight of the composition. Solid composition according to any one of the preceding claims, characterized in that it comprises one or more amphoteric surfactants, preferably chosen from alkyl(C ₈ -C ₂₀ )betaines, alkyl(C ₈ -C ₂₀ )amidoalkyl( C ₃ -C ₈ )betaines and their mixtures. Solid composition according to any one of the preceding claims, characterized in that it comprises one or more cationic polymers, preferably chosen from cationic polysaccharides and their mixtures. Solid composition according to any one of the preceding claims, characterized in that it comprises one or more polyols, preferably chosen from those of formula (XIII) below:

(XIII)
formula (XIII) in which:
- R' ₁ , R' ₂ , R' ₃ and R' ₄ , identical or different, independently designate a hydrogen atom, an alkyl radical, linear or branched, in C ₁ to C ₆ or a mono or polyhydroxyalkyl radical from C ₁ to C ₆ ,
- A designates an alkyl radical, saturated or unsaturated, linear or branched containing from 1 to 18 carbon atoms, this radical comprises from 0 to 9 oxygen atoms, but no hydroxyl group, and
- m designates 0 or 1. Solid composition according to any one of the preceding claims, characterized in that it comprises one or more C _1-6 carboxylic acid(s), preferably corresponding to the following formula (XIV):
(XIV)
in which :
A represents a monovalent group when n is 0, or a polyvalent group when n is greater than or equal to 1; A represents a saturated or unsaturated hydrocarbon group, cyclic or non-cyclic, aromatic or non-aromatic, comprising from 1 to 6 carbon atoms, optionally interrupted by one or more heteroatoms, and/or substituted by one or more hydroxy groups and/ or amino; preferably A represents a monovalent C ₁ -C ₆ alkyl or phenyl group, or a polyvalent C ₁ -C ₆ alkylene or phenylene group optionally substituted by one or more hydroxy groups;
n represents an integer ranging from 0 to 10, preferably from 0 to 5, better still from 0 to 2;
best chosen from salicylic acid, citric acid, glutaric acid and lactic acid. Process for the cosmetic treatment of keratin fibers, in particular human keratin fibers such as hair, comprising the application to said keratin fibers of a solid composition as defined in any one of the preceding claims; the solid composition being applied directly to said keratin fibers or after having been previously moistened with water. Packaging item including:
- an envelope defining at least one cavity, the envelope comprising one or more water-soluble and/or fat-soluble compounds;
- a solid composition as defined in any one of claims 1 to 14;
it being understood that the solid composition is found in one of the cavities defined by the envelope. Method for the cosmetic treatment of keratin fibers, in particular human keratin fibers such as hair, comprising a step of implementing a conditioning article as defined in claim 16, preferably, said cosmetic treatment method comprises the following steps :
i) mixing the packaging article in a composition capable of solubilizing, in whole or in part, the envelope of said packaging article,
ii) apply the composition obtained in step i) to the keratin fibers,
iii) possibly leave to pause,
iv) rinsing said keratin fibers, and
v) optionally drying said keratin fibers. Use of a solid composition as defined in any one of claims 1 to 14 or of a conditioning article as defined in claim 16 for the care of keratin fibers, in particular human keratin fibers such as hair .