FR3130154A1 - Cosmetic composition comprising an amino silicone, a bis-amino silicone and an associative polymer - Google Patents

Abstract

The present invention relates to a cosmetic composition comprising an amino silicone, a bis-amino silicone and an associative polymer. The invention also relates to a process for the cosmetic treatment of keratin materials, in particular the hair, using such a composition and its use for the cosmetic treatment of keratin materials.

Description

Cosmetic composition comprising an amino silicone, a bis-amino silicone and an associative polymer

The present invention relates to a cosmetic composition comprising at least one amino silicone, at least one alpha, omega-bis-amino silicone and at least one associative polymer. The invention also relates to a process for the cosmetic treatment of human keratin materials, in particular keratin fibers such as the hair, comprising the application to said keratin fibers of a composition as defined above. The invention further relates to the use of a composition as defined above for the cosmetic treatment of keratin materials, in particular human keratin fibers such as the hair.

Hair is generally damaged and weakened by the action of external atmospheric agents such as light and bad weather, as well as by mechanical or chemical treatments such as brushing, combing, dyeing, bleaching, perms and/or straightening, even repeated washing.

The hair is thus damaged by these various factors and can in the long run become dry, rough, brittle or dull, in particular in fragile places, and more particularly at the level of the ends.

Thus, to remedy these drawbacks, it is usual to have recourse to hair care which uses compositions intended to condition the hair by providing it with satisfactory cosmetic properties, in particular smoothing, shine, softness, suppleness, lightness, a natural feel and good detangling properties.

These hair care compositions, intended to be applied regularly to the hair, can be, for example, conditioners, masks or serums, and can be in the form of gels, hair lotions and conditioning creams. care more or less thick.

It is in particular known to use compositions in the form of oily serums, containing combinations of silicone or non-silicone oils.

However, such compositions still all too often lead to excessive lubrication of the keratin fibres, which results in a greasy or even sticky feel to them, and a heavy, heavy visual appearance.

In addition, the compositions containing oils, once applied to the hair, frequently lead to effects which are not very pleasant to the touch, in particular the hair tends to be rough and/or to "squeal" (that is to say produce a unpleasant sound effect) especially when rubbing the hair together while sliding the fingers along the hair from root to tip.

Furthermore, the hair treated with such compositions is not easy or quick to dry.

Finally, the immediate benefits provided by such compositions are not always sufficient for the most damaged hair; moreover, they tend to fade quickly and even disappear after shampooing.

The present invention aims to provide compositions which do not have the disadvantages mentioned above, and which are capable of conditioning keratin fibers in a lasting manner, in particular by giving them good cosmetic properties.

This object is achieved by the present invention, the subject of which is in particular a cosmetic composition comprising:
- (i) one or more alpha, omega-bis-amino silicones,
- (ii) one or more amino silicones different from the silicones (i), and
- (iii) one or more associative polymers.

The composition according to the invention makes it possible to confer good cosmetic properties on keratin materials, in particular on keratin fibers, in particular human fibers such as the hair, in particular in terms of disentangling, flexibility, smoothness to the touch and visually, softness, shine, discipline and frizz control.

In addition, the composition according to the invention has good qualities of use. It is easy to apply, to distribute on the keratin fibers and melts on application. It has a pleasant, homogeneous, smooth and unctuous texture.

If necessary, it is easily removed by simply rinsing the keratin fibres, without leaving any feel or greasy appearance.

Even in the absence of rinsing of the composition, when it is used as a leave-on for example, the fibers remain light, unloaded and non-sticky, and have a clean feel.

In addition, this composition has good durability of the effects over time (at least for 24 hours) and good persistence of the effects, for example to at least one shampoo.

In particular, the composition according to the invention makes it possible to confer on the hair, upon application, properties of smooth feel, softness, suppleness and lightness; after 1 shampoo, the level of care provided by the composition according to the invention remains very high, in particular on dry hair, on which it is observed that the smooth (slippery) feel is always present, and in a homogeneous manner from the roots to the tips of the hair.

The composition according to the invention makes it possible to provide good conditioning properties, in particular care properties, to the hair, although it contains a low silicone content and contains little, or even no, cationic surfactants. Preferably, the composition according to the invention does not contain cationic surfactants, in particular the total content of cationic surfactants is less than or equal to 1% by weight relative to the total weight of the composition, preferably 0.1% and even more preferably 0%.

A subject of the invention is also a process for the cosmetic treatment of keratin materials, in particular human keratin fibers such as the hair, comprising the application to said keratin materials, in particular keratin fibers, of a composition as defined above.

Another object of the present invention relates to the use of the composition as defined above for the cosmetic treatment, in particular the conditioning, of keratin fibers, in particular human keratin fibers such as the hair.

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

In the present application, and unless otherwise indicated, the term "at least one" is equivalent to "one or more"; and the limits of a range of values are included in this range, in particular in the expressions “included between” and “ranging from … to …”.

(i) Alpha, omega-bis-amino silicones

The composition according to the present invention comprises one or more alpha, omega-bis-amino silicones, that is to say comprising terminal amino groups; this means that the groups located at the end of the chain (the terminal groups in the alpha and omega positions) comprise an amino group. The amino group can be a primary, secondary or tertiary amine as well as a quaternary ammonium.

Preferably, the composition according to the present invention comprises one or more alpha, omega-bis-amino silicones corresponding to formula (I)

in which :
- the radicals R, independently of each other, represent a hydrogen atom, an OH group or an alkyl group, linear or branched, C1-C4,

- the R ₁ , R ₂ , R ₃ and R ₄ radicals, 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 amino silicone is between 5,000 and 200,000.
Preferably, the radicals R are identical and represent CH ₃ (methyl).
Preferably, R ₁ , R ₂ , R ₃ and R ₄ , independently of each other, represent a hydrogen atom, an alkyl group, preferably linear saturated, C ₁ -C ₄ , better still C2-C4, 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 still between 2 and 4, even better x=3.
Preferably, y is between 1 and 5, better still between 2 and 4, even better still 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.

In a preferred embodiment, the amino silicone corresponds to formula (I) in which R=methyl, x=y=3 and R ₁ =R ₂ =R ₃ =R ₄ =H; it is then a bis-aminopropyl dimethicone (INCI name).

The composition comprises a total content of alpha, omega-bis-amino silicone(s) with amino terminal groups preferably ranging from 0.001 to 10% by weight, preferably from 0.005 to 5% by weight, more preferably 0.01 to 1%, better still from 0.02 to 0.8% by weight, relative to the total weight of the composition.

The composition comprises a total content of alpha, omega-bis-amino silicone(s) of formula (I) preferably ranging from 0.001 to 10% by weight, preferably from 0.005 to 5% by weight, more preferably 0, 01 to 1%, better still from 0.02 to 0.8% by weight, relative to the total weight of the composition.

(ii) Amino silicones

The composition according to the present invention further comprises one or more amino silicones, other than alpha, omega-bis-amino (i) silicones.

Amino silicone denotes any silicone comprising at least one primary, secondary, tertiary amine or a quaternary ammonium group.

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

The amino silicone(s) capable of being used in the context of the invention may be chosen, alone or as a mixture, from:
1) the polysiloxanes corresponding to the formula (A):

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

2) the silicones called "trimethylsilylamodimethicone" corresponding to the 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 possibly denoting a number from 0 to 1999, and in particular from 49 to 149 and m possibly denoting a number from 1 to 2000, and in particular from 1 to 10.

3) silicones of the following formula (D):

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 possibly denoting a number from 0 to 999 and in particular from 49 to 249 and more particularly from 125 to 175 and m possibly denoting 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 2,000 to 1,000,000, more particularly from 3,500 to 200,000.

4) 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 possibly denoting a number from 0 to 999 and in particular from 49 to 349 and more particularly from 159 to 239 and q possibly denoting 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 alkoxy radical in C ₁ -C ₄ , at least one of the radicals R ₁ or R ₂ 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.

A product containing amino silicones of structure (D) is offered by WACKER under the name BELSIL® ADM 652. A product containing amino silicones of structure (E) is offered by WACKER under the name Fluid WR 1300®.

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

5) 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 being able to designate a number from 0 to 1999 and in particular from 49 to 149 and m being able to designate a number from 1 to 2000, and in particular from 1 to 10;
- A denotes 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 amino silicones preferably ranges from 2000 to 1000000 and even more particularly from 3500 to 200000.
A silicone corresponding to this formula is, for example, XIAMETER MEM 8299 EMULSION from DOW CORNING.

6) 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 being able to designate a number from 0 to 1999 and in particular from 49 to 149 and m being able to designate a number from 1 to 2000, and in particular from 1 to 10;
- A denotes 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 amino silicones preferably ranges from 500 to 1,000,000 and even more particularly from 1,000 to 200,000. A silicone corresponding to this formula is, for example, DC2-8566 Amino Fluid from DOW CORNING.

7) amino silicones corresponding to the 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 a C ₂ -C ₁₈ alkenyl radical, 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 Pat. No. 4,185,087.

8) amino silicones of formula (J):

in which :
- R ₁ , R ₂ , R ₃ and R ₄ , which are 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 ranging from 1 to 5,
- m is an integer ranging from 1 to 5, and
- x is chosen such that the amine number varies from 0.01 to 1 meq/g.

9) multiblock polyoxyalkylenated amino silicones, of (AB)n type, A being a polysiloxane block and B being a polyoxyalkylenated block comprising at least one amine group.
Said silicones preferably consist 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 and 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 hydrocarbon radical C ₂ -C ₁₂ , 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 CH ₂ CH ₂ CH ₂ OCH ₂ CH(OH)CH ₂ - radical;
- R′, which are 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 -CH(CH ₃ )-CH ₂ -.
The siloxane blocks preferably represent 50 and 95% by mole of the total weight of the silicone, more particularly from 70 to 85% by mole.
The amine content 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 5,000 and 1,000,000, more particularly between 10,000 and 200,000.
Mention may in particular be made of the silicones marketed under the names Silsoft A-843 or Silsoft A+ by Momentive.

Preferably, the amino silicone(s) are chosen from silicones of formulas A, C, F and G (families 1, 2, 5 and 6) and mixtures thereof, preferably from silicones of formula G and mixtures thereof.

Advantageously, the amino silicone(s) (ii) are present in the composition according to the invention in a total content preferably ranging from 0.001 to 10% by weight, preferably from 0.005 to 5% by weight, more preferably 0.01 to 1 %, better still from 0.02 to 0.8% by weight, relative to the total weight of the composition.

Preferably, the composition according to the invention comprises the amino silicone(s) of formulas A, C, F and G and mixtures thereof, in a total content ranging from 0.001 to 10% by weight, preferably from 0.005 to 5% by weight, more preferentially 0.01 to 1%, better still from 0.02 to 0.8% by weight, relative to the total weight of the composition.

The composition comprises a total content of amine(s) and bis-amine(s) silicone(s) ((i)+(ii)) preferably ranging from 0.001 to 15% by weight, preferably from 0.01 to 5% by weight, more preferably 0.05 to 2% by weight, relative to the total weight of the composition.

Preferably, the composition according to the invention has a weight ratio of total content of bis-amino silicone(s) (i) to total content of amino silicone(s) (ii), i.e. a weight ratio (i)/(ii), greater than or equal to 1, preferably strictly greater than 1; the total contents being expressed by weight relative to the total weight of the composition.

The composition comprises a total content of silicone(s) preferably ranging from 0.001 to 15% by weight, better still from 0.005 to 10% by weight, preferentially from 0.01 to 5% by weight, more preferentially 0.05 to 2% by weight, relative to the total weight of the composition.

(iii) Associative polymer

The composition according to the invention comprises one or more associative polymers. Preferably, the associative polymers are non-ionic.

Within the meaning of the present invention, the term "polymer" means any compound resulting from the polymerization by polycondensation or from the radical polymerization of monomers of which at least one is different from an alkylene oxide and from a monofunctional compound of formula RX, R denoting a C ₁₀ -C ₃₀ alkyl or alkenyl group, optionally hydroxylated, and X denoting a carboxylic acid, amine, amide, hydroxyl or ester group. In particular, all compounds resulting solely from the simple condensation of an alkylene oxide with a fatty alcohol, a fatty ester, a fatty acid, a fatty amide or a fatty amine are excluded.

Within the meaning of the present invention, the term "associative polymer" means an amphiphilic polymer capable, in an aqueous medium, of combining reversibly with itself or with other molecules. It generally comprises in its chemical structure, at least one hydrophilic zone, or group, and at least one hydrophobic zone, or group.

The associative polymers according to the invention are polymers comprising at least one fatty chain comprising from 8 to 30 carbon atoms and whose molecules are capable, in the formulation medium, of associating with each other or with molecules of other compounds. Preferably, the fatty chain contains from 10 to 30 carbon atoms.

A particular case of associative polymers are amphiphilic polymers, that is to say polymers comprising one or more hydrophilic parts or groups which make them soluble in water and one or more hydrophobic zones or groups (comprising at least one chain fat) by which the polymers interact and come together with each other or with other molecules.

By "hydrophobic group" is meant a group or a polymer with a hydrocarbon chain, saturated or not, linear or branched, which can contain one or more heteroatoms such as P, O, N, S, or a radical with a perfluorinated or silicone chain. When it designates a hydrocarbon group, the hydrophobic group contains at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and preferentially from 18 to 30 carbon atoms. Preferably, the hydrophobic hydrocarbon group comes from a monofunctional compound. By way of example, the hydrophobic group can be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol, decyl alcohol or else from a polyalkylenated fatty alcohol such as steareth-100. It can also designate a hydrocarbon-based polymer such as for example polybutadiene.

By "fatty chain" within the meaning of the present invention, is meant an alkyl or alkenyl chain, linear or branched, comprising at least 8 carbon atoms, preferably from 8 to 30 carbon atoms, and even better from 10 to 22 carbon atoms. of carbon.

By “fatty” compound, such as for example a fatty alcohol, a fatty acid or a fatty amide, is meant within the meaning of the present invention, a compound comprising in its main chain at least one hydrocarbon chain, saturated or unsaturated, such as alkyl or alkenyl, comprising at least 8 carbon atoms, preferably from 8 to 30 carbon atoms, and even better from 10 to 22 carbon atoms.

Among the anionic associative polymers, mention may be made in particular of:

- (A) those comprising at least one hydrophilic unit and at least one fatty chain allyl ether unit; and more particularly those:
the hydrophilic unit of which consists of an ethylenically unsaturated anionic monomer, more particularly still of a vinyl carboxylic acid and very particularly of an acrylic acid or a methacrylic acid or mixtures thereof; And
whose fatty chain allyl ether unit corresponds to the monomer of formula (I') below: CH ₂ =C(R')-CH ₂ OB _n R
in which R' denotes H or CH ₃ , B denotes the ethyleneoxy radical, n ranges from 0 to 100, and R denotes a hydrocarbon radical chosen from alkyl, arylalkyl, aryl, alkylaryl and cycloalkyl radicals, comprising from 8 to 30 atoms of carbon, preferably 10 to 24, and more particularly still from 12 to 18 carbon atoms. Preferably, R' denotes H, n=10 and R denotes a stearyl radical (C ₁₈ ).

Among these anionic associative polymers, polymers formed from 20 to 60% by weight of acrylic acid and/or methacrylic acid, from 5 to 60% by weight of (meth)acrylates of C ₁ -C ₄ , from 2 to 50% by weight of fatty chain allyl ether of formula (I'), and from 0 to 1% by weight of a crosslinking agent which is preferably a copolymerizable polyethylenic unsaturated monomer , such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methylene-bis-acrylamide.

Most particularly preferred are the crosslinked terpolymers of methacrylic acid, ethyl acrylate, polyethylene glycol (10 EO) stearyl alcohol ether (Steareth 10), in particular that sold by the company BASF under the name SALCARE SC 80 which is a 30% aqueous emulsion of a crosslinked terpolymer of methacrylic acid, ethyl acrylate and steareth-10-allyl ether (40/50/10), with INCI name Steareth-10 Allyl Ether/Acrylates Copolymer.

- (B) those comprising at least one hydrophilic unit of the olefinic unsaturated carboxylic acid type, and at least one hydrophobic unit of the (C ₁₀ -C ₃₀ ) alkyl ester type of unsaturated carboxylic acid.

Preferably, these polymers are chosen from those whose hydrophilic unit of olefinically unsaturated carboxylic acid type corresponds to the monomer of formula (II) below:

in which R ₁ denotes H, CH ₃ or C ₂ H ₅ , and whose hydrophobic unit of the (C ₁₀ -C ₃₀ ) alkyl ester type of unsaturated carboxylic acid corresponds to the monomer of formula (III) below:

in which R ₂ denotes H, CH ₃ or C ₂ H ₅ , and R ₃ denotes a C ₁₀ -C ₃₀ , preferably C ₁₂ -C ₂₂ , alkyl radical.

(C ₁₀ -C ₃₀ ) alkyl esters of unsaturated carboxylic acids in accordance with the invention include, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate , dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.

Among these anionic associative polymers, use will more particularly be made of polymers formed from a mixture of monomers comprising: (i) (meth)acrylic acid, (ii) an ester of formula (III) described above and in which R ₂ denotes H or CH ₃ , R ₃ denotes an alkyl radical having from 12 to 22 carbon atoms, and optionally (iii) a crosslinking agent, which is a well-known copolymerizable polyethylenic unsaturated monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate, and methylene-bis-acrylamide.

Among this type of anionic associative polymers, those consisting of 95 to 60% by weight of (meth)acrylic acid, 4 to 40% by weight of C ₁₀ -C ₃₀ alkyl acrylate, and 0 to 6% by weight of crosslinking polymerizable monomer, or else those consisting of 98 to 96% by weight of (meth)acrylic acid, 1 to 4% by weight of C ₁₀ -C ₃₀ and 0 alkyl acrylate, 1 to 0.6% by weight of crosslinking polymerizable monomer such as those described previously.

Mention may in particular be made of the products sold by the company LUBRIZOL under the trade names PEMULEN TR1, PEMULEN TR2, CARBOPOL 1382, CARBOPOL ETD 2020, CARBOPOL ULTREZ 20, CARBOPOL ULTREZ 21, the INCI name Acrylates/C10-30 Alkyl Acrylate Crosspolymer, and even more preferably PEMULEN TR1 and CARBOPOL 1382.

- (C) maleic anhydride/C ₃₀ -C ₃₈ α-olefin/alkyl maleate terpolymers such as maleic anhydride/C ₃₀ -C ₃₈ α-olefin/isopropyl maleate copolymer, in particular that sold under the name PERFORMA V 1608 by the company NEWPHASE TECHNOLOGIES (INCI name: C30-38 Olefin/Isopropyl Maleate/MA Copolymer).

- (D) acrylic terpolymers comprising (a) 20 to 70% by weight of an α,β-monoethylenically unsaturated carboxylic acid, (b) 20 to 80% by weight of an α,β-monoethylenically unsaturated monomer non-surfactant different from (a), and (c) 0.5 to 60% by weight of a non-ionic mono-urethane which is the reaction product of a monohydric surfactant with a monoethylenically unsaturated monoisocyanate.
Mention may in particular be made of the terpolymer methacrylic acid/methyl acrylate/dimethyl metaisopropenyl benzyl isocyanate of ethoxylated behenyl alcohol (40 EO), in particular in aqueous dispersion at 25% such as the product VISCOPHOBE DB1000 sold by the company AMERCHOL (DOW CHEMICAL) of INCI name Polyacrylate-3.

- (E) copolymers comprising among their monomers (i) an α,β-monoethylenically unsaturated carboxylic acid, such as acrylic or methacrylic acid, and (ii) an α,β-monoethylenically unsaturated carboxylic acid ester , in particular acrylic or methacrylic, and fatty alcohol in particular C8-C32 oxyalkylenated, in particular comprising 2 to 100 moles of ethylene oxide, in particular 4 to 50, or even 10 to 40 EO.

Mention may in particular be made, as monomers, of behenyl or stearyl (meth)acrylates, comprising 10 to 40 EO, in particular 18 to 30 EO.

Preferably, these compounds also comprise as monomer an ester of an α,β-monoethylenically unsaturated carboxylic acid and of a C1-C4 alcohol, in particular a C1-C4 alkyl (meth)acrylate.

Preferably, these copolymers comprise at least one (meth)acrylic acid monomer, at least one C1-C4 alkyl (meth)acrylate monomer and at least one oxyethylenated C8-C32 alkyl (meth)acrylate monomer comprising 2 to 100 moles EO, in particular 4 to 50 EO, or even 10 to 40 EO.

By way of examples, mention may be made of ACULYN 22 sold by the company ROHM and HAAS, which is a terpolymer of methacrylic acid/ethyl acrylate/oxyalkylenated stearyl methacrylate (INCI name Acrylates/Steareth-20 Methacrylate Copolymer), or also ACULYN 28 sold by ROHM and HAAS, which is a terpolymer of methacrylic acid/ethyl acrylate/oxyalkylenated behenyl methacrylate (INCI name Acrylates/Beheneth-25 Methacrylate Copolymer), as well as NOVETHIX L-10 POLYMER sold by Lubrizol.

- (F) associative polymers comprising at least one ethylenically unsaturated monomer containing a sulphonic group, in free or partially or totally neutralized form and comprising at least one hydrophobic part.

Among the polymers of this type, there may be mentioned more especially
-crosslinked or non-crosslinked copolymers, neutralized or not, comprising from 15 to 60% by weight of AMPS units (2-acrylamido-2-methylpropanesulfonic acid or salt) and from 40 to 85% by weight of units (C8-C16) alkyl (meth) acrylate with respect to the polymer, as described in application EP-A-750899
- the terpolymers comprising from 10 to 90% by mole of acrylamide units, from 0.1 to 10% by mole of AMPS units and from 5 to 80% by mole of n-(C6-C8)alkylacrylamide units, such as those described in patent US5089578
- copolymers of fully neutralized AMPS and dodecyl methacrylate as well as uncrosslinked and crosslinked copolymers of AMPS and n-dodecylmethacrylamide
- copolymers consisting of AMPS units and steareth-25 methacrylate units such as ARISTOFLEX HMS marketed by the company CLARIANT, (INCI name Ammonium Acryloyldimethyltaurate / Steareth-25 Methacrylate Crosspolymer) or beheneth-25 methacrylate, such as ARISTOFLEX HMB (INCI name Ammonium Acryloyldimethyltaurate/Beheneth-25 Methacrylate Crosspolymer) marketed by the company CLARIANT, or else steareth-8 methacrylate, such as ARISTOFLEX SNC from CLARIANT (INCI name ammonium acryloyldimethyltaurate/steareth-8 methacrylate copolymer).

- (G) associative polymers comprising at least one vinyllactam monomer and at least one α,β-monoethylenically unsaturated carboxylic acid monomer such as terpolymers of vinylpyrrolidone, acrylic acid and C ₁ -C ₂₀ alkyl methacrylate , for example lauryl, such as that marketed by the company ISP under the name ^ACRYLIDONE® LM (INCI name VP/Acrylates/Lauryl Methacrylate Copolymer).

Among the cationic associative polymers, mention may be made of:
- (A') cationic associative polyurethanes, which can be represented by the following general formula (Ia): RX-(P) _n -[L-(Y) _m ] _r -L'-(P') _p -X '-R'
in which :
R and R′, which are identical or different, represent a hydrophobic group or a hydrogen atom;
X and X', identical or different, represent a group comprising an amine function bearing or not a hydrophobic group, or else the group L";
L, L' and L", identical or different, represent a group derived from a diisocyanate;
P and P', identical or different, represent a group comprising an amine function bearing or not a hydrophobic group;
Y represents a hydrophilic group;
r is an integer comprised between 1 and 100 inclusively, preferably between 1 and 50 inclusively and in particular between 1 and 25 inclusively,
n, m, and p are each independently of the others between 0 and 1000 inclusive;
the molecule containing at least one protonated or quaternized amine function and at least one hydrophobic group.

Preferably, the only hydrophobic groups are the R and R' groups at the chain ends.

A preferred family of cationic associative polyurethanes is that corresponding to formula (Ia) described above in which:
R and R' both independently represent a hydrophobic group,
X, X' each represent a group L'',
n and p are integers which are inclusive between 1 and 1000 and
L, L', L'', P, P', Y and m have the meaning indicated above.

Another preferred family of cationic associative polyurethanes is that corresponding to formula (Ia) above in which:
n=p=0 (the polymers do not contain units derived from an amine functional monomer, incorporated into the polymer during polycondensation),
the protonated amine functions result from the hydrolysis of isocyanate functions, in excess, at the end of the chain, followed by the alkylation of the primary amine functions formed by alkylating agents with a hydrophobic group, that is to say compounds of RQ or R'Q type, in which R and R' are as defined above and Q denotes a leaving group such as a halide, a sulphate, etc.

Yet another preferred family of cationic associative polyurethanes is that corresponding to formula (Ia) above in which:
R and R' both independently represent a hydrophobic group,
X and X' both independently represent a group comprising a quaternary amine,
n = p = 0, and
L, L', Y and m have the meaning indicated above.

The number-average molecular mass (Mn) of the cationic associative polyurethanes is preferably between 400 and 500,000 inclusive, in particular between 1,000 and 400,000 inclusive and ideally between 1,000 and 300,000 inclusive.

Preferably, the hydrocarbon group comes from a monofunctional compound.

By way of example, the hydrophobic group can come from a fatty alcohol such as stearyl alcohol, dodecyl alcohol, decyl alcohol. It can also designate a hydrocarbon-based polymer such as for example polybutadiene.

When X and/or X' denote a group comprising a tertiary or quaternary amine, X and/or X' can represent one of the following formulas:
in which :
R ₂ represents an alkylene radical having from 1 to 20 carbon atoms, linear or branched, whether or not comprising a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced by a heteroatom chosen from N, S, O, P;
R ₁ and R ₃ , which are identical or different, denote a linear or branched C ₁ -C ₃₀ alkyl or alkenyl radical, an aryl radical, it being possible for at least one of the carbon atoms to be replaced by a heteroatom chosen from N, S, O, P;
A ^- is a physiologically acceptable anionic counterion such as a halide such as a chloride or bromide, or a mesylate.

The groups L, L' and L" represent a group of formula:
in which :
Z represents -O-, -S- or -NH-; And
R ₄ represents an alkylene radical having from 1 to 20 carbon atoms, linear or branched, whether or not comprising a saturated or unsaturated ring, an arylene radical, one or more of the carbon atoms possibly being replaced by a heteroatom chosen from N, S , O and P.

The groups P and P', comprising an amine function can represent at least one of the following formulas:

in which :
R ₅ and R ₇ have the same meanings as R ₂ defined previously;
R ₆ , R ₈ and R ₉ have the same meanings as R ₁ and R ₃ defined previously;
R ₁₀ represents an optionally unsaturated linear or branched alkylene group which may contain one or more heteroatoms chosen from N, O, S and P,
and A ^- is a physiologically acceptable anionic counterion such as the halide such as chloride or bromide or mesylate.

With regard to the meaning of Y, the term “hydrophilic group” means a polymeric or non-polymeric water-soluble group.

By way of example, mention may be made, when it is not a question of polymers, of ethylene glycol, diethylene glycol and propylene glycol.

In the case of a hydrophilic polymer, mention may be made, by way of example, of polyethers, sulphonated polyesters, sulphonated polyamides, or a mixture of these polymers. Preferably, the hydrophilic compound is a polyether and in particular a poly(ethylene oxide) or poly(propylene oxide).

The cationic associative polyurethanes of formula (Ia) according to the invention are formed from diisocyanates and various compounds possessing labile hydrogen functions. The labile hydrogen functions can be alcohol, primary or secondary amine or thiol functions giving, after reaction with the diisocyanate functions, respectively polyurethanes, polyureas and polythioureas. The term "polyurethanes" of the present invention encompasses these three types of polymers, namely polyurethanes proper, polyureas and polythioureas as well as copolymers thereof.

A first type of compound entering into the preparation of the polyurethane of formula (Ia) is a compound comprising at least one unit with an amine function. This compound can be multifunctional, but preferably the compound is difunctional, that is to say that according to a preferred embodiment, this compound comprises two labile hydrogen atoms carried for example by a hydroxyl function, primary amine, secondary amine or thiol. It is also possible to use a mixture of multifunctional and difunctional compounds in which the percentage of multifunctional compounds is low.

As indicated above, this compound may contain more than one unit with an amine function. It is then a polymer bearing a repetition of the unit with an amine function.

This type of compounds can be represented by one of the following formulas:
HZ-(P) _n -ZH, or HZ-(P') _p -ZH, in which Z, P, P', n and p are as defined above.

By way of example, mention may be made of N-methyldiethanolamine, N-tert-butyl-diethanolamine and N-sulfoethyldiethanolamine.

The second compound entering into the preparation of the polyurethane of formula (Ia) is a diisocyanate corresponding to the formula: O=C=NR ₄ -N=C=O in which R ₄ is defined above.

By way of example, mention may be made of methylenediphenyl-diisocyanate, methylenecyclohexanediisocyanate, isophoronediisocyanate, toluenediisocyanate, naphthalenediisocyanate, butanediisocyanate, hexanediisocyanate.

A third compound entering into the preparation of the polyurethane of formula (Ia) is a hydrophobic compound intended to form the terminal hydrophobic groups of the polymer of formula (Ia).

This compound consists of a hydrophobic group and a labile hydrogen function, for example a hydroxyl, primary or secondary amine, or thiol function.

By way of example, this compound can be a fatty alcohol, such as stearyl alcohol, dodecyl alcohol, decyl alcohol. When this compound comprises a polymeric chain, it may be, for example, alpha-hydroxylated hydrogenated polybutadiene.

The hydrophobic group of the polyurethane of formula (Ia) can also result from the quaternization reaction of the tertiary amine of the compound comprising at least one tertiary amine unit. Thus, the hydrophobic group is introduced by the quaternizing agent. This quaternizing agent is a compound of the RQ or R'Q type, in which R and R' are as defined above and Q designates a leaving group such as a halide, a sulphate etc.

The cationic associative polyurethane can further comprise a hydrophilic block. This sequence is provided by a fourth type of compound used in the preparation of the polymer. This compound can be multifunctional. It is preferably difunctional. It is also possible to have a mixture where the percentage of multifunctional compound is low.

The labile hydrogen functions are alcohol, primary or secondary amine, or thiol functions. This compound can be a polymer terminated at the ends of the chains by one of these labile hydrogen functions.

By way of example, mention may be made, when it is not a question of polymers, of ethylene glycol, diethylene glycol and propylene glycol.

In the case of a hydrophilic polymer, mention may be made, by way of example, of polyethers, sulphonated polyesters, sulphonated polyamides, or a mixture of these polymers. Preferably, the hydrophilic compound is a polyether and in particular a poly(ethylene oxide) or poly(propylene oxide).

The hydrophilic group denoted Y in formula (Ia) is optional. In fact, the units with a quaternary or protonated amine function may be sufficient to provide the solubility or the hydrodispersibility necessary for this type of polymer in an aqueous solution.

Although the presence of a hydrophilic Y group is optional, however, cationic associative polyurethanes having such a group are preferred.

- (B') quaternized cellulose derivatives, and in particular:
- i) quaternized celluloses modified with groups comprising at least one fatty chain, such as linear or branched alkyl, linear or branched arylalkyl, linear or branched alkylaryl comprising at least 8 carbon atoms, or mixtures thereof ;

- ii) quaternized hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as linear or branched alkyl, linear or branched arylalkyl, linear or branched alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof ;

- iii) hydroxyethylcelluloses of formula (Ib):

in which :
R and R', identical or different, represent an ammonium group R _a R _b R _c N ⁺ -, Q ^- in which R _a , R _b , R _c , identical or different, represent a hydrogen atom, an alkyl group, linear or branched, C ₁ -C ₃₀ preferably C ₁ -C ₂₀ , such as methyl or dodecyl; and Q- represents an anionic counterion such as a halide such as chloride or bromide; And
n, x and y, identical or different, represent an integer between 1 and 10000.

The alkyl radicals carried by the quaternized celluloses i) or hydroxyethylcelluloses ii) above preferably contain from 8 to 30 carbon atoms. The aryl radicals preferably designate the phenyl, benzyl, naphthyl or anthryl groups.

Mention may be made, as examples of quaternized alkylhydroxyethylcelluloses with C ₈ -C ₃₀ fatty chains, of the product QUATRISOFT LM 200, marketed by the company AMERCHOL/DOW CHEMICAL (INCI name Polyquaternium-24) and the products CRODACEL QM (INCI name PG-Hydroxyethylcellulose Cocodimonium Chloride), CRODACEL QL (C ₁₂ alkyl) (INCI name PG-Hydroxyethylcellulose Lauryldimonium Chloride) and CRODACEL QS (C18 alkyl) (INCI name PG-Hydroxyethylcellulose Stearyldimonium Chloride) marketed by the company CRODA.

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

More particularly, the polymers of formula (Ib) are those whose viscosity is between 2000 and 3000 cPs inclusive. Preferably, the viscosity is inclusively between 2700 and 2800 cPs. Typically SOFTCAT POLYMER SL-5 has a viscosity of 2500 cPs, SOFTCAT POLYMER SL-30 has a viscosity of 2700 cPs, SOFTCAT POLYMER SL-60 has a viscosity of 2700 cPs and SOFTCAT POLYMER SL-100 has a viscosity of 2800 cps.

- (C′) cationic polyvinyllactams, in particular those comprising:
- a) at least one monomer of the vinyllactam or alkylvinyllactam type;
- b) at least one monomer of the following structures (Ic) or (IIc):

in which :
X denotes an oxygen atom or an NR6 radical,
R1 and R6 denote, independently of each other, a hydrogen atom or a linear or branched C1-C5 alkyl radical,
R2 denotes a linear or branched C1-C4 alkyl radical,
R3, R4 and R5 denote, independently of one another, a hydrogen atom, a linear or branched C1-C30 alkyl radical or a radical of formula (IIIc):
in which :
Y, Y1 and Y2 denote, independently of one another, a linear or branched C2-C16 alkylene radical,
R7 denotes a hydrogen atom, or a linear or branched C1-C4 alkyl radical or a linear or branched C1-C4 hydroxyalkyl radical,
R8 denotes a hydrogen atom or a linear or branched C1-C30 alkyl radical,
p, q and r denote, independently of each other, either the value zero or the value 1,
m and n denote, independently of each other, an integer ranging inclusively from 0 to 100,
x denotes an integer ranging inclusively from 1 to 100,
Z denotes an anionic counterion of organic or mineral acid, such as the halide such as chloride or bromide or mesylate;
provided that :
- at least one of the substituents R3, R4, R5 or R8 denotes a linear or branched C9-C30 alkyl radical,
- if m or n is different from zero, then q is equal to 1,
- if m or n are equal to zero, then p or q is equal to 0.

The cationic poly(vinyllactam) polymers according to the invention can be crosslinked or non-crosslinked and can also be block polymers.

Preferably, the counterion Z- of the monomers of formula (Ic) is chosen from halide ions, phosphate ions, methosulfate ion, tosylate ion.

Preferably R3, R4 and R5 denote, independently of one another, a hydrogen atom or a linear or branched C1-C30 alkyl radical.

More preferentially, the monomer b) is a monomer of formula (Ic) for which, preferentially, m and n are equal to zero.

The vinyllactam or alkylvinyllactam monomer is preferably a compound of structure (IVc):

in which s denotes an integer ranging from 3 to 6; R9 denotes a hydrogen atom or a linear or branched C1-C5 alkyl radical and R10 denotes a hydrogen atom or a linear or branched C1-C5 alkyl radical, provided that at least one of the radicals R9 and R10 denotes a hydrogen atom.

Even more preferentially, the monomer (IVc) is vinylpyrrolidone.

The cationic poly(vinyllactam) polymers according to the invention can also contain one or more additional monomers, preferably cationic or nonionic.

As particularly preferred compounds, mention may be made of the following terpolymers comprising at least:
a)-a monomer of formula (IVc),
b) a monomer of formula (Ic) in which p=1, q=0, R3 and R4 denote, independently of one another, a hydrogen atom or a C1-C5 alkyl radical and R5 denotes a linear or branched C9-C24 alkyl radical and
c) a monomer of formula (IIc) in which R3 and R4 denote, independently of one another, a hydrogen atom or a linear or branched C1-C5 alkyl radical.

Even more preferably, terpolymers comprising, by weight, 40 to 95% of monomer (a), 0.1 to 55% of monomer (c) and 0.25 to 50% of monomer (b) will be used. Such polymers are described in particular in patent application WO-00/68282.

As cationic poly(vinyllactam) polymers according to the invention, the following are used in particular:
- vinylpyrrolidone/dimethylaminopropylmethacrylamide/dodecyldimethylmethacrylamidopropylammonium tosylate terpolymers,
- vinylpyrrolidone/dimethylaminopropylmethacrylamide/cocoyldimethylmethacrylamidopropylammonium tosylate terpolymers,
- vinylpyrrolidone/dimethylaminopropylmethacrylamide/tosylate or lauryldimethylmethacrylamidopropylammonium chloride terpolymers.

The vinylpyrrolidone/dimethylaminopropyl methacrylamide/lauryl dimethylmethacrylamidopropylammonium chloride terpolymer is in particular offered by the company ISP under the names Styleze W10 or Styleze W20L (INCI name Polyquaternium-55).

The molecular mass by weight (Mw) of the cationic poly(vinyllactam) polymers is preferably between 500 and 20,000,000, more particularly between 200,000 and 2,000,000 and preferentially between 400,000 and 800,000.

- (D') cationic polymers obtained by polymerization of a mixture of monomers comprising one or more vinyl monomers substituted by one or more amino groups, one or more hydrophobic nonionic vinyl monomers, and one or more associative vinyl monomers, such as described in patent application WO2004/024779.

Among these polymers, mention may more particularly be made of the products of the polymerization of a mixture of monomers comprising:
- a di(C1-C4 alkyl)amino(C1-C6 alkyl) methacrylate,
- one or more C1-C30 alkyl esters and (meth)acrylic acid,
- a polyethoxylated C10-C30 alkyl methacrylate (20-25 moles of ethylene oxide unit),
- a 30/5 polyethylene glycol/polypropylene glycol allyl ether,
- a hydroxy(C2-C6 alkyl) methacrylate, and
- an ethylene glycol dimethacrylate.

Such a polymer is, for example, the compound marketed by the company LUBRIZOL under the name CARBOPOL AQUA CC and which corresponds to the INCI name Polyacrylate-1 crosspolymer.

The nonionic associative polymers are preferably chosen from, alone or as a mixture:

(1) Cellulose modified with groups comprising at least one fatty chain, in particular C8-C32 alkyl, better still C14-C28; preferably from:
- hydroxyethylcelluloses modified with groups comprising at least one fatty chain such as alkyl, arylalkyl, alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C ₈ -C ₂₂ , such as cetylhydroxyethyl cellulose marketed in particular under the reference NATROSOL PLUS GRADE 330 CS (C ₁₆ alkyls) sold by the company Ashland, or the product Polysurf 67CS sold by the company Ashland,
- hydroxyethylcellulosess modified with polyalkylene glycol ether alkyl phenol groups, such as the product AMERCELL POLYMER HM-1500 (polyethylene glycol (15) ether of nonyl phenol) sold by the company AMERCHOL,
- and mixtures thereof.

(2) Hydroxypropylguars modified with groups comprising at least one fatty chain, in particular C8-C32 alkyl, better still C14-C28, better still C22, C20 or C14, such as the product ESAFLOR HM ₂₂ (C22 alkyl chain) sold by the company LAMBERTI, the products RE210-18 (C ₁₄ alkyl chain) and RE205-1 (C ₂₀ alkyl chain) sold by the company RHODIA.

(3) Copolymers of vinylpyrrolidone and fatty chain hydrophobic monomers, in particular C8-C32 alkyl, better still C14-C28 alkyl. We can cite as an example:
- the vinylpyrrolidone/hexadecene copolymer and in particular the ANTARON V216 or GANEX V216 products sold by the company ISP
- the vinylpyrrolidone/eicosene copolymer and in particular the ANTARON V220 or GANEX V220 products sold by the company ISP

(4) Copolymers of C ₁ -C ₆ alkyl methacrylates or acrylates and of amphiphilic monomers comprising at least one fatty chain, in particular C8-C32 alkyl, better still C14-C28, such as for example the acrylate copolymer of methyl/oxyethylenated stearyl acrylate sold by the company GOLDSCHMIDT under the name ANTIL 208.

(5) Copolymers of hydrophilic methacrylates or acrylates and hydrophobic monomers comprising at least one fatty chain, in particular C8-C32 alkyl, better still C14-C28, such as for example polyethylene glycol methacrylate/lauryl methacrylate copolymer.

(6) Polyether polyurethanes comprising in their chain both hydrophilic sequences, most often of a polyoxyethylenated nature, and hydrophobic sequences which may be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences.

(7) Polymers with an ether aminoplast backbone possessing at least one fatty chain, in particular C8-C32 alkyl, better still C14-C28, such as the PURE THIX compounds offered by the company SUD-CHEMIE.

Preferably, the polyether polyurethanes comprise at least two lipophilic hydrocarbon chains, having from 8 to 30 carbon atoms, separated by a hydrophilic sequence, the hydrocarbon chains possibly being pendant chains or chains at the end of a hydrophilic sequence. In particular, it is possible that one or more hanging chains are provided. In addition, the polymer may comprise a hydrocarbon chain at one end or at both ends of a hydrophilic block.

Polyether polyurethanes can be multiblock, in particular in triblock form. The hydrophobic blocks can be at each end of the chain (for example: triblock copolymer with a hydrophilic central block) or distributed both at the ends and in the chain (multiblock copolymer for example). These same polymers can also be in grafts or in stars.

The nonionic polyurethane polyethers with a fatty chain can be triblock copolymers whose hydrophilic sequence is a polyoxyethylenated chain comprising from 50 to 1000 oxyethylenated groups. Non-ionic polyether polyurethanes have a urethane bond between the hydrophilic sequences, hence the origin of the name.

By extension, non-ionic polyurethane polyethers with a fatty chain also include those whose hydrophilic sequences are linked to the lipophilic sequences by other chemical bonds.

As examples of nonionic polyether polyurethanes with a fatty chain that can be used in the invention, it is also possible to use Rhéolate 205® with a urea function sold by the company RHEOX or else Rhéolates® 208, 204 or 212, as well as Acrysol RM 184®. Mention may also be made of the product ELFACOS T210® with a C12-14 alkyl chain and the product ELFACOS T212® with a C18 alkyl chain from AKZO. The DW 1206B® product from ROHM & HAAS with a C20 alkyl chain and urethane bond, offered at 20% dry matter in water, can also be used.

It is also possible to use solutions or dispersions of these polymers, in particular in water or in an aqueous-alcoholic medium. By way of example, such polymers include RHEOLATE® 255, RHEOLATE® 278 and RHEOLATE® 244 sold by the company RHEOX. It is also possible to use the DW 1206F and DW 1206J products offered by ROHM & HAAS.

The polyurethane polyethers which can be used according to the invention are in particular those described in the article by G. Fonnum, J. Bakke and Fk. Hansen - Colloid Polym. Sci. 271, 380,389 (1993).

More particularly still, it is preferred to use a polyether polyurethane capable of being obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 moles of ethylene oxide, (ii) stearyl alcohol or decyl alcohol and (iii) at least one diisocyanate.

Such polyether polyurethanes are sold in particular by the company ROHM & HAAS under the names ACULYN 46® and ACULYN 44® [ACULYN 46® is a polycondensate of polyethylene glycol with 150 or 180 moles of ethylene oxide, stearyl alcohol and methylene bis(4-cyclohexyl-isocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%) and water (81%); ACULYN 44® is a polycondensate of polyethylene glycol with 150 or 180 moles of ethylene oxide, decyl alcohol and methylene bis(4-cyclohexylisocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol ( 39%) and water (26%)].

Preferably, the composition comprises one or more nonionic associative polymers, preferably chosen from polyether polyurethanes.

Preferably, the associative polymer(s) are present in the composition in a total content ranging from 0.01 to 10% by weight, preferentially 0.05 to 5% by weight, more preferentially from 0.1 to 1.5% by weight. weight, better still from 0.2 to 0.8% by weight relative to the total weight of the composition.

Preferably, the nonionic associative polymer(s) are present in the composition in a total content ranging from 0.01 to 10% by weight, preferentially 0.05 to 5% by weight, more preferentially from 0.1 to 1.5 % by weight, better still from 0.2 to 0.8% by weight relative to the total weight of the composition.

Preferably, the nonionic associative polymer(s) chosen from polyether polyurethanes are present in the composition in a total content ranging from 0.01 to 10% by weight, preferentially 0.05 to 5% by weight, more preferentially from 0, 1 to 1.5% by weight, better still from 0.2 to 0.8% by weight relative to the total weight of the composition.

(iv) Cationic polymer

The composition according to the invention may also comprise one or more polymers chosen from cationic polymers different from the associative polymers described above.

The term “cationic polymer” is understood to mean any polymer comprising cationic groups and/or groups which can be ionized into cationic groups, and not comprising any anionic groups and/or groups which can be ionized into anionic groups.

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

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

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

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

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

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

Among these copolymers of family (1), mention may be made of:
- copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulphate or with a dimethyl halide, such as that sold under the name HERCOFLOC by the company HERCULES,
- copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride, such as those sold under the name BINA QUAT P 100 by the company CIBA GEIGY,
- the copolymer of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate, such as that sold under the name RETEN by the company HERCULES,
- vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers, quaternized or not, such as the products sold under the name "GAFQUAT" by the company ISP, such as for example "GAFQUAT 734" or "GAFQUAT 755" or else the products called "COPOLYMER 845 , 958 and 937". These polymers are described in detail in French patents 2,077,143 and 2,393,573;
- dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers, such as the product sold under the name GAFFIX VC 713 by the company ISP,
- vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers, such as those marketed under the name STYLEZE CC 10 by ISP;
- quaternized 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 dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homo- or copolymerization being followed by cross-linking with an olefinically unsaturated compound, in particular methylene bisacrylamide. Mention may in particular be made of Polyquaternium-37 (INCI name). It is more particularly possible to use a crosslinked acrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion comprising 50% by weight of the said copolymer in mineral oil. This dispersion is marketed under the name "SALCARE® SC 92" by the company CIBA. It is also possible to use a crosslinked homopolymer of methacryloyloxyethyltrimethylammonium chloride comprising approximately 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are marketed under the names “SALCARE® SC 95” and “SALCARE® SC 96” by the company CIBA.

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

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

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

Cationic galactomannan gums are described more particularly in patents US3589578 and US4031307, and mention may be made of guar gums comprising cationic trialkylammonium groups. For example, guar gums modified with a salt (for example a chloride) of 2,3-epoxypropyl trimethylammonium are used. Such products are marketed in particular under the names JAGUARC13S, JAGUARC15, JAGUAR C 17 or JAGUAR C162 by the company RHODIA.

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

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

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

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

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

in which
- k and t are equal to 0 or 1, the sum k + t being equal to 1;
- R ₁₂ denotes a hydrogen atom or a methyl radical;
- R ₁₀ and R ₁₁ , independently of one another, denote a C ₁ -C ₆ alkyl group, a C ₁ -C ₅ hydroxyalkyl group, a C ₁ -C ₄ amidoalkyl group; or alternatively R ₁₀ and R ₁₁ can denote, together with the nitrogen atom to which they are attached, a heterocyclic group such as piperidinyl or morpholinyl; R ₁₀ and R ₁₁ , independently of one another, preferably denote a C ₁ -C ₄ alkyl group;
- 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 with the INCI name Polyquaternium-6, and the copolymers of salts (for example chloride) of diallyldimethylammonium and acrylamide marketed in particular under the name “MERQUAT 550” or “MERQUAT 7SPR” with the INCI name Polyquaternium-7.

(8) Diquaternary ammonium polymers comprising recurring units of formula (III):

in which :
- R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ , which are identical or different, represent aliphatic, alicyclic or arylaliphatic radicals comprising from 1 to 20 carbon atoms or C ₁ -C ₁₂ hydroxyalkylaliphatic radicals, or alternatively R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ , together or separately, constitute with the nitrogen atoms to which they are attached heterocycles optionally comprising a second heteroatom other than nitrogen, or alternatively R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ represent a linear or branched C ₁ -C ₆ alkyl radical 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, linear or branched, saturated or unsaturated, and which may contain, linked to or intercalated in the main chain, one or more aromatic rings, or one or several oxygen atoms, sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and
- X ^- denotes an anion derived from a mineral or organic acid;
it being understood that A ₁ , R ₁₃ and R ₁₅ can form with the two nitrogen atoms to which they are attached a piperazine ring;
in addition, if A ₁ denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B ₁ can also denote a group (CH ₂ )n-CO-D-OC-(CH ₂ )p-, with n and p, identical or different, being integers ranging from 2 to 20, and D denoting:
a) a glycol residue of formula -OZO-, where Z denotes a linear or branched hydrocarbon radical or a group corresponding to one of the following formulas: -(CH ₂ CH ₂ O)x-CH ₂ CH ₂ - and - [CH ₂ CH(CH ₃ )O]y-CH ₂ CH(CH ₃ )- where x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or any number 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 denotes a linear or branched hydrocarbon radical, or else the divalent radical -CH ₂ -CH ₂ -SS-CH ₂ -CH ₂ -;
d) a ureylene group of formula -NH-CO-NH-.

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

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

in which R1, R2, R3 and R4, identical or different, denote an alkyl or hydroxyalkyl radical having from 1 to 4 carbon atoms, n and p are integers ranging from 2 to 20, and X- is an anion derived from an inorganic or organic acid.

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

(9) Quaternary polyammonium polymers comprising units of formula (V):

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

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

(10) Quaternary polymers of vinylpyrrolidone and vinylimidazole, such as for example the products marketed under the names Luviquat® FC 905, FC 550 and FC 370 by the company B.A.S.F.

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

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

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

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

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

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

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

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

Other cationic polymers which can be used in the context of the invention are cationic proteins or hydrolysates of cationic proteins, polyalkyleneimines, in particular polyethyleneimines, polymers comprising vinylpyridine or vinylpyridinium units, condensates of polyamines and of epichlorohydrin, quaternary polyureylenes and derivatives of chitin.

Preferably, the cationic polymers are chosen from those of families (1), (2), (7) and (10) mentioned above.

Among the cationic polymers, it is possible to preferably use cationic polysaccharides, in particular celluloses and cationic galactomannan gums, and in particular quaternary cellulose ether derivatives such as the products sold under the name "JR 400" by the Company AMERCHOL, cationic cyclopolymers, in particular homopolymers or copolymers of salts (for example chloride) of dimethyldiallylammonium, sold under the names MERQUAT 100, MERQUAT 550 and MERQUAT S by the company NALCO, quaternary polymers of vinylpyrrolidone and vinylimidazole, homopolymers or optionally crosslinked copolymers of methacryloyloxy(C ₁ -C ₄ )trialkyl(C ₁ -C ₄ )ammonium salts; and their mixtures.

Preferably, the cationic polymer(s) may be chosen from optionally crosslinked homopolymers or copolymers of methacryloyloxy(C ₁ -C ₄ )trialkyl(C ₁ -C ₄ )ammonium salts and mixtures thereof, in particular from homopolymers of methacryloyloxyalkyl( C1-C4) trimethyl ammonium, and better among the polymers of INCI name Polyquaternium-37.

When they are present in the composition, the composition according to the invention comprises the cationic polymers in an amount of between 0.01 and 5% by weight, preferably from 0.05 to 3% by weight, preferably from 0.1 at 2% by weight, relative to the total weight of the composition.

fatty alcohol

The composition according to the present invention may also comprise one or more fatty alcohols.

By “fatty alcohol”, is meant a long-chain aliphatic alcohol comprising from 8 to 40 carbon atoms, preferably from 10 to 30 carbon atoms and comprising at least one OH hydroxyl group. These fatty alcohols are neither oxyalkylenated nor glycerolated. Preferably, the fatty alcohols are chosen from solid fatty alcohols (25° C., 1 atm).

The solid fatty alcohols can be saturated or unsaturated, linear or branched, and contain from 8 to 40 carbon atoms, preferably from 10 to 30 carbon atoms, better still from 12 to 30 carbon atoms. Preferably, the solid fatty alcohols have an R-OH structure with R denoting a linear alkyl group, optionally substituted by one or more hydroxy groups, comprising from 8 to 40, preferably from 10 to 30 carbon atoms, better still from 12 to 30 , or even from 12 to 24 atoms, even better from 14 to 22 carbon atoms.

The solid fatty alcohols which can be used are preferably chosen from saturated, linear or branched (mono)alcohols, preferably linear and saturated, comprising from 8 to 40 carbon atoms, better still from 10 to 30, or even from 12 to 24 atoms, even better from 14 to 22 carbon atoms.

The solid fatty alcohols which can be used alone or as a mixture can be chosen from:
- myristic or myristyl alcohol (or 1-tetradecanol);
- cetyl alcohol (or 1-hexadecanol);
- stearyl alcohol (or 1-octadecanol);
- arachidyl alcohol (or 1-eicosanol);
- behenyl alcohol (or 1-docosanol);
- lignoceryl alcohol (or 1-tetracosanol);
- cerylic alcohol (or 1-hexacosanol);
- montanyl alcohol (or 1-octacosanol);
- myricyl alcohol (or 1-triacontanol).

Preferably, the solid fatty alcohol is chosen from cetyl alcohol, stearyl alcohol, behenyl alcohol, myristic alcohol, arachidyl alcohol and mixtures thereof, such as cetylstearyl or cetearyl alcohol. Particularly preferably, the solid fatty alcohol is chosen from cetyl alcohol, stearyl alcohol or mixtures thereof such as cetearyl alcohol, better still the solid fatty alcohol is cetearyl alcohol.

When present, the composition according to the invention may comprise the fatty alcohol(s) in a total amount of between 0.5 and 15% by weight, preferably from 1 to 10% by weight, preferably from 2 to 8% by weight, relative to the total weight of the composition.

The compositions according to the invention may comprise water, preferably in a content ranging from 60 to 99% by weight, preferably from 70 to 98% by weight, better still from 80 to 95%, or even from 85 to 94% by weight relative to the total weight of the composition.

They may also comprise one or more organic solvents chosen in particular from linear or branched C1-C6 monoalcohols such as ethanol and isopropanol; C2-C10 polyols and polyol ethers, such as 2-butoxyethanol, propylene glycol (1,2-propanediol), propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, hexylene glycol; aromatic alcohols such as benzyl alcohol or phenoxyethanol.

Preferably, the organic solvents are chosen from C ₁ -C ₄ monoalcohols, in particular ethanol and isopropanol; diols such as butane-1,4-diol, butane-1,2-diol, butane-1,3-diol, butane-2,3-diol, propane-1,2-diol (propylene glycol), pentane-1,2-diol, pentane-1,5-diol, pentane-2,4-diol, pentane-1,3-diol, hexane-1,6-diol, hexane-1,2-diol , hexane-2,5-diol, 2-methyl-2,4-pentanediol (hexylene glycol), diethylene glycol, dipropylene glycol, triethylene glycol; triols such as hexane-1,2,6-triol, glycerol; tetraols such as erythriol; benzyl alcohol; phenoxyethanol; and their mixtures.

Preferably the compositions according to the invention are aqueous.

The compositions in accordance with the invention may also comprise various adjuvants conventionally used in compositions for the cosmetic treatment of keratin materials, such as, alone or as a mixture: nonionic surfactants; organic or inorganic thickening agents other than the associative polymers described previously; antioxidant agents; penetrants; sequestering agents; perfumes ; dispersing agents; conditioning agents; film-forming agents; ceramides; preservatives and opacifying agents.

Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the composition in accordance with the invention are not, or substantially not, altered by the addition(s) considered.

The above adjuvants may generally be present in an amount comprised for each of them between 0.01 and 20% by weight relative to the total weight of each composition containing them.

The compositions according to the invention may be in various galenic forms, such as a powder, a lotion, a foam, a cream, a gel or in any other form suitable for carrying out a cosmetic treatment of keratin materials. They can also be packaged in a pump bottle without propellant or under pressure in an aerosol bottle in the presence of a propellant and form a foam.

A subject of the invention is also a process for the cosmetic treatment of keratin materials, in particular keratin fibers, in particular human fibers such as the hair, comprising the application to said materials, in particular keratin fibers, of a composition as defined above.

The composition according to the invention can be applied to dry or wet keratinous materials, possibly having previously undergone washing with a shampoo. Preferably, the composition according to the invention is applied to wet keratin materials, in particular fibres.

The composition according to the invention can be applied according to an exposure time which can range from 1 to 15 minutes, preferably from 2 to 10 minutes.

After application of the composition according to the invention, the keratin materials can be rinsed with water, before being dried or left to dry.

A further subject of the invention is the use of a composition as defined above for the cosmetic treatment of keratin materials, in particular keratin fibres, in particular human keratin fibers such as the hair.

The composition can be used on damp or dry hair, in rinse-out or leave-in mode, and preferably in rinse-out mode (that is to say that the keratin fibers are rinsed out after application of the composition).

According to a preferred embodiment, the composition according to the invention comprises:
- one or more alpha, omega-bis-amino silicones corresponding to the formula (I)

in which :
the R radicals, independently of each other, represent a hydrogen atom or a C ₁ -C ₄ alkyl group,
the radicals R ₁ , R ₂ , R ₃ and R ₄ , 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 amino silicone is between 5,000 and 200,000;
preferably present in a total content ranging from 0.001 to 10% by weight, preferably from 0.005 to 5% by weight, more preferably 0.01 to 1%, better still from 0.02 to 0.8% by weight, relative to the total weight of the composition;

- one or more amino silicones chosen from amino silicones A, C, F and G and mixtures thereof, preferably present in a total content ranging from 0.001 to 10% by weight, preferably from 0.005 to 5% by weight, more preferably 0 0.01 to 1%, better still from 0.02 to 0.8% by weight, relative to the total weight of the composition; And

- one or more non-ionic associative polymers, preferably present in a total content ranging from 0.01 to 10% by weight, preferably 0.05 to 5% by weight, more preferably from 0.1 to 1.5% by weight, better still from 0.2 to 0.8% by weight relative to the total weight of the composition.

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

Example 1

A hair care composition A1 according to the invention and a comparative hair care composition B1 are prepared from the following ingredients (% by weight of active ingredient MA):

Ingredients A1
(invention) B1
(comparative) Amodimethicone 0.05 0.05 Bis-aminopropyl dimethicone 0.05 0.05 PEG-150/decyl alcohol/SMDI copolymer (Aculyn 44 Polymer) 0.72 - Hydroxypropyl guar - 0.72 Polyquaternium 37 (Salcare SC96) 0.95 0.95 Cetearyl alcohol 6.5 6.5 Water Qsp 100 Qsp100

Compositions A1 and B1 were applied to moderately sensitized locks of Caucasian hair:
- step 1: apply 0.4 g of Elseve Total Repair 5 treating shampoo (L'Oréal Paris) per g of lock, mix and lather, leave on for 30 seconds then rinse the lock with water for 15 seconds (flow = 300 L/h – temperature = 35°C)
- step 2: on the hair that has been washed and is still wet, 0.4 g of hair care composition A1 or B1 is applied per g of lock; leave on for 2 minutes then rinse the lock with water for 10 seconds (flow rate = 300 L/h – temperature = 35°C) and dry the locks with a hair dryer.

The sensory performances of compositions A1 and B1 are evaluated on three criteria (smooth feel and coating):
- on damp hair, after having rinsed off the hair care compositions, and
- on dried hair, after the hair dryer step.
The rating from 0 [not] to 5 [very] is carried out blindly by two evaluators.

The following results are obtained (average of the scores):

A1 (invention) B1 (comparative) Wet hair Smooth touch 4 3 Coating 4 3 Dried hair Smooth touch 4 3 Coating 4 3

It is found that the composition according to the invention makes it possible to significantly increase the cosmetic level on the criteria tested, whether on damp hair or on dried hair, compared with composition B1.

Example 2

A hair care composition A2 according to the invention and two comparative hair care compositions B2 and C2 are prepared from the following ingredients (% by weight of active ingredient):

Ingredients A2
(invention) B2
(comparative) C2
(comparative) Amodimethicone 0.5 1 - Bis-aminopropyl dimethicone 0.5 - 1 PEG-150/decyl alcohol/SMDI copolymer (Aculyn 44 Polymer) 0.72 0.72 0.72 Cetearyl alcohol 6.5 6.5 6.5 Polyquaternium 37 (Salcare SC96) 0.95 0.95 0.95 Water Qsp 100 Qsp 100 Qsp 100

Compositions A2, B2 and C2 were applied to locks of Caucasian hair sensitized by a bleaching treatment:
- step 1: apply 0.4 g of Elseve Total Repair 5 treatment shampoo per g of lock, mix and lather then leave on for 30 seconds then rinse the lock with water for 15 seconds (flow rate = 300 L/h – temperature = 35°C)
- step 2: on the hair that has been washed and is still wet, 0.4 g of hair care composition A2, B2 or C2 is applied per g of lock; leave on for 2 minutes then rinse the lock with water for 10 seconds (flow rate = 300 L/h – temperature = 35°C) and dry the locks with a hair dryer.

The sensory performances of compositions A2, B2 and C2 are evaluated on three criteria (smooth touch and suppleness):
- on damp hair, after having rinsed off the hair care compositions, and
- on dried hair, after the hair dryer step.
The rating from 0 [not] to 5 [very] is carried out blindly by two evaluators.

The following results are obtained (average of the scores):

A2 B2 C2 Wet hair Smooth touch 4.5 4 4 Flexibility 4 3 3 Dried hair Smooth touch 4 3 3 Flexibility 4 2.5 3

It is found that the composition according to the invention makes it possible to significantly increase the cosmetic level on the criteria tested compared to a comparative composition comprising an amino silicone alone or a bis-amino silicone alone.

It is observed that the compositions A1 and A2 according to the invention can be used as a leave-on (application without subsequent rinsing) on the hair, in particular on damaged hair. They bring a good level of care to the hair, in particular a smooth touch, softness and lightness. After application, the hair is supple, individualized and disciplined (no 'packages' and no cardboard effect). These effects are homogeneous from the root to the tip of the hair.

Claims (15)

Cosmetic composition comprising:
- (i) one or more alpha, omega-bis-amino silicones,
- (ii) one or more amino silicones different from the silicones (i), and
- (iii) one or more associative polymers. Composition according to the preceding claim, in which the alpha, omega-bis-amino silicone(s) (i) are chosen from the silicones corresponding to the following formula (I):

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 R ₁ , R ₂ , R ₃ and R ₄ radicals, 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 amino silicone is between 5,000 and 200,000;
preferably chosen from silicones of formula (I) in which:
- the R radicals are identical and represent CH ₃ (methyl), and/or
- R ₁ , R ₂ , R ₃ and R ₄ , independently of each other, represent a hydrogen atom, an alkyl group, preferably linear saturated, C1-C4, especially C2-C4, especially 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 ), and/or
- x is between 1 and 5, better between 2 and 4, even better x=3, and/or
- y is between 1 and 5, better between 2 and 4, even better y=3;
preferentially chosen from amino silicones of formula (I) in which R = methyl, x = y = 3 and R ₁ = R ₂ = R ₃ = R ₄ = H. Composition according to any one of the preceding claims, in which the composition comprises a total content of alpha,omega-bis-amino silicone(s) ranging from 0.001 to 10% by weight, preferably from 0.005 to 5% by weight, more preferentially 0.01 to 1%, better still from 0.02 to 0.8% by weight, relative to the total weight of the composition. Composition according to any one of the preceding claims, in which the amino silicones (ii) different from the alpha,omega-bis-amino silicones (i), are chosen from, alone or as a mixture:
1) the polysiloxanes corresponding to the formula (A):

in which x' and y' are integers such that the weight-average molecular weight (Mw) is between 5,000 and 500,000 approximately;
2) the silicones called "trimethylsilylamodimethicone" corresponding to the 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 possibly denoting a number from 0 to 1999, and in particular from 49 to 149 and m possibly denoting a number from 1 to 2000, and in particular from 1 to 10.
3) silicones of the following formula (D):

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 possibly denoting a number from 0 to 999 and in particular from 49 to 249 and more particularly from 125 to 175 and m possibly denoting 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.

4) 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 possibly denoting a number from 0 to 999 and in particular from 49 to 349 and more particularly from 159 to 239 and q possibly denoting 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 alkoxy radical in C ₁ -C ₄ , at least one of the radicals R ₁ or R ₂ designating an alkoxy radical.

5) 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 being able to designate a number from 0 to 1999 and in particular from 49 to 149 and m being able to designate a number from 1 to 2000, and in particular from 1 to 10;
- A denotes a linear or branched alkylene radical having from 4 to 8 carbon atoms and preferably 4 carbon atoms.
6) 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 being able to designate a number from 0 to 1999 and in particular from 49 to 149 and m being able to designate a number from 1 to 2000, and in particular from 1 to 10;
- A denotes a linear or branched alkylene radical having from 4 to 8 carbon atoms and preferably 4 carbon atoms.
7) amino silicones corresponding to the 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 or C ₂ -C ₁₈ alkenyl radical, 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.

8) amino silicones of formula (J):

in which :
- R ₁ , R ₂ , R ₃ and R ₄ , which are 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 ranging from 1 to 5,
- m is an integer ranging from 1 to 5, and
- x is chosen such that the amine number varies from 0.01 to 1 meq/g.
9) multiblock polyoxyalkylenated amino silicones, of (AB)n type, A being a polysiloxane block and B being a polyoxyalkylenated block comprising at least one amine group;

preferably chosen from, alone or as a mixture, silicones of formula A, C, F and/or G, even better from silicones of formula G and mixtures thereof. Composition according to any one of the preceding claims, comprising a total content of amino silicone(s) (ii) ranging from 0.001 to 10% by weight, preferably from 0.005 to 5% by weight, more preferably from 0, 01 to 1% by weight, better still from 0.02 to 0.8% by weight, relative to the total weight of the composition. Composition according to any one of the preceding claims, in which the weight ratio between the total content of bis-amino silicone(s) (i) over the total content of amino silicone(s) (ii) is greater than or equal to 1, preferably strictly greater than 1. Composition according to any one of the preceding claims, characterized in that the associative polymers are chosen from nonionic associative polymers, preferably from alone or as a mixture:
(1) Cellulose modified with groups comprising at least one fatty chain, in particular C8-C32 alkyl, better still C14-C28; preferably from hydroxyethylcelluloses modified with groups comprising at least one fatty chain such as alkyl, arylalkyl, alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C8-C22, such as cetylhydroxyethyl cellulose; hydroxyethyl celluloses modified with polyalkylene glycol ether alkyl phenol groups, and mixtures thereof;
(2) Hydroxypropylguars modified with groups comprising at least one fatty chain, in particular C8-C32 alkyl, better still C14-C28;
(3) Copolymers of vinylpyrrolidone and fatty chain hydrophobic monomers, in particular C8-C32, better still C14-C28 alkyl; such as the vinylpyrrolidone/hexadecene copolymer or the vinylpyrrolidone/eicosene copolymer;
(4) Copolymers of C1-C6 alkyl methacrylates or acrylates and amphiphilic monomers comprising at least one fatty chain, in particular C8-C32 alkyl, better still C14-C28, such as for example the methyl acrylate copolymer /oxyethylenated stearyl acrylate;
(5) Copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain, in particular C8-C32 alkyl, better still C14-C28 alkyl, such as for example polyethylene glycol methacrylate/lauryl methacrylate copolymer;
(6) Polyether polyurethanes comprising in their chain both hydrophilic sequences, most often of a polyoxyethylenated nature, and hydrophobic sequences which may be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences.
(7) Polymers with an ether aminoplast backbone possessing at least one fatty chain, in particular C8-C32 alkyl, better still C14-C28. Composition according to any one of the preceding claims, in which the associative polymers are chosen from polyether polyurethanes and in particular those comprising at least two lipophilic hydrocarbon chains, having from 8 to 30 carbon atoms, separated by a hydrophilic sequence, the hydrocarbon chains possibly be pendant chains or end chains of a hydrophilic sequence; preferably chosen from polyether polyurethanes obtainable by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 moles of ethylene oxide, (ii) stearyl alcohol or decyl alcohol and (iii) at least one diisocyanate. Composition according to any one of the preceding claims, comprising a total content of associative polymer(s) ranging from 0.01 to 10% by weight, better still from 0.05 to 5% by weight, even better still from 0.1 to 1.5% by weight, preferably from 0.2 to 0.8% by weight relative to the total weight of the composition. Composition according to any one of the preceding claims, characterized in that it comprises one or more cationic polymers; preferably chosen from cationic polysaccharides, cationic cyclopolymers, quaternary polymers of vinylpyrrolidone and vinylimidazole, optionally crosslinked homopolymers or copolymers of methacryloyloxyalkyl(C ₁ -C ₄ )trialkyl(C ₁ -C ₄ )ammonium salts. Composition according to Claim 10, comprising a total content of cationic polymers ranging from 0.01 to 5% by weight, preferably from 0.05 to 3% by weight, preferably from 0.1 to 2% by weight, relative to the total weight of the composition. Composition according to any one of the preceding claims comprising one or more fatty alcohols, preferably chosen from solid fatty alcohols, and better still from fatty alcohols of formula R-OH with R denoting a linear alkyl group, optionally substituted by one or more hydroxy groups, comprising from 8 to 40, preferably from 10 to 30 carbon atoms, better from 12 to 30, even from 12 to 24 atoms, even better from 14 to 22 carbon atoms. Composition according to any one of the preceding claims, characterized in that the composition comprises water, preferably in a content ranging from 60 to 99% by weight, preferably from 70 to 98% by weight, better still from 80 to 95 %, or even from 85 to 94% by weight relative to the total weight of the composition. Process for the cosmetic treatment of keratin materials, in particular keratin fibers, in particular human fibers such as the hair, comprising the application to the keratin materials of a composition according to any one of the preceding claims. Use of a composition as defined by any one of Claims 1 to 13, for the cosmetic treatment of keratin materials, in particular keratin fibers, in particular human fibres, such as the hair.