WO2015001074A2 - Self-foaming non-colouring hair composition comprising a particular anionic copolymer, an alkaline agent, a surfactant and a propellant gas - Google Patents

Abstract

The invention relates to a self-foaming non-co louring hair composition comprising : - from 2% to 60% by weight, relative to the total weight of the composition, o f one or more anionic copolymers derived from at least one unsaturated carboxylic acid and from at least one ester of an unsaturated carboxylic acid and of a monoalcohol comprising from 1 to 6 carbon atoms, - one or more surfactants chosen from anionic, non-ionic and amphoteric surfactants, - one or more alkaline agents, and - one or more propellant gases. The invention also relates to the use of the said composition for cleansing and/or conditioning the hair.

Description

Self-foaming non-colouring hair composition comprising a particular anionic copolymer, an alkaline agent, a surfactant and a propellant gas

The present invention relates to a self-foaming non-co louring hair composition comprising at least 2% by weight, relative to the total weight of the self-foaming non-co louring hair composition, o f at least one particular anionic polymer, at least one anionic, nonionic, amphoteric or cationic surfactant, at least one alkaline agent and at least one propellant gas .

The invention also relates to the use of the said composition for cleansing and/or conditioning human hair.

It is known practice to cleanse the hair with shampoos which are aqueous compositions containing high proportions of surfactants . These surfactants are generally anionic surfactants alone or in combination with amphoteric or nonionic surfactants. The concentrations o f surfactants used usually exceed 10% by weight expressed as active materials.

These surfactants are for the mo st part aggressive towards the scalp and frequently lead to irritation, reflected by redness or sensations o f discomfort. These surfactants are also aggressive towards the eyes.

In addition, the rinsing of compositions with these high contents of surfactants is often long.

Moreover, these surfactants degrade the cosmetic properties of the hair, leading to the need to add conditioning ingredients such as cationic po lymers, silicones or non-silicone oils.

Finally, to avoid running on application and especially running into the eyes, shampoos must be thickened. The thickening o f compositions containing high contents of surfactants is difficult and frequently poses stability problems. There is thus a need for compositions that can cleanse the hair while at the same time reducing the standard surfactants that are the cause of these drawbacks .

Cosmetic compositions, in particular detergent compositions, containing copolymers of methacrylic acid and of alkyl acrylate as stabilizer or suspension agent for water-inso luble ingredients, for instance silicones or fatty substances, are known. Such compositions have been especially described in patent application WO 01 /76552.

However, the compositions thus obtained still have insufficient foaming nature. In addition, the cosmetic properties imparted to the hair are still not entirely satisfactory, in particular on dry hair.

The Applicant has discovered, surprisingly and unexpectedly, that the combination o f 2% to 60% by weight, relative to the total weight of the non-co louring hair composition, of certain anionic copolymers as described below, with one or more anionic, nonionic, or amphoteric surfactants and one or more alkaline agents, in the presence of one or more propellant gases, makes it possible to overcome the drawbacks mentioned above, and is especially capable o f generating an adequate foam, in terms of quality and quantity, and o f giving the hair satisfactory cosmetic properties, such as sheen, so ftness, smoothness, disentangling and suppleness, most particularly on dry hair.

In particular, these compositions are self-foaming, i.e. the fo am expands after the product has been dispensed, in particular when it is spread onto the head of hair.

One subj ect of the invention is thus a self-foaming non- co louring hair composition comprising :

from 2% to 60% by weight, relative to the total weight of the composition, o f one or more anionic copolymers derived from at least one unsaturated carboxylic acid and from at least one ester of an unsaturated carboxylic acid and of a monoalcohol comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms, one or more surfactants chosen from anionic, non-ionic and amphoteric surfactants, one or more alkaline agents, and

one or more propellant gases .

The compositions according to the invention are rinsed out faster than standard shampoos. They intrinsically have a more pronounced treating nature and give the hair more lightness, especially on wet hair. They do not necessarily require the addition o f viscosity enhancers, and can afford varied textures. They are better tolerated by the scalp and the eyes. Furthermore, they are easy to spread onto the head o f hair.

A subj ect of the present invention is also the use o f a composition according to the invention for cleansing and/or conditioning human hair.

Another subj ect of the invention consists of a process for cleansing and/or conditioning human hair, comprising the use of the self-foaming non-co louring hair composition as described below.

Other subj ects, characteristics, aspects and advantages of the invention will emerge even more clearly on reading the description and the examples that follow.

In the text hereinbelow, unless otherwise indicated, the limits of a range o f values are included in that range, especially in the expressions "between" and "ranging from ... to

Moreover, the expression " at least one" used in the present description is equivalent to the expression "one or more" .

According to the invention, the self-foaming non-co louring hair composition comprises :

from 2% to 60% by weight, relative to the total weight of the composition, of one or more anionic copolymers derived from one or more unsaturated carboxylic acids and from one or more esters of an unsaturated carboxylic acid and of a monoalcohol comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms, one or more surfactants chosen from anionic, non-ionic and amphoteric surfactants,

one or more alkaline agents, and

one or more propellant gases . The composition according to the invention is non-co louring. According to the present invention, the term "non-co louring composition" means a composition not containing any dye for keratin fibres such as direct dyes or oxidation dye precursors (bases and/or couplers) . If they are present, their content does not exceed 0.005 % by weight, relative to the total weight of the composition. Specifically, at such a content, only the composition would be dyed, i. e. no dyeing effect would be observed on the keratin fibres.

For the purposes of the present invention, the term "polymer" means any compound derived from the polymerization by polycondensation or from the radical polymerization o f monomers, at least one of which is other than an alkylene oxide, and of a mono functional compound o f formula RX, R denoting an optionally hydroxylated C 1 0 - C 30 alkyl or alkenyl group, and X denoting a carboxylic acid, amine, amide, hydroxyl or ester group . Any compound derived so lely from the simp le condensation of an alkylene oxide with a fatty alcoho l, a fatty ester, a fatty acid, a fatty amide or a fatty amine is in particular excluded.

Unless otherwise mentioned, in the present description o f the invention, the term "fatty" compound, for instance a fatty alcoho l, a fatty acid or a fatty amide, denotes a compound comprising, in its main chain, at least one saturated or unsaturated hydrocarbon-based chain, such as alkyl or alkenyl, comprising at least 8 carbon atoms, preferably from 8 to 30 carbon atoms, and better still from 10 to 22 carbon atoms.

The anionic copolymers used in the composition o f the invention are copo lymers comprising among their monomers one or more unsaturated carboxylic acids, which are more particularly α, β- monoethylenically unsaturated, and one or more esters of unsaturated carboxylic acids, which are more particularly α,β-monoethylenically unsaturated, and of a monoalcohol comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms . More particularly, the unsaturated carboxylic acid, which is especially α, β-monoethylenically unsaturated, is a monomer corresponding to formula (I) below:

H₂C=C— C— OH

R O

(I) in which formula R¹ denotes H or CH₃ or C₂H₅ , which corresponds to acrylic acid, methacrylic acid or ethacrylic acid units.

Preferably, the other monomeric ester of an unsaturated carboxylic acid and of a monoalcoho l comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms is a monomer o f formula (II) below :

in which formula R¹ denotes H or CH₃ or C₂Hs (i. e. acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH₃ (methacrylate units), and R₂ denotes an alkyl group comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms .

As esters of an unsaturated carboxylic acid and of a fatty monoalcoho l comprising from 1 to 6 carbon atoms according to formula (II), mention may be made more particularly o f methyl acrylate, ethyl acrylate, propyl acrylate and butyl acrylate, and the corresponding methacrylates, methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate.

According to one embodiment, these anionic copolymers may be crosslinked, for example, with a crosslinking agent, which is a well-known copolymerizable polyethylenic unsaturated monomer, for instance diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methylenebisacrylamide.

Examples o f anionic copolymers as defined above are the crosslinked copolymer of acrylic acid and of ethyl acrylate sold under the trade name Aculyn 33 by the company Rohm & Haas, which is in aqueous dispersion containing 28% by weight of active material, the methacrylic acid/ethyl acrylate crosslinked copolymer in the form o f an aqueous dispersion at 30%> by weight sold under the name Carbopol Aqua SF- 1 Polymer by the company Lubrizol, and the copolymer o f (meth)acrylic acid and of a C ₁ - C4 alkyl (meth)acrylate so ld under the name Synthalen W400 by the company 3V Sigma, at 30% by weight of active material in water.

Preferably, the anionic copolymer(s) used in the invention are chosen from crosslinked copolymers of (meth)acrylic acid and o f a C i - C₄ alkyl (meth)acrylate, and better still from crosslinked copolymers of (meth)acrylic acid and of ethyl (meth)acrylate.

The anionic copo lymer(s) of the invention are present in an amount ranging from 2% to 60% by weight, preferably ranging from 2.2% to 40% by weight and better still ranging from 2.5 % to 30% by weight, or even 2.9%> to 20%> by weight, relative to the total weight o f the composition.

The compositions o f the invention comprise one or more surfactants chosen from anionic, nonionic and amphoteric surfactants .

The term "anionic surfactant" means a surfactant comprising, as ionic or ionizable groups, only anionic groups . These anionic groups are preferably chosen from the fo llowing groups : -CO₂H, - C(V, - S O3H, - S O3 ^", -O S O3H, -O S O3 ^", -H2PO3 , -HPO3^", -PO3^{2 "}, -H2PO2 ,

As examples of anionic surfactants that may be used in the composition according to the invention, mention may be made o f alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylarylpolyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, a-olefin sulfonates, paraffin sulfonates, alkylsulfo succinates, alkylether sulfosuccinates, alkylamide sulfo succinates, alkylsulfoacetates, acylsarcosinates, acylglutamates, alkylsulfosuccinamates, acylisethionates and N- acyltaurates, salts of alkyl monoesters of polyglycoside- polycarboxylic acids, acyllactylates, D-galactoside uronic acid salts, alkyl ether carboxylic acid salts, alkylaryl ether carboxylic acid salts, alkylamido ether carboxylic acid salts; and the corresponding non- salified forms of all these compounds; the alkyl and acyl groups of all these compounds comprising from 6 to 40 carbon atoms and preferably from 6 to 24 carbon atoms, and the aryl group denoting a phenyl group .

These compounds can be oxyethylenated and then preferably comprise from 1 to 50 ethylene oxide units.

The salts o f C₆ - C24 alkyl monoesters of polyglycoside- polycarboxylic acids may be chosen from C₆ - C24 alkyl po lyglycoside- citrates, C₆ - C24 alkyl polyglycoside-tartrates and C₆ - C24 alkyl poly glycoside-sulfo succinates .

When the anionic surfactant(s) are in salt form, they may be chosen from alkali metal salts such as the sodium or potassium salt and preferably the sodium salt, the ammonium salts, the amine salts and in particular the amino alcoho l salts or the alkaline-earth metal salts such as the magnesium salt.

Examples o f amino alcoho l salts that may especially be mentioned include monoethano lamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2-methyl- 1 -propanol salts, 2- amino-2-methyl- 1 ,3 -propanediol salts and tris(hydroxymethyl)amino methane salts.

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

In a first variant, the anionic surfactants are chosen from (C₆- C24)alkyl sulfates, (C₆ - C24)alkyl ether sulfates comprising from 2 to 50 ethylene oxide units, especially in the form o f alkali metal, ammonium, amino alcohol and alkaline-earth metal salts, or a mixture of these compounds.

Better still, it is preferred to use in this variant (C i 2 - C2o)alkyl sulfates, (C i 2 - C2o)alkyl ether sulfates comprising from 2 to 20 ethylene oxide units, especially in the form o f alkali metal, ammonium, amino alcohol and alkaline-earth metal salts, or a mixture of these compounds. Even better still, sodium lauryl ether sulfate containing 2.2 mol of ethylene oxide is preferred.

In a second variant, the anionic surfactants are chosen from surfactants bearing anionic groups chosen from -C(0)OH, -C(0)0^", -S0³H and -S(0)₂0^~, such as alkylsulfonates, alkylamide sulfonates, alkylsulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfoacetates, acyl sarcosinates, acyl glutamates, alkylsulfosuccinamates, acylisethionates and N-acyltaurates, acyl lactylates and N-acyl glycinates, the alkyl and acyl groups of all these compounds comprising from 6 to 40 carbon atoms and preferably from 6 to 24 carbon atoms.

Most particularly, use may be made of (C₆-4o acyl)glutamates, better still (C₆-₂4 acyl)glutamates, for instance the disodium cocoyl glutamate sold under the trade name Plantapon ACG LC by the company BASF, or (C₆-4o acyl)isethionates and better still (C₆-₂4 acyl)isethionates, for instance the sodium lauroyl methyl isethionate sold by the company Innospec under the trade name Iselux LQ-CLR- SB.

Examples of nonionic surfactants that may be used in the non- colouring hair composition according to the invention are described, for example, in the Handbook of Surfactants by M.R. Porter, published by Blackie & Son (Glasgow and London), 1991, pp. 116-178. They are especially chosen from polyethoxylated, polypropoxylated and/or polyglycerolated alcohols, a-diols and (Ci-C₂o)alkylphenols, containing at least one fatty chain comprising, for example, from 8 to 18 carbon atoms, the number of ethylene oxide and/or propylene oxide groups possibly ranging especially from 2 to 50, and the number of glycerol groups possibly ranging especially from 2 to 30.

Mention may also be made of condensates of ethylene oxide and of propylene oxide with fatty alcohols, polyethoxylated fatty amides preferably having from 2 to 30 ethylene oxide units, polyglycerolated fatty amides containing on average 1 to 5 glycerol groups, and in particular 1.5 to 4, ethoxylated fatty acid esters of sorbitan containing from 2 to 30 ethylene oxide units, fatty acid esters of sucrose, fatty acid esters of polyethylene glycol, (C₆-C₂₄ alkyl)- mono- or polyglycosides, N-(C₆-C24 alkyl)glucamine derivatives, amine oxides such as (C₁₀-C₁₄ alkyl)amine oxides or N-(C₁₀-C₁₄ acyl)aminopropylmorpholine oxides.

The nonionic surfactants that are particularly preferred are (C₆-

C₂₄ alkyl)-mono- or polyglycosides.

The amphoteric or zwitterionic surfactants capable of being used in the present invention can in particular be derivatives of optionally quaternized secondary or tertiary aliphatic amines containing at least one anionic group, such as, for example, a carboxylate, sulfonate, sulfate, phosphate or phosphonate group, and in which the aliphatic group or at least one of the aliphatic groups is a linear or branched chain comprising from 8 to 22 carbon atoms.

Mention may be made in particular of (C₈-C₂o)alkylbetaines, sulfobetaines, (C₈-C₂o)alkylamido(Ci-C₆)alkylbetaines such as cocamidopropylbetaine, and (C₈-C₂o)alkylamido(Ci-

C₆)alkylsulfobetaines.

Among the optionally quaternized secondary or tertiary aliphatic amine derivatives that may be used, mention may also be made of the products having the following respective structures (III) and (IV):

R_a-CONHCH₂CH₂- N⁺(R_b)(Rc)(CH₂COO^") (III) in which:

R_a represents a C₁₀-C30 alkyl or alkenyl group derived from an acid R_a-COOH preferably present in hydrolysed coconut oil, or a heptyl, nonyl or undecyl group;

R_b represents a β-hydroxyethyl group, and

R_c represents a carboxymethyl group; R_a<-CONHCH₂CH₂-N(B)(B') (IV)

in which:

B represents -CH₂CH₂OX*,

X* represents the -CH₂-COOH, -CH₂-COOZ', -CH₂CH₂-COOH or CH₂CH₂-COOZ' group or a hydrogen atom, B' represents -(CH₂)_Z-Y', with z = 1 or 2,

Y^* represents -COOH, -COOZ', or the -CH₂-CHOH-S0₃H or -CH₂-CHOH-S0₃Z' group,

Z' represents an ion derived from an alkali or alkaline-earth metal, such as sodium, potassium or magnesium; an ammonium ion; or an ion derived from an organic amine and in particular from an amino alcohol, such as monoethanolamine, diethanolamine and triethanolamine, monoisopropanolamine, diisopropanolamine or triisopropanolamine, 2 -amino -2 -methyl- 1 -propanol, 2 -amino -2 -met hyl- 1 ,3-propanediol and tris(hydroxymethyl)aminomethane.

R_a' represents a Cio-C₃o alkyl or alkenyl group of an acid R_a'COOH preferably present in coconut oil or in hydrolysed linseed oil, an alkyl group, especially of C₁₇ and its iso form, or an unsaturated C₁₇ group.

These compounds are also classified in the CTFA dictionary,

5th edition, 1993, under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate, disodium capryloamphodipropionate, lauroamphodipropionic acid and cocoamphodipropionic acid.

By way of example, mention may be made of the cocoamphodiacetate sold by the company Rhodia under the trade name Miranol^® C2M Concentrate.

Use may also be made of compounds of formula (IVa):

Ra'-NH-CH(Y")-(CH2)n-C(0)-NH-(CH₂)n-N(Rd)(Re)

(IVa) in which formula:

Y" represents the group -C(0)OH, -C(0)OZ", -CH₂-CH(OH)- S0₃H or the group -CH₂-CH(OH)-S0₃-Z";

R_d and R_e represent, independently of each other, a C1-C4 alkyl or hydroxyalkyl group; Z " represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;

R_a" represents a C 10 - C30 alkyl or alkenyl group of an acid R_a"-C(0)OH preferably present in coconut oil or in hydro lysed linseed oil;

n and n' denote, independently o f each other, an integer ranging from 1 to 3.

Among the compounds of formula (IVa), mention may be made of the compound classified in the CTFA dictionary under the name sodium diethylaminopropyl cocoaspartamide and sold by the company Chimex under the name Chimexane HB .

Preferably, the amphoteric or zwitterionic surfactants are chosen from (C₈ - C2o)alkylbetaines, (C₈-C₂o)alkylamido(C i - Ce)alkylbetaines and (C₈-C₂o)alkyl amphodiacetates, the sodium salt o f diethylaminopropyl laurylaminosuccinamate, and mixtures thereof.

Preferably, the amphoteric or zwitterionic surfactants are chosen, alone or as a mixture, from cocoylamidopropyl betaine, cocoyl betaine and cocoamphodiacetate.

The compositions of the invention may further comprise one or more cationic surfactants .

The cationic surfactant(s) that may be used in the composition according to the invention comprise in particular salts o f optionally polyoxyalkylenated primary, secondary or tertiary fatty amines, quaternary ammonium salts, and mixtures thereo f.

Examples of quaternary ammonium salts that may especially be mentioned include :

- those corresponding to the general formula (V) below:

(V) in which the groups Rs to Rn, which may be identical or different, represent a linear or branched aliphatic group comprising from 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, at least one of the groups Rs to Rn comprising from 8 to 30 carbon atoms and preferably from 12 to 24 carbon atoms. The aliphatic groups may comprise heteroatoms especially such as oxygen, nitrogen, sulfur and halogens.

The aliphatic groups are chosen, for example, from C₁-C30 alkyl, C1-C30 alkoxy, polyoxy(C₂-C6)alkylene, C1-C30 alkylamide, (C₁₂-C₂₂)alkylamido(C₂-C₆)alkyl, (Ci₂-C₂₂)alkyl acetate, and C₁-C30 hydroxyalkyl groups, X^" is an anion chosen from the group of halides, phosphates, acetates, lactates, (Ci-C₄)alkyl sulfates, and (Ci-C₄)alkyl- or (Ci-C₄)alkylarylsulfonates.

Among the quaternary ammonium salts of formula (V), those that are preferred are, on the one hand, tetraalkylammonium chlorides, for instance dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl group comprises approximately from 12 to 22 carbon atoms, in particular behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium or benzyldimethylstearylammonium chlorides, or, on the other hand, palmitylamidopropyltrimethylammonium chloride or stearamidopropyldimethyl(myristyl acetate)ammonium chloride sold under the name Ceraphyl^® 70 by the company Van Dyk.

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

(VI) in which Ri2 represents an alkenyl or alkyl group comprising from 8 to 30 carbon atoms, for example fatty acid derivatives of tallow,

Ri3 represents a hydrogen atom, a C₁-C₄ alkyl group or an alkenyl or alkyl group comprising from 8 to 30 carbon atoms,

Ri4 represents a C1-C4 alkyl group,

Ri5 represents a hydrogen atom, a C₁-C₄ alkyl group, X^" is an anion chosen from the group of halides, phosphates, acetates, lactates, (Ci-C₄)alkyl sulfates and (Ci-C₄)alkyl- or (Ci-C₄)alkylarylsulfonates.

Preferably, R12 and R13 denote a mixture of alkenyl or alkyl groups comprising from 12 to 21 carbon atoms, for example fatty acid derivatives of tallow, R14 denotes a methyl group, and R15 denotes a hydrogen atom. Such a product is sold, for example, under the name Rewoquat^® W 75 by the company Rewo.

- quaternary diammonium or triammonium salts, particularly of formula (VII) below:

(VII) in which Ri₆ denotes an alkyl group comprising approximately from 16 to 30 carbon atoms, which is optionally hydroxylated and/or interrupted with one or more oxygen atoms,

Ri7 is chosen from hydrogen, an alkyl group comprising from 1 to 4 carbon atoms or a group -(CH₂)3-N⁺(Ri6a)(Ri7a)(Ri8a),

Ri6a, Ri7a, Ri8a, Ri8, Ri9, R₂o and R₂1 , which may be identical or different, are chosen from hydrogen and an alkyl group comprising from 1 to 4 carbon atoms, and

X^" is an anion chosen from the group of halides, acetates, phosphates, nitrates, (Ci-C₄)alkyl sulfates, (Ci-C₄)alkyl- or (Ci- C₄)alkylarylsulfonates, in particular methyl sulfate and ethyl sulfate. Such compounds are, for example, Finquat CT-P, sold by the company Finetex (Quaternium 89), and Finquat CT, sold by the company Finetex (Quaternium 75).

- quaternary ammonium salts containing one or more ester functions, for instance those of formula (VIII) below:

(VIII)

in which:

P22 is chosen from Ci-C₆ alkyl groups and Ci-C₆ hydroxyalkyl or dihydroxyalkyl groups,

P23 is chosen from:

O

- the group R— c—

- linear or branched, saturated or unsaturated C1-C22 hydrocarbon-based groups R27,

- a hydrogen atom,

R25 is chosen from:

O

- the group ¾— c— ,

linear or branched, saturated or unsaturated Ci-C₆ hydrocarbon-based groups R29,

- a hydrogen atom,

R24, R26 and R28, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C7-C21 hydrocarbon-based groups,

r, s and t, which may be identical or different, are integers ranging from 2 to 6,

rl and tl, which may be identical or different, are equal to 0 or 1, r2 + r l = 2 r and t l + t2 = 2 t,

y is an integer ranging from 1 to 1 0,

x and z, which may be identical or different, are integers ranging from 0 to 1 0,

X^" is a simp le or complex, organic or mineral anion,

with the proviso that the sum x + y + z is from 1 to 15 , that when x is 0 then R₂3 denotes R₂₇, and that when z is 0 then R₂₅ denotes R₂ g .

The alkyl groups R₂₂ may be linear or branched, and more particularly linear.

Preferably, R₂₂ denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl group , and more particularly a methyl or ethyl group .

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

When R₂₃ is a hydrocarbon-based group R₂₇, it may be long and contain from 12 to 22 carbon atoms, or may be short and contain from 1 to 3 carbon atoms.

When R₂₅ is an R₂₉ hydrocarbon-based group , it preferably contains 1 to 3 carbon atoms.

Advantageously, R₂₄, R₂₆ and R₂s , which may be identical or different, are chosen from linear or branched, saturated or unsaturated C _{1 1} -C_{2 1} hydrocarbon-based groups, and more particularly from linear or branched, saturated or unsaturated C n -C_{2 1} alkyl and alkenyl groups .

Preferably, x and z, which may be identical or different, are equal to 0 or 1 .

Advantageously, y is equal to 1 .

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

The anion X^" is preferably a halide, preferably chloride, bromide or iodide, a (C i -C₄)alkyl sulfate or a (C ₁ -C₄)alkyl- or (C i - C₄)alkylarylsulfonate. However, it is possible to use methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate or lactate, or any other anion that is compatible with the ammonium containing an ester function.

The anion X^" is even more particularly chloride, methyl sulfate or ethyl sulfate. Use is made more particularly, in the composition according to the invention, of the ammonium salts of formula (VIII) in which:

- R22 denotes a methyl or ethyl group,

- x and y are equal to 1,

- z is equal to 0 or 1,

- r, s and t are equal to 2,

- R23 is chosen from:

O

- the group R— c—

- methyl, ethyl or C14-C22 hydrocarbon-based groups,

- a hydrogen atom,

- R25 is chosen from:

O

- the group ¾— c— ,

- a hydrogen atom,

- R24, R26 and R28, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C₁₃-C₁₇ hydrocarbon-based groups, and preferably from linear or branched, saturated or unsaturated C₁₃-C₁₇ alkyl and alkenyl groups.

The hydrocarbon-based groups are advantageously linear.

Among the compounds of formula (VIII), examples that may be mentioned include salts, especially the chloride or methyl sulfate, of diacyloxyethyldimethyl ammonium, diacyloxyethylhydroxyethyl- methylammonium, mo no acyloxyethyldihydroxyethylmethyl ammonium, triacyloxyethylmethylammonium or monoacyloxyethylhydroxyethyl- dimethylammonium, and mixtures thereof. The acyl groups preferably contain 14 to 18 carbon atoms and are obtained more particularly from a plant oil, such as palm oil or sunflower oil. When the compound contains several acyl groups, these groups may be identical or different.

These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, an alkyldiethanolamine or an alkyldiisopropanolamine, which are optionally oxyalkylenated, with fatty acids or with fatty acid mixtures of vegetable or animal origin, or by transesterification o f the methyl esters thereof. This esterification is fo llowed by a quaternization by means of an alkylating agent such as an alkyl halide, preferably methyl or ethyl halide, a dialkyl sulfate, preferably dimethyl or diethyl sulfate, methyl methanesulfonate, methyl para-toluenesulfonate, glyco l chlorohydrin or glycerol chlorohydrin.

Such compounds are, for example, sold under the names

Dehyquart^® by the company Henkel, Stepanquat^® by the company Stepan, Noxamium^® by the company Ceca or Rewoquat^® WE 1 8 by the company Rewo-Witco .

The composition according to the invention may contain, for example, a mixture o f quaternary ammonium monoester, diester and triester salts with a weight majority o f diester salts .

Examples o f such compounds that may be mentioned include distearoylethylhydroxyethylmethylammonium or dipalmitoylethyl- hydroxyethylmethylammonium salts, and in particular the methosulfates.

It is also possible to use the ammonium salts containing at least one ester function that are described in patents US-A-4 874 554 and

US-A-4 137 1 80.

Use may also be made o f behenoylhydroxypropyltrimethyl- ammonium chloride, for example, sold by the company KAO under the name Quartamin BTC 13 1 .

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

Among the cationic surfactants, it is more particularly preferred to choose cetyltrimethylammonium, behenyltrimethyl- ammonium and dipalmitoylethylhydroxyethylmethylammonium salts, and mixtures thereof, and more particularly behenyltrimethyl- ammonium chloride, cetyltrimethylammonium chloride, and dipalmitoylethylhydroxyethylammonium methosulfate, and mixtures thereo f. In one embodiment of the invention, the self-foaming non- co louring hair composition comprises one or more surfactants chosen from nonionic and anionic surfactants and in particular from nonionic surfactants such as ( C 6 - C 24 alkyl)-mono- or polyglycosides, and anionic surfactants, in particular (C₆ -4 o acyl)glutamates or (C₆ -4 o acyl)isethionates .

The non-co louring hair composition according to the invention preferably has a total content of surfactants of less than or equal to 10% by weight, better still less than 8 % by weight and even better still less than 7.5 % by weight, relative to the total weight of the composition.

More particularly, the total content of surfactant(s) may range from 0. 1 % to 10% by weight, better still from 0.5 % to 8 % by weight and even more preferentially from 1 % to 7.5 % by weight, relative to the total weight of the composition.

The weight ratio of the total amount of surfactant(s) to the total amount of anionic copolymer(s) derived from at least one unsaturated carboxylic acid and from at least one ester of an unsaturated carboxylic acid and o f a monoalcoho l comprising from 1 to 6 carbon atoms is preferably less than 3 , better still ranging from 0.0 1 to 2.8 and even better still ranging from 0.05 to 2.5 , or even ranging from 0. 1 to 2. 1 .

The self-foaming non-co louring hair composition according to the invention also contains one or more alkaline agent(s) .

The term " alkaline agent" means any agent for increasing the pH of the composition in which it is present.

The alkaline agent may be a Bronsted-Lowry or Lewis base . It may be mineral or organic.

In particular, the alkaline agent(s) may be chosen from:

a) aqueous ammonia,

b) alkanolamines such as mono-, di- and triethanolamines, isopropanolamine and 2-amino-2-methyl- 1 -propanol, and also derivatives thereo f,

c) oxyethylenated and/or oxypropylenated ethylenediamines, d) mineral or organic hydroxides,

e) alkali metal silicates such as sodium metasilicates,

f) amino acids, preferably basic amino acids, such as arginine, lysine, ornithine, citrulline and histidine,

g) carbonates and bicarbonates, particularly of a primary amine, secondary amine or tertiary amine, or of an alkali metal or alkaline-earth metal, or of ammonium, and

h) the compounds of formula (IX) below:

Rx Rz

\

N W N

Ry Rt (IX) in which W is a Ci-C₆ alkylene residue optionally substituted with a hydroxyl group or a Ci-C₆ alkyl group; Rx, Ry, Rz and Rt, which may be identical or different, represent a hydrogen atom or a Ci-C₆ alkyl, Ci-C₆ hydroxyalkyl or Ci-C₆ aminoalkyl group.

Examples of such compounds of formula (IX) that may be mentioned include 1 ,3-diaminopropane, 1 ,3-diamino-2-propanol, spermine and spermidine.

The mineral or organic hydroxides are preferably chosen from hydroxides of an alkali metal, hydroxides of an alkaline-earth metal, for instance sodium hydroxide or potassium hydroxide, hydroxides of a transition metal, such as hydroxides of metals from groups III, IV, V and VI of the Periodic Table of the Elements, hydroxides of lanthanides or actinides, quaternary ammonium hydroxides and guanidinium hydroxide.

The hydroxide may be formed in situ, for instance guanidine hydroxide, by reacting calcium hydroxide and guanidine carbonate.

The preferred alkaline agents are in particular aqueous ammonia, ammonium carbonate, sodium carbonate, ammonium bicarbonate, sodium bicarbonate, arginine and alkanolamines. Better still, the alkaline agent is chosen from alkanolamines, in particular monoethano lamine, triethanolamine and 2-amino-2-methyl- 1 -propanol.

The alkaline agent(s) as defined previously may represent, for example, from 0.01 % to 5 % by weight, and preferably from 0. 1 % to 3 % by weight, relative to the total weight of the composition.

The propellant gas(es) used in the self-foaming non-co louring hair composition are preferably chosen from C i _₅ alkanes, for instance propane, isopropane, butane, isobutane, pentane or isopentane, and mixtures thereo f. Even more preferentially, the propellant gas(es) are chosen from isobutane and isopentane, and mixtures thereof. Better still, a mixture of isopentane and isobutane is used.

The propellant gas(s) as defined previously may represent, for example, from 1 % to 20% by weight, preferably from 1 % to 10% by weight and better still from 1 % to 5 % by weight, relative to the total weight of the composition.

The composition according to the invention may also contain one or more associative polymers .

These associative po lymers may be anionic, cationic, amphoteric or nonionic. They are preferably chosen from nonionic associative po lymers.

For the purposes of the present invention, the term " fatty chain" means a linear or branched alkyl or alkenyl chain comprising at least 8 carbon atoms, preferably from 8 to 30 carbon atoms and better still from 10 to 22 carbon atoms .

The nonionic associative po lymers that may be used in the invention are preferably chosen from:

( 1 ) cellulo ses mo dified with groups comprising at least one fatty chain. Examples that may be mentioned include :

- hydroxyethylcellulo ses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C 8 -C₂₂ , for instance the products Natrosol Plus Grade 330 C S (C i ₆ alkyls) or Polysurf 67 C S so ld by the company Ashland, or the product Bermocoll EHM 100 sold by the company Berol Nobel,

- these mo dified with alkylphenyl polyalkylene glycol ether groups, such as the product Amercell Polymer HM 1500 (nonylphenyl polyethylene glycol ( 15 ) ether) sold by the company Amercho l.

(2) hydroxypropyl guars modified with groups comprising at least one fatty chain, such as the product Esaflor HM 22 (C₂₂ alkyl chain) so ld by the company Lamberti, and the products RE210- 1 8 (C _{1 4} alkyl chain) and RE205 - 1 (C₂₀ alkyl chain) sold by the company Rhodia Chimie.

(3) inulins modified with groups comprising at least one fatty chain, such as alkyl carbamate inulins and in particular the lauryl carbamate inulin sold by the company Orafti under the name Inutec SP 1 .

(4) copolymers of vinylpyrrolidone and of fatty-chain hydrophobic monomers, of which examples that may be mentioned include :

the products Antaron V2 16 or Ganex V21 6 (vinylpyrro lidone/hexadecene copolymer) sold by the company ISP, - the products Antaron V220 or Ganex V220

(vinylpyrro lidone/eicosene copolymer) sold by the company ISP.

(5) copolymers of C i -C₆ alkyl methacrylates or acrylates and o f amphiphilic monomers comprising at least one fatty chain, for instance the oxyethylenated methyl acrylate/stearyl acrylate copolymer sold by the company Go ldschmidt under the name Antil 208.

(6) copolymers of hydrophilic methacrylates or acrylates and o f hydrophobic monomers comprising at least one fatty chain, for instance the polyethylene glycol methacrylate/lauryl methacrylate copolymer.

(7) polyurethane polyethers comprising in their chain both hydrophilic blo cks usually of polyoxyethylenated nature and hydrophobic blo cks, which may be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences. (8) polymers with an aminoplast ether backbone bearing at least one fatty chain, such as the Pure Thix compounds so ld by the company Sud-Chemie.

Preferably, the polyurethane polyethers comprise at least two hydrocarbon-based lipophilic chains containing from 6 to 30 carbon atoms, separated by a hydrophilic blo ck, the hydrocarbon-based chains possibly being pendent chains or chains at the end of a hydrophilic blo ck. In particular, it is possible for one or more pendent chains to be envisaged. In addition, the polymer may comprise a hydrocarbon-based chain at one end or at both ends of a hydrophilic block.

The po lyurethane po lyethers may be multiblock, in particular in triblock form. The hydrophobic blo cks may be at each end of the chain (for example : triblock copolymer containing a hydrophilic central blo ck) or distributed both at the ends and in the chain (for example multiblock copolymer) . These same polymers may also be graft polymers or star polymers.

The nonionic fatty-chain polyurethane polyethers may be triblo ck copolymers in which the hydrophilic blo ck is a polyoxyethylenated chain comprising from 50 to 1000 oxyethylene groups . The nonionic po lyurethane po lyethers comprise a urethane bond between the hydrophilic blo cks, whence arises the name.

By extension, also included among the nonionic fatty-chain polyurethane polyethers are those in which the hydrophilic blocks are linked to the lipophilic blocks via other chemical bonds.

As examples of nonionic fatty-chain polyurethane polyethers that may be used in the invention, it is also possible to use Rheolate 205 containing a urea function, so ld by the company Elementis, or Rheo late 208 , 204 or 212, and also Acrysol RM 1 84.

Mention may also be made o f the product Elfacos T21 0 containing a C _{1 2}-C _{1 4} alkyl chain, and the product Elfacos T2 12 containing a C _{1 8} alkyl chain, from Akzo .

The product DW 1206B from Rohm & Haas containing a C₂o alkyl chain and a urethane bond, sold at a solids content of 20% in water, may also be used. Use may also be made of solutions or dispersions of these polymers, especially in water or in aqueous-alcoholic medium. Examples of such polymers that may be mentioned are Rheolate 255, Rheolate 278 and Rheolate 244 sold by the company Elementis. The products DW 1206F and DW 1206J sold by the company Rohm & Haas may also be used.

The polyurethane polyethers that may 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).

In a first variant, use is made of an associative nonionic polyurethane polyether that may be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 100 to 180 mol of ethylene oxide, (ii) a polyoxyethylenated stearyl alcohol comprising 100 mol of ethylene oxide, and (iii) a diisocyanate.

Such a polymer is especially sold by the company Elementis under the name Rheolate FX 1100®, which is a polycondensate of polyethylene glycol containing 136 mol of ethylene oxide, of stearyl alcohol polyoxyethylenated with 100 mol of ethylene oxide and of hexamethylene diisocyanate (HDI) with a weight-average molecular weight (Mw) of 30000 (INCI name: PEG- 136/Steareth- 100/HDI Copolymer).

In a second variant, use may also be made of a polyurethane polyether that may be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide, (ii) stearyl alcohol or decyl alcohol, and (iii) at least one diisocyanate.

Such polyurethane polyethers are sold especially by the company Rohm & Haas under the names Aculyn 46 and Aculyn 44 [Aculyn 46 is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of stearyl alcohol and of methylenebis(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 containing 150 or 180 mol of ethylene oxide, of decyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 35 % by weight in a mixture of propylene glyco l (39%) and water (26%)] .

When one or more additional, preferably nonionic, associative polymer(s) are present, the amount thereof ranges from 0.0 1 % to 20% by weight, preferably from 0. 1 % to 10% by weight and better still from 0.5 % to 5 % by weight relative to the total weight of the self- foaming non-co louring hair composition.

The composition according to the invention may also comprise one or more polymers other than the anionic copolymers according to the invention, and especially chosen from cationic and amphoteric polymers, and also mixtures thereof.

The term "cationic po lymer" means any polymer comprising cationic groups and/or groups that can be ionized to cationic groups. Preferably, the cationic po lymer is hydrophilic or amphiphilic. The preferred cationic polymers are chosen from those that contain units comprising primary, secondary, tertiary and/or quaternary amine groups that may either form part of the main polymer chain or may be borne by a side substituent directly connected thereto .

The cationic po lymers that may be used preferably have a weight-average mo lar mass (Mw) o f between 500 and 5 x 10⁶ approximately and preferably between 10³ and 3 x 10⁶ approximately.

Among the cationic po lymers, 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 o f the fo llowing formulae :

in which :

- R₃ , which may be identical or different, denote a hydrogen atom or a CH₃ group ;

- A, which may be identical or different, represent a linear or branched divalent alkyl group of 1 to 6 carbon atoms , preferably 2 or 3 carbon atoms , or a hydroxyalkyl group of 1 to 4 carbon atoms ;

- R₄ , R₅ and R₆ , which may be identical or different, represent an alkyl group containing from 1 to 1 8 carbon atoms or a benzyl group , and preferably an alkyl group containing from 1 to 6 carbon atoms ;

- Ri and R₂ , which may be identical or different, represent a hydrogen atom or an alkyl group containing from 1 to 6 carbon atoms , and 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 o f family ( 1 ) may also contain one or more units derived from comonomers which may be chosen from the family o f acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen with C ₁ -C₄ alkyls, acrylic or methacrylic acids or esters thereof, vinyllactams such as vinylpyrro lidone or vinylcapro lactam, and vinyl esters .

Among these copolymers of family ( 1 ), mention may be made o f: - copolymers o f acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with a dimethyl halide, such as the product sold under the name Herco flo c by the company Hercules,

copolymers o f acrylamide and of methacryloyloxyethyl- trimethylammonium chloride, such as those sold under the name Bina Quat P 100 by the company Ciba Geigy,

the copolymer of acrylamide and of methacryloyloxyethyl- trimethylammonium methosulfate, such as the product sold under the name Reten by the company Hercules,

- quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers, such as the products sold under the name Gafquat by the company ISP, for instance Gafquat 734 or Gafquat 755 , or alternatively the products known as 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 7 13 by the company ISP,

vinylpyrro lidone/methacrylamidopropyldimethylamine copo lymers, such as those so ld under the name Styleze CC 10 by ISP;

- quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers such as the product sold under the name Gafquat HS 100 by the company ISP,

- preferably crosslinked polymers of methacryloyloxy(C i -C₄)alkyl tri(C i -C₄)alkylammonium salts, such as the polymers obtained by homopolymerization o f dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homo- or copolymerization being fo llowed by crosslinking with an olefinically unsaturated compound, more particularly methylenebisacrylamide. A crosslinked acrylamide/ methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form o f a dispersion comprising 50% by weight of the said copolymer in mineral oil may be used more particularly. This dispersion is so ld under the name Salcare® SC 92 by the company Ciba. A crosslinked methacryloyloxyethyltrimethylammonium chloride homopolymer comprising about 50% by weight of the homopolymer in mineral oil or in a liquid ester can also be used. These dispersions are so ld under the names Salcare® SC 95 and Salcare® SC 96 by the company Ciba.

(2) Cationic po lysaccharides, especially cationic cellulo ses and cationic galactomannan gums . Among the cationic polysaccharides, mention may be made more particularly o f cellulose ether derivatives comprising quaternary ammonium groups, cationic cellulo se copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and cationic galactomannan gums.

The cellulo se ether derivatives comprising quaternary ammonium groups are especially described in FR 1 492 597, and mention may be made o f the po lymers so ld under the name Ucare Po lymer "JR" (JR 400 LT, JR 125 and JR 30M) or "LR" (LR 400 or LR 30M) by the company Amercho l. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethyl cellulose that have reacted with an epoxide substituted with a trimethylammonium group .

Cationic cellulo se copolymers or cellulose derivatives grafted with a water-so luble quaternary ammonium monomer are described especially in US patent 4 13 1 576, and mention may be made o f hydroxyalkyl cellulo ses, for instance hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses grafted, in particular, with a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethyl- ammonium or dimethyldiallylammonium salt. The commercial products corresponding to this definition are more particularly the products sold under the names Celquat L 200 and Celquat H 100 by the company National Starch.

The cationic galactomannan gums are described more particularly in US patents 3 589 578 and 4 03 1 307, and mention may be made o f guar gums comprising cationic trialkylammonium groups . Use is made, for examp le, of guar gums modified with a 2,3 - epoxypropyltrimethylammonium salt (for examp le, a chloride) . Such products are especially sold under the names Jaguar C 13 S , Jaguar C 15 , Jaguar C 17 or Jaguar C I 62 by the company Rhodia.

(3) Polymers composed of piperazinyl units and o f divalent alkylene or hydroxyalkylene groups containing linear or branched chains, optionally interrupted by oxygen, sulfur or nitrogen atoms or by aromatic or heterocyclic rings, and also the oxidation and/or quaternization products of these polymers.

(4) Water-so luble po lyamino amides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyamino amides can be crosslinked with an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-halo acyldiamine, a bis-alkyl halide or alternatively with an o ligomer resulting from the reaction of a difunctional compound which is reactive with a bis-halohydrin, a bis- azetidinium, a bis-halo acyldiamine, a bis-alkyl halide, an epihalohydrin, a diepoxide or a bis-unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mo l per amine group of the po lyamino amide; these polyaminoamides can be alkylated or, if they comprise one or more tertiary amine functions, they can be quaternized.

(5) Polyamino amide derivatives resulting from the condensation o f polyalkylene polyamines with polycarboxylic acids fo llowed by alkylation with difunctional agents. Mention may be made, for example, of adipic acid/dialkylaminohydroxyalkyldialkylenetriamine polymers in which the alkyl group comprises from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl. Among these derivatives, mention may be made more particularly o f the adipic acid/dimethylaminohydroxypropyl/diethylenetriamine polymers sold under the name Cartaretine F, F4 or F8 by the company Sandoz.

(6) Polymers obtained by reacting a po lyalkylene po lyamine 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 containing from 3 to 8 carbon atoms; the mole ratio between the polyalkylene polyamine and the dicarboxylic acid preferably being between 0.8:1 and 1.4:1; the resulting polyamino amide being reacted with epichlorohydrin in a mole ratio of epichlorohydrin relative to the secondary amine group of the polyamino amide preferably of between 0.5:1 and 1.8:1. Polymers of this type are sold in particular under the name Hercosett 57 by the company Hercules Inc. or alternatively under the name PD 170 or Delsette 101 by the company Hercules in the case of the adipic acid/epoxypropyl/diethylenetriamine copolymer.

(7) Cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium, such as the homopolymers or copolymers containing, as main constituent of the chain, units corresponding to formula (PI) or (PII): 2

(C

in which

- k and t are equal to 0 or 1, the sum k + t being equal to 1;

- Ri2 denotes a hydrogen atom or a methyl group;

- Rio and Rn, independently of each other, denote an alkyl group containing from 1 to 6 carbon atoms, a hydroxyalkyl group in which the alkyl group contains 1 to 5 carbon atoms, a C1-C4 amidoalkyl group; or alternatively Rio and Rn may denote, together with the nitrogen atom to which they are attached, heterocyclic groups such as piperidyl or morpholinyl; Rio and Rn, independently of each other, preferably denote an alkyl group containing from 1 to 4 carbon atoms.

- Y^" is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate. Mention may be made more particularly of the dimethyldiallylammonium salt (for example chloride) homopolymer for example sold under the name Merquat 100 by the company Nalco (and homologues thereof of low weight-average molar masses) and the copolymers of diallyldimethylammonium salts (for example chloride) and of acrylamide, sold especially under the name Merquat 550 or Merquat 7SPR.

(8) quaternary diammonium polymers comprising repeating units of formula:

1³ I 15

in which:

- Pi3, Pi4, Ri5 and Ri₆, which may be identical or different, represent aliphatic, alicyclic or arylaliphatic groups comprising from 1 to 20 carbon atoms or C₁-C4 hydroxyalkylaliphatic groups, or alternatively Ri3, Ri4, Ri5 and Ri₆, together or separately, constitute, with the nitrogen atoms to which they are attached, heterocycles optionally comprising a second heteroatom other than nitrogen, or alternatively Ri3, Ri4, Ri5 and Ri₆ represent a linear or branched Ci-C₆ alkyl group substituted with a nitrile, ester, acyl or amide group or a group -CO-O- R17-D or -CO-NH-Ri7_D where R17 is an alkylene and D is a quaternary ammonium group;

- Ai and Bi represent divalent polymethylene groups comprising from 2 to 20 carbon atoms which may be linear or branched, and saturated or unsaturated, and which may contain, linked to or inserted in the main chain, one or more aromatic rings, or one or more oxygen or 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_ls R13 and R15 can form, with the two nitrogen atoms to which they are attached, a piperazine ring. In addition, if Al denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene group, Bi can also denote a group (CH₂)„-CO-D-OC-(CH₂)„- in which D denotes:

a) a glycol residue of formula -0-Z-0-, in which Z denotes a linear or branched hydrocarbon-based group, or a group corresponding to one of the following formulae: -(CH₂-CH₂-0)_x-CH₂-CH₂- and -[CH₂- CH(CH₃)-0]_y-CH₂-CH(CH₃)-, 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-, in which Y denotes a linear or branched hydrocarbon group, or alternatively the divalent group -CH₂-CH₂-S-S-CH₂-CH₂-;

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 of between 1000 and 100000.

Mention may be made more particularly of polymers that are composed of repeating units corresponding to the formula:

-

in which R_ls R₂, R₃ and R₄, which may be identical or different, denote an alkyl or hydroxyalkyl group containing from 1 to 4 carbon atoms approximately, n and p are integers ranging from 2 to 20 approximately, and X^" is an anion derived from a mineral or organic acid.

A compound of formula (PIV) that is particularly preferred is the one for which R_ls R₂, R₃ and R₄ represent a methyl group and n = 3, p = 6 and X = CI, which is known as Hexadimethrine chloride according to the INCI (CTFA) nomenclature.

(9) Polyquaternary ammonium polymers comprising units of formula (PV): R, R 20

— N+ - (CH₂)_r - NH - CO - (CH₂)_q - CO - NH (CH₂)_S - N+ - A—

R 19 (PV) R

X- 21 in which:

- Ri8, Ri9, R₂₀ and R₂₁, which may be identical or different, represent a hydrogen atom or a methyl, ethyl, propyl, β-hydroxyethyl, β- hydroxypropyl or -CH₂CH₂(OCH₂CH₂)_pOH group, where p is equal to 0 or to an integer between 1 and 6, with the proviso that Ri₈, R19, R₂₀ and R₂₁ do not simultaneously represent a hydrogen atom,

- r and s, which may be identical or different, are integers between 1 and 6,

- q is equal to 0 or to an integer between 1 and 34,

- X^" denotes an anion such as a halide,

- A denotes a radical of a dihalide or preferably represents -CH₂-CH₂-0-

Examples that may be mentioned include the products Mirapol® A 15, Mirapol® AD1, Mirapol® AZ1 and Mirapol® 175 sold by the company Miranol.

(10) Quaternary polymers of vinylpyrrolidone and of vinylimidazole, for instance the products sold under the names Luviquat® FC 905, FC 550 and FC 370 by the company BASF.

(11) Polyamines such as Polyquart® H sold by Cognis, referred to under the name Polyethylene glycol (15) tallow polyamine in the CTFA dictionary.

(12) Polymers comprising in their structure:

(a) one or more units corresponding to formula (A) below:

— CH₂— CH—

NH₂ (A)

(b) optionally, one or more units corresponding to formula (B) below: NH— C-H

I I

O

In other words, these polymers may be chosen especially from homopolymers or copolymers comprising one or more units derived from vinylamine and optionally one or more units derived from vinylformamide.

Preferably, these cationic po lymers are chosen from po lymers comprising, in their structure, from 5 mo l% to 100 mo l% of units corresponding to formula (A) and from 0 to 95 mo l% of units corresponding to formula (B), preferentially from 10 mo l% to 1 00 mo l% of units corresponding to formula (A) and from 0 to 90 mo l% of units corresponding to formula (B) .

These po lymers may be obtained, for example, by partial hydro lysis o f po lyvinylformamide . This hydrolysis may be performed in an acidic or basic medium.

The weight-average mo lecular mass of the said po lymer, measured by light scattering, may range from 1000 to 3 000 000 g/mo l, preferably from 10 000 to 1 000 000 g/mol and more particularly from

100 000 to 500 000 g/mo l.

The cationic charge density o f these polymers may range from 2 to 20 meq/g, preferably from 2.5 to 1 5 meq/g and more particularly from

3.5 to 10 meq/g.

The po lymers comprising units o f formula (A) and optionally units o f formula (B) are sold especially under the name Lupamin by the company BASF, for instance, in a non-limiting manner, the products so ld under the names Lupamin 9095 , Lupamin 5095 , Lupamin 1095 , Lupamin 9030 (or Luviquat 9030) and Lupamin 9010.

Other cationic po lymers that may be used in the context of the invention are cationic proteins or cationic protein hydrolysates, polyalkyleneimines, in particular polyethyleneimines, polymers comprising vinylpyridine or vinylpyridinium units, condensates o f polyamines and of epichlorohydrin, quaternary polyureylenes and chitin derivatives.

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

Among the cationic po lymers mentioned above, the ones that may preferably be used are cationic po lysaccharides, especially cationic cellulo ses and cationic galactomannan gums, and in particular quaternary cellulo se ether derivatives such as the products so ld under the name JR 400 by the company Amercho l, cationic cyclopo lymers, in particular dimethyldiallylammonium salt (for example chloride) homopolymers or copolymers, sold under the names Merquat 100, Merquat 550 and Merquat S by the company Nalco, and homo logues thereo f o f low weight-average mo lecular weights, quaternary polymers of vinylpyrro lidone and o f vinylimidazo le, optionally crosslinked homopolymers or copolymers of methacryloyloxy(C i -C₄)alkyltri(C i - C₄)alkylammonium salts; and mixtures thereof.

It is also possible to use amphoteric polymers, which may preferably be chosen from amphoteric polymers comprising a repetition of:

(i) one or more units derived from a monomer o f (meth)acrylamide type,

(ii) one or more units derived from a monomer o f (meth)acrylamidoalkyltrialkylammonium type, and

(iii) one or more units derived from an acidic monomer o f (meth)acrylic acid type.

Preferably, the units derived from a monomer o f (meth)acrylamide type (i) are units of structure (la) below :

in which Ri denotes H or CH₃ and R₂ is chosen from an amino, dimethylamino, tert-butylamino, dodecylamino or -NH-CH₂OH group .

Preferably, the said amphoteric po lymer comprises a repetition of only one unit of formula (la) .

The unit derived from a monomer o f (meth)acrylamide type o f formula (la) in which Ri denotes H and R₂ is an amino group (NH₂) is particularly preferred. It corresponds to the acrylamide monomer per se.

Preferably, the units derived from a monomer o f (meth)acrylamidoalkyltrialkylammonium type (ii) are units of structure (Ila) below :

in which:

- R₃ denotes H or CH₃ ,

- R₄ denotes a group (CH₂)_k with k being an integer ranging from 1 to 6 and preferably from 2 to 4;

- R₅ , R₆ and R₇, which may be identical or different, each denote an alkyl group containing from 1 to 4 carbon atoms;

- Y^" is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate .

Preferably, the said amphoteric po lymer comprises a repetition of only one unit of formula (Ila) .

Among these units derived from a monomer o f (meth)acrylamidoalkyltrialkylammonium type of formula (Ila), the ones that are preferred are those derived from the methacrylamidopropyltrimethylammonium chloride monomer, for which R₃ denotes a methyl group, k is equal to 3 , R₅ , R₆ and R₇ denote a methyl group, and Y^" denotes a chloride anion.

Preferably, the units derived from a monomer of (meth)acrylic acid type (iii) are units of formula (Ilia) :

in which R₈ denotes H or CH₃ and Rg denotes a hydroxyl group or a -NH-C(CH₃)₂-CH₂-S0₃H group.

The preferred units of formula (Ilia) correspond to the acrylic acid, methacrylic acid and 2-acrylamino-2-methylpropanesulfonic acid monomers.

Preferably, the unit derived from a monomer of (meth)acrylic acid type of formula (Ilia) is that derived from acrylic acid, for which Its denotes a hydrogen atom and Rg denotes a hydroxyl group.

The acidic monomer(s) of (meth)acrylic acid type may be non- neutralized or partially or totally neutralized with an organic or mineral base.

Preferably, the said amphoteric polymer comprises a repetition of only one unit of formula (Ilia).

According to a preferred embodiment of the invention, the amphoteric polymer(s) of this type comprise at least 30 mol% of units derived from a monomer of (meth)acrylamide type (i). Preferably, they comprise from 30 mol% to 70 mol% and more preferably from 40 mol% to 60 mol% of units derived from a monomer of (meth)acrylamide type.

The content of units derived from a monomer of (meth)acrylamidoalkyltrialkylammonium type (ii) may advantageously be from 10 mol% to 60 mol% and preferentially from 20 mol% to 55 mol%.

The content of units derived from an acidic monomer of (meth)acrylic acid type (iii) may advantageously be from 1 mol% to 20 mol% and preferentially from 5 mol% to 15 mol%.

According to a particularly preferred embodiment of the invention, the amphoteric polymer of this type comprises:

- from 30 mol% to 70 mol% and more preferably from 40 mol% to 60 mol% of units derived from a monomer of (meth)acrylamide type (i),

- from 10 mol% to 60 mol% and preferentially from 20 mol% to 55 mo l% o f units derived from a monomer o f (meth)acrylamidoalkyltrialkylammonium type (ii), and

- from 1 mo l% to 20 mo l% and preferentially from 5 mo l% to 15 mo l% of units derived from a monomer of (meth)acrylic acid type (iii) .

Amphoteric polymers of this type may also comprise additional units, other than the units derived from a monomer of (meth)acrylamide type, of (meth)acrylamidoalkyltrialkylammonium type and of (meth)acrylic acid type as described above.

However, according to a preferred embodiment of the invention, the said amphoteric po lymers consist so lely o f units derived from monomers o f (meth)acrylamide type (i), of (meth)acrylamidoalkyl- trialkylammonium type (ii) and of (meth)acrylic acid type (iii) .

As examples of amphoteric po lymers that are particularly preferred, mention may be made of acrylamide/methylacrylamidopropyl- trimethylammonium chloride/acrylic acid terpolymers. Such polymers are listed in the CTFA International Cosmetic Ingredient Dictionary, 10th edition 2004 , under the name Polyquaternium 53. Corresponding products are especially sold under the names Merquat 2003 and Merquat 2003 PR by the company Nalco .

As another type o f amphoteric polymer that may be used, mention may also be made of copo lymers based on (meth) acrylic acid and on a dialkyldiallylammonium salt, such as copolymers of (meth) acrylic acid and of dimethyldiallylammonium chloride. An example that may be mentioned is Merquat 280 so ld by the company Nalco .

When it is/they are present, the composition according to the invention may comprise the cationic and/or amphoteric polymers in an amount ranging from 0.01 % to 5 % by weight, especially from 0.05 % to 3 % by weight and preferentially from 0. 1 % to 2% by weight, relative to the total weight of the composition.

The composition according to the invention is preferably aqueous and then comprises water at a concentration preferably ranging from 5 % to 98%o by weight, especially from 20%> to 95 % by weight and better still from 50% to 95 % by weight, relative to the total weight of the composition. The composition may also comprise one or more organic solvents that are liquid at 25 °C and 1 .013 x 10⁵ Pa, and especially water-so luble, such as C 1 - C7 alcoho ls, especially C 1 - C7 aliphatic or aromatic monoalcoho ls, and C3 - C7 polyo ls and polyo l ethers, which may thus be used alone or as a mixture with water. Advantageously, the organic so lvent may be chosen from ethano l and isopropano l, and mixtures thereo f.

The pH of the composition, if it is aqueous, is preferably between 3 and 9 and especially between 3 and 7.

The composition according to the invention may also contain one or more additives chosen from silanes such as aminopropyltriethoxysilane (APTES) or octadecyltriethoxysilane (OTES), fatty substances such as C 12 - C30 fatty alcoho ls, fatty esters such as isopropyl myristate, mineral, plant or synthetic oils such as a- olefins; silicones, ceramides, natural or synthetic thickeners or viscosity regulators other than the polymers described above; antidandruff active agents, vitamins or provitamins; nacreous agents; pH stabilizers, preserving agents; dyes; and mixtures thereof.

These additives may be present in the composition according to the invention in an amount ranging from 0 to 20% by weight, relative to the total weight of the composition.

A person skilled in the art will take care to select these optional additives and the amounts thereof such that they do not harm the properties of the compositions of the present invention.

The compositions according to the invention may be, in a non- limiting manner, in the form o f products for washing human hair, especially shampoos, conditioning products such as hair conditioners, or both.

The self-foaming non-co louring hair composition according to the invention may be packaged in an aeroso l device that is common in cosmetics.

The aeroso l device may consist of an outer aerosol can which contains both the propellant(s) and the other ingredients of the composition in a single compartment. Preferably, the said device is equipped with a valve with an inner restriction o f 0.3 to 3 mm and better still from 0.5 to 1 .5 mm, an inner nozzle of 0.3 to 3 mm and better still from 0.5 to 1 .5 mm, and an additional gas intake of 0.3 to 3 mm and better still from 0.5 to 1 .5 mm. The device also comprises a push button which is equipped with a direct outlet orifice with a diameter of between 0.25 and 1 mm and preferably between 0.4 and 0.7 mm.

According to another variant, the aerosol device may be in two compartments, formed from an outer aerosol can comprising an inner bag hermetically welded to a valve. The various ingredients of the composition are introduced into the inner bag and a compressed gas is introduced between the bag and the can at a sufficient pressure to make the product come out in the form of a spray through a nozzle orifice. Preferably, the said device is equipped with a valve with an inner restriction of 0.3 to 3 mm and better still from 0.5 to 1 .5 mm, an inner nozzle o f 0.3 to 3 mm and better still from 0.5 to 1 .5 mm. The device also comprises a push button which is equipped with a direct outlet orifice with a diameter of between 0.25 and 1 mm and preferably between 0.4 and 0.7 mm. Such a device is sold, for example, under the name EP Spray by the company EP-Spray System SA. The said compressed gas is preferably used at a pressure o f between 1 and 12 bar and better still between 9 and 1 1 bar.

A subj ect of the invention is also the use of the composition as defined previously for cleansing and/or conditioning human hair.

The present invention also relates to a process for washing/cleansing and/or conditioning human hair, which consists in applying to the human hair an effective amount of a composition as described above, and in rinsing it out.

The invention is illustrated by the examples that fo llow.

Examples

The compositions according to the invention are prepared from the ingredients indicated in the table below. The amounts indicated are expressed as weight percentages of product in its existing form, relative to the total weight of the composition.

Self-foaming detergent compositions are obtained, which may be used for cleansing the hair, and which lead to good cosmetic properties on dry hair.

Claims

1. Self-foaming non-colouring hair composition comprising: from 2% to 60% by weight, relative to the total weight of the composition, of one or more anionic copolymers derived from one or more unsaturated carboxylic acids and from one or more esters of an unsaturated carboxylic acid and of a monoalcohol comprising from 1 to 6 carbon atoms,

one or more surfactants chosen from anionic, non-ionic and amphoteric surfactants,

one or more alkaline agents, and

one or more propellant gases.

2. Composition according to Claim 1, characterized in that anionic copolymer(s) are chosen from those comprising:

a monomer corresponding to formula (I) below:

H₉C=C C— OH

R O

(I) in which formula R¹ denotes H or CH₃ or C₂H₅,

- and a monomer of formula (II) below:

in which formula R¹ denotes H or CH₃ or C₂H₅ and preferably H or CH₃, and R₂ denotes an alkyl group comprising from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms.

3. Composition according to Claim 1 or 2, characterized in that the anionic copolymer(s) are present in an amount ranging from 2.5% to 40%) by weight, preferably from 2.5%> to 30%> by weight and better still from 2.9% to 20% by weight, relative to the total weight o f the self-foaming non-co louring hair composition.

4. Composition according to any one of the preceding claims, characterized in that the surfactants are chosen from nonionic surfactants, in particular (C₆ - C 24 alkyl)-mono- or polyglycosides, and anionic surfactants, in particular (C₆ -4 o acyl)glutamates or (C₆ -4 o acyl)isethionates .

5. Composition according to any one of the preceding claims, characterized in that the surfactant(s) are present in a total amount of less than or equal to 10% by weight, better still ranging from 0. 1 % to 10%) by weight, preferably from 0.5 %> to 8% by weight, or even from 1 % to 7.5 % by weight, relative to the total weight of the composition.

6. Composition according to any one of the preceding claims, characterized in that the weight ratio of the total amount o f surfactant(s) to the total amount of anionic copolymer(s) derived from at least one unsaturated carboxylic acid and from at least one ester of an unsaturated carboxylic acid and of a monoalcoho l comprising from 1 to 6 carbon atoms is less than 3 , preferably ranging from 0.01 to 2.8 and better still from 0.05 to 2.5.

7. Composition according to any one of the preceding claims, characterized in that the alkaline agent(s) are chosen from:

a) aqueous ammonia,

b) alkano lamines such as mono-, di- and triethanolamines, isopropanolamine and 2-amino-2-methyl- 1 -propanol, and also derivatives thereo f,

c) oxyethylenated and/or oxypropylenated ethylenediamines,

d) mineral or organic hydroxides,

e) alkali metal silicates such as sodium metasilicates,

f) amino acids, preferably basic amino acids, such as arginine, lysine, ornithine, citrulline and histidine,

g) carbonates and bicarbonates, particularly of a primary amine, secondary amine or tertiary amine, or of an alkali metal or alkaline- earth metal, or of ammonium, and

h) the compounds o f formula (IX) below: Rx Rz

W N

^Ry (IX) in which W is a Ci-C₆ alkylene residue optionally substituted with a hydroxyl group or a Ci-C₆ alkyl group; Rx, Ry, Rz and Rt, which may be identical or different, represent a hydrogen atom or a Ci-C₆ alkyl, Ci-C₆ hydroxyalkyl or Ci-C₆ aminoalkyl group,

preferably from alkanolamines and better still from monoethanolamine, triethanolamine and 2-amino-2-methyl- 1 -propanol.

8. Composition according to any one of the preceding claims, characterized in that the alkaline agent(s) are present in an amount ranging from 0.01% to 5% by weight and preferably from 0.1% to 3% by weight, relative to the total weight of the hair composition.

9. Composition according to any one of the preceding claims, characterized in that the propellant gas(es) are chosen from isobutane and isopentane, and mixtures thereof, and better still is a mixture of isopentane and isobutane.

10. Composition according to any one of the preceding claims, characterized in that the propellant gas(es) are present in an amount ranging from 1% to 20% by weight, preferably from 1% to 10% by weight and better still from 1% to 5% by weight, relative to the total weight of the composition.

11. Composition according to any one of the preceding claims, characterized in that it comprises one or more associative polymers, which are preferably nonionic.

12. Composition according to any one of the preceding claims, characterized in that it comprises one or more cationic and/or amphoteric polymers, preferably in an amount ranging from 0.01% to 5% by weight, relative to the total weight of the composition.

13. Use of the composition according to any one of the preceding claims, for cleansing and/or conditioning human hair.

14. Process for washing human hair, comprising the application o f a composition according to any one o f Claims 1 to 12 to human hair, and rinsing it out.