Composition for peroxidisingly colouring creatine fibre, containing oxyalkylenated etherocarboxylic acid, mono- or polyglycerolated surfactant as well as non-ionic oxyalkylenated surfactant and some predetermined polymer

(12) PATENT DESCRIPTION (19) PL (11) 206730 (13) B1 (21) Application number: 357922 ^{(51) Int.Cl.}

A61K 8/34 (2006.01) A61K 8/39 (2006.01) A61K 8/41 (2006.01) (22) Date of notification: 20.12.2002 _{A61K 8/81 (2006.01)}

A61K 8/86 (2006.01) A61Q 5/10 (2006.01)

Keratin fiber oxidation dyeing composition, ready-to-use keratin fiber oxidation dyeing composition, keratin fiber dyeing method, multi-compartment utensil or kit for dyeing human keratin fibers (30) Priority:

December 21, 2001, FR, 0116742 (43) Application announced:

30.06.2003 BUP 13/03 (45) The following was announced about the grant of the patent:

30.09.2010 WUP 09/10 (73) Authorized by the patent:

L'OREAL, Paris, FR (72) Inventor (s):

PATRICIA DESENNE, Levallois Perret, FR

CECILE BEBOT, Clichy, FR

FLORENCE LAURENT, Asnieres, FR (74) Agent:

item. stalemate. Krajewska Krystyna PATPOL limited liability company

PL 206 730 B1

Description of the invention

The invention relates to compositions for the oxidation dyeing of keratin fibers, in particular human keratin fibers, and in particular the hair, a ready-to-use composition for the oxidation dyeing of keratin fibers, as well as multi-compartment utensils or kits for dyeing human keratin fibers and methods for dyeing keratin fibers using said composition. .

It is known to dye keratin fibers, and in particular human hair, with dyeing compositions containing oxidation dye precursors, generally called "oxidation bases, in particular o- or p-phenylenediamines, o- or p-aminophenols and heterocyclic bases.

Oxidation dye precursors are initially colorless or weakly colored compounds which develop their ability to dye the hair in the presence of oxidants, leading to the formation of colored compounds. The formation of these color compounds is the result of either the oxidative condensation of the "oxidation bases with each other or the oxidative condensation of the" oxidation bases "with the dye modifier compounds or" couplers that are generally present in dye compositions used for oxidative dyeing and are especially m phenylene diamines, m-aminophenols, m-diphenols and certain heterocycles.

The variety of molecules considered, which are on the one hand "oxidation bases" and on the other hand "couplers, make it possible to obtain a wide range of colors.

Oxidation bases and couplers are used to formulate carriers or substrates which allow them to be applied to keratin fibers when mixed with an oxidizing agent.

These bases are generally aqueous and usually contain one or more surfactants.

Until now, it has been recommended to use anionic surfactants of the etheralkyl carboxylic acid type in combination with nonionic alkoxylated surfactants. The mentioned combinations create oxidation dyeing compositions which give shades with very good dyeing properties. However, it has been observed that when the oxidation dyes are used in the form of the hydrochloride or sulfate, such combinations of surfactants lead to inhomogeneous, opaque compositions.

WO 01/93819 relates to a process for dyeing human keratin fibers using in a first step indole or indole type compounds. Such compounds are optionally removed and an oxidation dye precursor or precursors are used in a second step. One illustrative composition of this prior art comprises an oxidative dye precursor in the form of sulfate, glycerol monooleate, polyoxyethylene C12-C14 carboxylic acid, ethoxylated cetyl stearyl alcohol, and saturated C12-C18 and C15-C18 fatty alcohols.

This document does not disclose compositions containing simultaneously one or more hydrochloride or sulfate oxidizable dyes, one or more polyoxyalkylenated ether carboxylic acids, one or more mono- or polyglycerolated alkoxylated nonionic surfactants.

Now, after serious research has been carried out on the matter, the Applicant has found that it is possible to obtain oxidizable dye compositions that are rich in oxidizable dyes with a hydrochloride or sulfate content, that are clear and that make it possible to obtain shades with very good dyeing properties by partially replacing in said dye composition, alkylene nonionic surfactant, mono- or polyglycerolated nonionic surfactant.

This finding forms the basis of the present invention.

The present invention therefore relates to a composition for the oxidation dyeing of keratin fibers, in particular human keratin fibers, and in particular hair, comprising in a substrate suitable for dyeing at least one hydrochloride or sulfate oxidizable dye, characterized in that it also contains at least one a polyoxyalkylenated ether carboxylic acid of the formula I, or a salt thereof:

R - [- O-C3H6-] p - [- O-C2H4-] nO-CH2-COO-A (1) where:

PL 206 730 B1

R represents a group or mixture of linear or branched C8-C22-alkyl or C8-C22-alkenyl groups, a (C8-C9) phenyl alkyl group or a R'CONH-CH2-CH2- group, with R 'representing a C11-C21-alkyl group or C11-C21-alkenyl linear or branched, n is an integer or a decimal fraction in the range 2-24, p is an integer or a decimal fraction in the range 0-6,

A is hydrogen or Na, K, Li, 1 / 2Mg or a monoethanolamine, ammonium or triethanolamine residue;

at least one mono- or polyglycerolated nonionic surfactant selected from mono- or polyglycerolated fatty alcohols; and at least one non-ionic alkoxylated surfactant.

Said dyeing composition also makes it possible to obtain a more transparent appearance for preparations which contain it and which are liquid.

Moreover, the shades obtained have good durability.

Another object of the invention relates to a ready-to-use composition for the oxidation dyeing of keratin fibers, in particular human keratin fibers such as hair, characterized in that it is obtained by mixing a dyeing composition as defined above and an oxidizing composition containing at least one oxidant.

For the purposes of the present invention, the expression "ready-to-use composition" means a composition intended to be applied immediately to the keratin fibers, that is, which can be stored before use without further modification or obtained by the admixture of two or more compositions.

The invention also relates to a method for the oxidation dyeing of keratin fibers, in particular human keratin fibers such as hair, by applying to the fibers at least one dyeing composition comprising, in a substrate suitable for dyeing, at least one oxidizable dye in the form of a hydrochloride or sulphate, wherein the color is developed at an alkaline, neutral or acid pH using an oxidizing composition including, in a base suitable for dyeing, at least one oxidant which is mixed with the dye composition at the time of use, or which is applied sequentially without intermediate rinsing, the dye composition and the oxidizing composition also comprising, arbitrarily therebetween, at least one polyoxyalkylenated ether carboxylic acid of formula I as defined above, or a salt thereof, at least one mono- or polyglycerolated nonionic surfactant selected from mono- or polyglycerolated fatty alcohols and at least one nonionic alkoxylated surfactant.

According to an embodiment of the process according to the invention, polyoxyalkylenated ether (s) or salts thereof, mono-or polyglycerolated non-ionic surfactant (s) and non-ionic alkoxylated (s) ) the surfactant (s) are combined in the same dye or oxidation composition, and more particularly in the dye composition.

The invention also relates to a multi-compartment dyeing tool or "kit for the oxidation dyeing of keratin fibers, in particular human keratin fibers, and in particular hair, which includes one compartment containing the dye composition, and includes a base suitable for dyes, at least one oxidizable dye in the form of a hydrochloride or sulfate and a second compartment containing the oxidizing composition, comprising an oxidant in a substrate suitable for dyeing, the dye composition and the oxidizing composition further comprising, arbitrarily distributed therebetween, at least one polyoxyalkylene ether carboxylic acid of formula I as defined above or a salt thereof. at least one mono- or polyglycerolated nonionic surfactant selected from mono- or polyglycerolated fatty alcohols and at least one nonionic alkoxylated surfactant.

According to an embodiment of the inventive device, polyoxyalkylenated ether carboxylic acid (s) or salts thereof, mono- or polyglycerolated nonionic agent (s): (i) surfactant (s) and non-ionic alkoxylated (s) e) the surfactant (s) are combined in the same dye or oxidation composition, and more particularly in the dye composition.

Alkoxylated ether carboxylic acids and their salts

By the expression "alkoxylated ether carboxylic acid" is meant any compound of the formula 1 below:

R - [- O-C3H6-] p - [- O-C2H4-] nO-CH2-COO-A (1) where:

PL 206 730 B1

R represents a group or mixture of linear or branched (C8-C22) -alkyl or (C8-C22) -alkenyl groups, a (C8-C9) phenyl group or an R'CONH-CH2-CH2- group, with R 'being the group ( C11-C21) -alkyl or (C11-C21) -alkenyl linear or branched, n is an integer or a decimal fraction in the range 2-24, p is an integer or a decimal fraction in the range 0-6,

A is hydrogen or Na, K, Li, 1 / 2Mg or a monoethanolamine, ammonium or triethanolamine residue.

Alkoxylated ether carboxylic acids and their salts used preferably according to the present invention, are selected from those compounds of formula I wherein R is a group or mixture of alkyl (C12-C14), oleyl, cetyl, stearyl groups; nonylphenyl or octylphenyl group, A is hydrogen or sodium, p = 0 and n ranges from 2-20, preferably 2-10.

Even more preferably, compounds of formula I are used in which R is a C12-alkyl group, A is hydrogen or sodium, p = 0 and n ranges from 2-10.

Among the commercial products, the products sold by Chem Y under the names:

Akypo® NP 70 (R = nonylphenyl, n = 7, p = 0, A = H)

Akypo® NP 40 (R = nonylphenyl, n = 4, p = 0, A = H)

Akypo® OP 40 (R = octylphenyl, n = 4, p = 0, A = H)

Akypo® OP 80 (R = octylphenyl, n = 8, p = 0, A = H)

Akypo® OP 190 (R = octylphenyl, n = 19, p = 0, A = H)

Akypo® RLM 38 (R = alkyl (C12-C14), n = 3.8, p = 0, A = H)

Akypo® RLM 38 NV (R = alkyl (C12-C14), n = 4, p = 0, A = Na)

Akypo® RLM 45 (R = alkyl (C12-C14), n = 4.5, p = 0, A = H)

Akypo® RLM 45 NV (R = alkyl (C12-C14), n = 4.5, p = 0, A = Na)

Akypo® RLM 100 (R = alkyl (C12-C14), n = 10, p = 0, A = H)

Akypo® RLM 100 NV (R = alkyl (C12-C14), n = 10, p = 0, A = Na)

Akypo® RLM 130 (R = alkyl (C12-C14), n = 13, p = 0, A = H)

Akypo® RLM h160 NV (R = alkyl (C12-C14), n = 16, p = 0, A = Na)

Akypo® RO 20 (R = oleil, n = 2, p = 0, A = H)

Akypo® RO 90 (R = oleil, n = 9, p = 0, A = H)

Akypo® RCS 60 (R = cetyl / stearyl, n = 6, p = 0, A = H)

Akypo® RS 60 (R = stearyl, n = 6, p = 0, A = H)

Akypo® RS 100 (R = stearyl, n = 10, p = 0, A = H)

Akypo® RO 50 (R = oleil, n = 5, p = 0, A = H) or by Sandoz under the names:

Sandopan ACA-48 (R = cetyl / stearyl, n = 24, p = 0, A = H)

Sandopan DTC-Acid (R = C13 alkyl, n = 6, p = 0, A = H)

Sandopan DTC (R = C13 alkyl, n = 6, p = 0, A = Na)

Sandopan LS 24 (R = alkyl (C12-C14), n = 12, p = 0, A = Na)

Sandopan JA 36 (R = C13 alkyl, n = 18, p = 0, A = H), especially products sold under the following names:

Akypo® NP 70

Akypo® NP 40

Akypo® OP 40

Akypo® OP 80

Akypo® RLM 25

Akypo® RLM 45

Akypo® RLM 100

Akypo® RO 20

Akypo® RO 50

Akypo® RLM 38.

Alkoxylated ether carboxylic acids or their salts constitute about 2-15%, preferably about

3-10% by weight of the total weight of the dye composition and about 0.5-15%, preferably about 0.7-10% of the total weight of the ready-to-use composition (containing oxidant).

Mono- or polyglycerolated nonionic surfactants

PL 206 730 B1

Mono- or polyglycerolated nonionic surfactants are especially chosen from mono- or polyglycerolated fatty alcohols.

The term "mono- or polyglycerolated fatty alcohol means any compound of the following formula (2):

<img file="PL206730B1_D0001.tif" />

wherein

R is a saturated or unsaturated linear or branched group containing 8-40 carbon atoms, preferably 10-30 carbon atoms;

m is a number in the range 1-30 and preferably 1-10.

Compounds of this type that may be mentioned include lauryl alcohol containing 4 moles of glycerol (INCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcohol containing 1.5 moles of glycerol, oleyl alcohol containing 4 moles of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether) ), oleyl alcohol containing 2 moles of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether), cetearyl alcohol containing 2 moles of glycerol, cetearyl alcohol containing 6 moles of glycerol, oleocetyl alcohol containing 6 moles of glycerol and octadecanol containing 6 moles of glycerol.

The fatty alcohol can be a mixture of fatty alcohols in that the m value is a statistical value, meaning that several types of polyglycerolated fatty alcohols can coexist in the commercial product as a mixture.

Among the particularly preferred mono- or polyglycerolated fatty alcohols used are a C8 / C10 alcohol containing one mole of glycerol, a C10 / C12 alcohol containing one mole of glycerol, and a C12 alcohol containing 1.5 moles of glycerol.

Oxyalkylenated nonionic surfactants

According to the invention, the expression "alkoxylated nonionic surfactants" means nonionic surfactants which carry in their molecule one or more groups selected from the following groups: -CH2-CH2-O-, -CH2-CH2-CH2-O-, CH2- CH (CH3) -O- or mixtures thereof.

Among the alcohols, mention may be made of α-diols, ethoxylated or propoxylated alkylphenols having a fatty chain containing e.g. 8-22 carbon atoms, the number of ethylene oxide or propylene oxide groups possibly being in the range 1-50, ethylene oxide and propylene oxide condensates with fatty alcohols, ethoxylated vegetable oils, polyoxyethylene fatty amides having 2-30 moles of ethylene oxide, esters fatty acids and polyethylene glycols and polyoxyethylene sorbitol fatty acid esters containing 2-30 moles of ethylene oxide.

Ethoxylated nonionic surfactants particularly preferred according to the invention are fatty alcohols containing 8-22 carbon atoms and ethoxylated with 1-10 moles of ethylene oxide (1-10EO). Among them, mention may be made, in particular, of lauryl alcohol 2 EO, lauryl alcohol 3 EO and decyl alcohol 5 EO.

The mono- or polyglycerolated nonionic alkoxylated surfactant (s) comprises approximately 2-40%, preferably approximately 4-20% of the total weight of the ready-to-use dye composition (containing oxidant).

Preferably, these two types of nonionic surfactant are used in a mono- or polyglycerolated nonionic surfactant / alkoxylated nonionic surfactant ratio in the range 0.5-2.

Oxidable dyes

The composition of the present invention comprises at least one oxidizable dye in the form of a hydrochloride or sulfate.

Suitable oxidation dyes according to the invention are selected from oxidation bases and / or couplers.

Preferably the compositions according to the invention contain at least one oxidation base.

Suitable oxidation bases for use in the present invention are selected from those conventionally known in the field of oxidation dyeing, which include in particular o- and p-phenylenediamines, double bases, o- and p-aminophenols, the following heterocyclic bases as well as their salts acid addition.

The following can be mentioned in particular:

(I) p-phenylenediamines of formula (3) below and acid addition salts thereof:

<img file="PL206730B1_D0002.tif" />

wherein

R1 is a hydrogen atom or a (C1-C4) -alkyl group, a monohydroxy (C1-C4) -alkyl group, a polyhydroxy (C2-C4) -alkyl group, an alkoxy (C1-C4) alkyl (C1-C4) group, a (C1-C4) group -C4) -alkyl substituted with nitrogen, phenyl or 4'-aminophenyl;

R2 is hydrogen or (C1-C4) alkyl, monohydroxy (C1-C4) alkyl or polyhydroxy (C2-C4) alkyl, alkoxy (C1-C4) alkyl (C1-C4) or (C1-C4) -alkyl substituted nitrogen group;

R1 and R2 may also form, with the nitrogen atom to which they are bound, a 5- or 6-membered nitrogen-containing heterocyclic group, optionally substituted with one or more alkyl, hydroxyl or ureido groups;

R3 represents a hydrogen atom, a halogen atom such as a chlorine atom or a (C1-C4) -alkyl group, a sulfo group, a carboxy group, a monohydroxy (C1-C4) -alkyl group or a hydroxy (C1-C4) -alkoxy group, an acetylamino group (C1-C4) -alkoxy, mesylamino (C1-C4) -alkoxy or carbamoylamino (C1-C4) -alkoxy;

R4 represents a hydrogen atom, a halogen atom or a (C1-C4) alkyl group.

Among the nitrogen groups of formula III above, mention may be made in particular of amino, monoalkyl (C1-C4) amino, dialkyl (C1-C4) amino, trialkyl (C1-C4) amino, monohydroxyalkyl (C1-C4) amino, imidazolinium and ammonium.

Among the p-phenylenediamines of the above formula (3), mention may be made in particular of p-phenylenediamine, p-tolylene diamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4 -amino-N, N-bis- (e-hydroxyethyl) -2-methylaniline, 4-amino-N, N-bis (e-hydroxyethyl) -2-chloroaniline, 2-e-hydroxyethyl-p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (e-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N-ethyl-N- (e-hydroxyethyl) -p-phenylenediamine, N- (e, Y-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine , 2-e-hydroxyethyloxy-p-phenylenediamine, 2-e-acetylaminoethyloxy-p-phenylenediamine, N- (e-methoxyethyl) -p-phenylenediamine, 2-methyl-1- N-hydroxyethyl-p-phenylenediamine and N- (4-aminophenyl) -3-hydroxypyrrolidine, and acid addition salts thereof.

Among the p-phenylenediamines of formula III above, p-phenylenediamine, p-tolylene diamine, 2-isopropyl-p-phenylenediamine, 2-e-hydroxyethyl-p-phenylenediamine,

2-e-hydroxyethyloxy-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, N, N-bis (e-hydroxyethyl) -p-phenylenediamine, 2-chloro-p-phenylenediamine, and acid addition salts thereof.

- (II) According to the invention, the term double bases denotes compounds containing at least two aromatic molecules, bearing amino and / or hydroxyl groups.

Among the double bases which can be used as oxidation bases in the dyeing compositions according to the invention, mention may be made, in particular, of the compounds according to formula (4) below and their acid addition salts:

PL 206 730 B1

<img file="PL206730B1_D0003.tif" />

- Z1 and Z2, which may be identical or different, represent a hydroxyl group or -NH2 which may be substituted by a (C1-C4) -alkyl group or by a Y-linkage;

- the linking member Y is an alkylene chain containing 1-14 carbon atoms, straight or branched and which may be interrupted or terminated with one or more nitrogen groups and / or one or more heteroatoms, such as oxygen, sulfur or nitrogen, and optionally substituted with one or more hydroxyl or C1-C6-alkoxy groups,

- R5 and R6 represent a hydrogen or halogen atom, a C1-C4-alkyl group, a monohydroxy (C1-C4) -alkyl group, a polyhydroxy (C2-C4) -alkyl group, an amino (C1-C4) -alkyl group or a Y-linking member ;

- R7, R8, R9, R10, R11 and R12, which may be identical or different, represent a hydrogen atom, a Y-linkage or a C1-C4-alkyl group; provided that the compounds of formula (4) contain only one Y-binding member per molecule.

Nitrogen groups of formula (4) above include especially amino, monoalkyl (C1-C4) amino, dialkyl (C1-C4) amino, trialkyl (C1-C4) amino, monohydroxyalkyl (C1-C4) amino, imidazolinium and ammonium.

Among the double bases of formula (4) above, N, N'-bis (e-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diaminopropanol, N, N'-bis ( e-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (e-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-bis- (ethyl) -N, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine, 1,8-bis (2,5-diaminophenoxy) -3,5-dioxaoctane and acid addition salts thereof.

Of these double bases of formula (4), N, N'-bis (e-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diaminopropanol and 1,8-bis (2 , 5-diaminophenoxy) -3,5-dioxaoctane or one of their acid addition salts.

- (III) p-Aminophenols corresponding to the formula (5) below and their acid addition salts:

<img file="PL206730B1_D0004.tif" />

wherein:

R13 is hydrogen, halogen such as fluoro or C1-C4-alkyl, monohydroxy (C1-C4) -alkyl, (C1-C4) alkoxy (C1-C4) alkyl, amino (C1-C4) -alkyl or hydroxy (C1-C4) -alkylamino (C1-C4) -alkyl,

R14 represents a hydrogen atom or a halogen atom such as fluoro, C1-C4-alkyl, o, monohydroxy (C1-C4) -alkyl, polyhydroxy (C2-C4) -alkyl, o, amino (C1-C4) -alkyl, cyano ( C1-C4) -alkyl or (C1-C4) -alkoxy (C1-C4) alkyl.

Among the p-aminophenols of the above formula (5) there may be mentioned in particular p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol,

4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (e-hydroxyethylaminomethyl) phenol, and acid addition salts thereof.

PL 206 730 B1

- (IV) o-Aminophenols suitable for use as oxidation bases in the context of the present invention are selected in particular from 2-aminophenol, 2-amino-1-hydroxy-5-methylbenzene, 2-amino-1-hydroxy-6- methylbenzene, 5-acetamido-2-aminophenol, and their acid addition salts.

- (V) Among the heterocyclic bases suitable for use as oxidation bases in the dyeing compositions according to the invention, mention may, in particular, be made of pyridine derivatives, pyrimidine derivatives, pyrazole derivatives and acid addition salts thereof.

Among the pyridine derivatives, mention may be made in particular of the compounds described, for example, in GB 1,026,978 and GB 1,153,196, such as 2,5-diaminopyridine, 2- (4-methoxy-phenyl) amino-3-aminopyridine, 2,3-diamino 6-methoxypyridine, 2- (e-methoxyethyl) amino-3-amino-6-methoxypyridine, and 3,4-diaminopyridine and their acid addition salts.

Among the pyrimidine derivatives, mention may be made in particular of the compounds described, e.g. in German patents DE 2 359 399 or Japanese JP 88- 169 571 and JP 91-10659 or in patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5, 6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2 750,048, among which mention may be made of pyrazolo [1,5-a] pyrimidine-3,7-diamine; 2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine; pyrazolo [1,5-a] pyrimidine-3,5-diamine; 2,7-dimethylpyrazolo [1,5-a] pyrimidine-3,5-diamine; 3-aminopyrazolo [1,5-a] pyrimidin-7-ol; 3-aminopyrazolo [1,5-a] pyrimidin-5-ol; 2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol; 2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol; 2 - [(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol; 2 - [(7-amino-pyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] -ethanol; 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine; 2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine; 2,5, N7, N7-tetramethylpyrazolo [1,5-a] pyrimidine-3,7-diamine; 3-amino-5-methyl-7-imidazolylpropylaminopyrazolo [1,5-a] pyrimidine, and their addition salts, and their tautomeric forms, if there is a tautomeric equilibrium, and their acid addition salts.

Among the pyrazole derivatives, mention may be made in particular of the compounds described in DE 3 843 892, DE 4 133 957 and WO 94/08969 and WO 94/08970, FR-A-2 733 749 and DE 195 43 988, such as 4, 5-diamino-1-methylpyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3- methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1- (e-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1- (e-hydroxyethyl) pyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4 , 5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl -1-isopropylpyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole, 3,5-diamino-4- (e-hydroxyethyl) amino-1 -methylpyrazole; and acid addition salts thereof.

According to the present invention, the oxidation bases preferably constitute about 0.0005-12% by weight of the total weight of the composition, and even more preferably about 0.005-8% by weight of that weight.

Couplers suitable for use in the dyeing process of the invention are those conventionally used in oxidation dye compositions, i.e., m-aminophenols, m-phenylenediamines, m-diphenols, naphthols and heterocyclic coupling agents such as e.g. indole derivatives, indoline derivatives, sesamol and its derivatives, pyridine derivatives, pyrazolotriazole derivatives, pyrazolones, indazoles, benzimidazoles, benzothiazoles, benzoxazoles, quinoline 1,3-benzodioxoles and their acid addition salts.

These coupling agents are especially selected from 2,4-diamino-1- (e-hydroxyethyloxy) benzene, 2-methyl-5-aminophenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene. , 4-chloro-1,3-dihydroxybenzene, 2-amino-4- (e-hydroxyethylamino) -1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis (2,4-diaminophenoxy) propane, sesamol, 1 -amino-2-methoxy-4,5-methylenedioxybenzene, α-naphthol, 6-hydroxyindoline, 4-hydroxyindole, 4-hydroxy-Ne-hydroxyethylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2-amino-3-hydroxypyridine, 3,6-dimethylpyrazolo [3,2- c] -1,2,4-triazole, 2,6-dimethylpyrazolo [1,5-b] -1,2,4-triazole, and acid addition salts thereof.

When present, these coupling agents preferably constitute about 0.0001-10% by weight of the total weight of the composition, and even more preferably about 0.005-5% by weight.

PL 206 730 B1

In general, the acid addition salts of the oxidation bases and coupling agents are selected in particular from hydrochlorides, hydrobromides, sulfates, tartrates, lactates and acetates.

The dye composition according to the invention may also contain one or more direct dyes, in particular to modify the shades or to enrich them with reflections. These direct dyes can in particular be selected from neutral, cationic or anionic nitro dyes, azo dyes or anthraquinone dyes, conventionally used or those described in particular in 1 patent applications FR-2 782 450, 2 782 451, 2 782 452 and EP-1 025 834 , in an amount by weight of about 0.001-20%, preferably 0.01-10%, of the total weight of the composition.

The ready-to-use composition according to the invention may also include in the dye composition and / or the oxidizing composition, rheology regulating agents such as fatty acid amides (monoethanolamide or coconut diethanolamide, ethoxylated etheralkylcarboxylic acid monoethanolamide), cellulose thickeners (hydroxyethyl cellulose, hydroxypropyl cellulose, etc. .), guar gum and its derivatives (hydroxypropyl guar, etc.), gums of microbial origin (xanthan gum, scleroglucan gum, etc.), cross-linked homopolymers of acrylic acid or acrylamidopropanesulfonic acid and associative polymers as described below.

Associative polymers that can be used in the present invention

Associative polymers are water-soluble polymers capable of reversibly associating with each other or with other molecules in an aqueous medium.

Their chemical structure includes hydrophilic zones and hydrophobic zones characterized by at least one fatty chain.

The associative polymers of the invention may be of the anionic, cationic, amphoteric and preferably non-ionic type.

Their concentration by weight in the coloring composition may be in the range of about 0.01-10% of the total weight of the composition, and in a ready-to-use composition (containing an oxidant) about 0.0025-10% of the total weight of the composition. More preferably, this amount is in the range of about 0.1-5% by weight in the dye composition and about 0.025-10% in the ready to use composition.

Polymers that form anionic type associations:

These include:

- (I) The polymers comprise at least one hydrophilic moiety and at least one fatty chain allyl ether moiety, especially those in which the hydrophilic moiety is constituted by an ethylenically unsaturated anionic monomer, more particularly a vinyl carboxylic acid and above all an acrylic acid , methacrylic acid or mixtures thereof, in which the fatty chain allyl ether moiety corresponds to the monomer of the following formula:

CH2 = CR'CH2OBnR where R 'is H or CH3, B is ethyleneoxy, n is zero or an integer in the range 1-100, R is a hydrocarbon group selected from alkyl, arylalkyl, aryl, alkylaryl and cycloalkyl groups, including 8-30 carbon atoms, preferably 10-24 and even more preferably 12-18 carbon atoms. A moiety of the formula CH2 = CR'CH2OBnR, more particularly preferred according to the present invention, is a moiety wherein R 'is H, n is equal to 10 and R is a stearyl group (C18).

Anionic associative polymers of this type are described and prepared according to the emulsion polymerization process in EP-0 216 479.

Among these anionic associative polymers, polymers made up of 20-60% by weight of acrylic acid and / or methacrylic acid are particularly preferred according to the invention,

5-60 wt% lower alkyl (meth) acrylates, 2-50 wt% allyl ether with a fatty chain of formula CH2 = CR'CH2OBnR and 0-1 wt% crosslinker which is a well known monomer with multiple ethylenic unsaturations capable of polymerizations such as phthalandiallyl, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate and methylenebisacrylamide.

Among the latter polymers, cross-linked terpolymers of methacrylic acid, ethyl acrylate, polyethylene glycol (10 EO) ether and stearyl alcohol (Steareth-10) are particularly preferred, especially those sold by Allied Colloids under the names Salcare SC80® and Salcare SC90®,

Which are water emulsions of 30% cross-linked terpolymer of methacrylic acid, ethyl acrylate and steareth-10-allyl ether (40/50/10).

- (II) polymers containing at least one unsaturated olefinic carboxylic acid hydrophilic moiety and at least one unsaturated carboxylic acid ester hydrophobic moiety.

Preferably, these polymers are selected from those polymers in which the olefinically unsaturated carboxylic acid hydrophilic moiety corresponds to the monomer of the following formula (6):

CH₂= CC-OH (6)

Ri O where R.₁ is H, CH₃ or C.₂H.₅, that is acrylic acid, methacrylic acid or ethacrylic acid moieties and in which the hydrophobic moiety of the alkyl ester (C10-C30) type of unsaturated carboxylic acid corresponds to the monomer of the following formula (7):

CH₂= CC-OR₃ (7)

I II r₂ in which R.₂ is H, CH₃ or C.₂H.₅, (i.e. acrylate, methacrylate or ethacrylate acid moieties), preferably H (acrylate moieties) or CH3 (methacrylate moieties), R3 is a C10-C30 alkyl group and preferably a C12-C22 alkyl group.

The alkyl esters of (C10-C30) unsaturated carboxylic acids according to 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 isodecyl methacrylate.

Anionic polymers of this type are described and prepared e.g.

US 3,915,921 and US 4,509,949.

Among the associative anionic polymers of this type, more particularly used are polymers made up of a monomer mixture comprising:

(i) essentially acrylic acid, (ii) an ester of formula (7) as described above, wherein R2 is H or CH3, wherein R3 is an alkyl group having 12-22 carbon atoms, (iii) and a crosslinker which is well the known copolymerizable polyunsaturated monomer such as diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate and methylene bisacrylamide.

Among the associative anionic polymers of this type, more particularly used are polymers composed of 95-60% by weight of acrylic acid (hydrophilic group), 4-40% by weight of a C10-C30-alkyl acrylate (hydrophobic group) and 0-6% by weight of a cross-linking monomer capable of for polymerization or also formed from 98-96% by weight of acrylic acid (hydrophilic group), 1-4% by weight of a C10-C30-alkyl acrylate (hydrophobic group) and 0.1-0.6% by weight of a cross-linking monomer, polymerizable as described above.

Among the polymers mentioned above, more particularly preferred according to the present invention are the products sold by Goodrich under the trade names Pemulen TR1®, Pemulen TR2®, Carbopol 1382®, even more preferably Pemulen TR1® and the product sold by the company SEPPIC under the name Coatex SX®.

- (III) maleic anhydride / α-olefin terpolymers containing C.₃₀-C₃₈/ alkyl maleate like product (maleic anhydride copolymer / alpha-olefin containing C₃₀-C₃₈(isopropyl maleate) sold under the name Performa V 1608® by Newphase Technologies.

- (IV) acrylic terpolymers comprising:

(a) about 20-70% by weight of a carboxylic acid with an unsaturated α, β-monoethylene bond,

(B) about 20-80% by weight of a non-surfactant α, β-monoethylene unsaturated monomer other than (a), (c) about 0.5-60% by weight of a non-ionic monourethane which is is the reaction product of a monohydric surfactant with a monoisocyanate with an unsaturated monoethylene bond, such as that described in the patent application EP-A-0 173 109, especially described in example 3, namely methacrylic acid / methyl acrylate / behenyl alcohol dimethyl m-isopropenyl benzylisocyanate (40 EO) terpolymer in a 25% aqueous dispersion.

(V) Copolymers containing an α, β-monoethylene unsaturated carboxylic acid and an α, β-monoethylene unsaturated carboxylic acid ester of an alkoxylated fatty alcohol among their monomers.

These compounds preferably also include, as the monomer, a carboxylic acid ester with an unsaturated bond of α, β-monoethylene and C₁-C₄-alcohol.

As an example of a compound of this type, mention may be made of Aculyn 22® sold by the company Rohm &amp; Haas, which is a methacrylic acid / ethyl acrylate / stearyl methacrylate alkoxylated terpolymer.

Polymers forming associations of the cationic type

These include:

(I) cationic associative polyurethanes the family of which has been described by the Applicant in French Patent Application FR 0 009 609; it can be represented by the following general formula:

RX- (P) n- [L- (Y) m] r-L '- (P') p-X'-R 'where:

R and R ', which may be identical or different, represent a hydrophobic group or a hydrogen atom;

X and X ', identical or different, represent a group containing an amino functional group, bearing or not bearing a hydrophobic group, or else an L group;

L, L 'and L, which may be identical or different, represent a group derived from a diisocyanate;

P and P ', identical or different, represent a group containing an amino group, optionally bearing or not bearing a hydrophobic group;

Y is a hydrophilic group;

r is an integer from 1-100, preferably 1-50 and in particular 1-25, each with n, m and p are each independently 0-1000;

the molecule having at least one protonated or quaternized amine functional group and at least one hydrophobic group.

In a preferred embodiment of these polyurethanes, the only hydrophobic groups are the R and R 'groups at the ends of the chain.

A preferred family of cationic associative polyurethanes is that corresponding to the formula RX- (P) n- [L- (Y) m] r-L '- (P') p-X'-R 'described above, wherein:

R and R 'are both independently hydrophobic, X and X' are each L, n and p are 1-1000 and L, L ', L, P, P', Y and m are as defined above.

Another preferred family of cationic associative polyurethanes is that of the formula RX- (P) n- [L- (Y) m] r-L '- (P') p-X'-R 'above:

R and R 'are both independently a hydrophobic group, X, X' are each L, n and p are 0 and L, L ', L, Y and m are as defined above.

From the fact that n and p are 0, it follows that these polymers do not contain moieties derived from an amine functional monomer incorporated into the polymer during polycondensation. The protonated amino functions of these polyurethanes result from the hydrolysis of excess isocyanate groups at the end of the chain and subsequent alkylation of the formed primary amino groups by hydrophobic alkylating agents, i.e. compounds of the RQ or R'Q type where R and R 'are as as defined above and Q is a leaving group like halide, sulfate etc.

Yet another preferred family of cationic associative polyurethanes is that of the formula RX- (P) n- [L- (Y) m] r-L '- (P') p-X'-R 'above, wherein:

both R and R 'independently represent a hydrophobic group, X, X' both independently represent a quaternary amine containing group, n and p are 0 and L, L ', Y and m are as defined above.

The number average molecular weight of the cationic associative polyurethanes is preferably 400-500,000, in particular 1,000-400,000, and ideally 1,000-300,000.

PL 206 730 B1

The expression "hydrophobic group" means a linear or branched hydrocarbon chain group or polymer, whether saturated or not, which may contain one or more heteroatoms such as P, O, N or S, or a perfluorinated or silicone chain group. When it is a hydrocarbyl group, the hydrophobic group then contains at least 10 carbon atoms, preferably 10-30 carbon atoms, in particular 12-30 carbon atoms and even more preferably 18-30 carbon atoms.

Preferably the hydrocarbyl group is derived from a monofunctional compound.

For example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol, decyl alcohol. It may also be a hydrocarbon polymer such as polybutadiene, for example.

When X and / or X 'is (s) a tertiary or quaternary amine containing group, X and / or X' may be one of the following formulas (8), (9), (10), (11), (12), (13), (14) or (15):

<img file="PL206730B1_D0005.tif" />

in which:

R2 is an alkylene group having 1-20 carbon atoms, linear or branched, optionally containing a saturated or unsaturated ring, or an arylene group, one or more carbon atoms may be replaced by a heteroatom selected from N, S, O, P;

R1 and R3, which may be identical or different, represent a linear or branched C1-C30-alkyl or C1-C30-alkenyl group, an aryl group, at least one of the carbon atoms may be replaced by a heteroatom selected from N, S, O, P;

A - is a physiologically acceptable counterion.

The groups L, L 'and L represent the group of formula (16):

<img file="PL206730B1_D0006.tif" />

wherein:

Z is -O-, -S- or -NH and R4 is a linear or branched alkylene group having 1-20 carbon atoms, optionally containing a saturated or unsaturated ring, an arylene group, one or more carbon atoms may be replaced by a heteroatom selected from N , S, O, and P.

The P and P 'groups containing an amino functional group may exhibit at least one of the following formulas (17), (18), (19), (20), (21) or (22):

PL 206 730 B1

<img file="PL206730B1_D0007.tif" />

in which:

R5 and R7 have the same meanings as R2 as previously defined;

R6, R8 and R9 have the same meanings as R1 and R3 previously defined;

R10 is a linear or branched, optionally unsaturated, alkylene group which may contain one or more heteroatoms selected from N, O, S and P;

and A- is a physiologically acceptable counterion.

Regarding the meaning of Y, by "hydrophilic group" is meant a water-soluble polymeric or non-polymeric group.

For example, when it is not a polymer, mention may be made of ethylene glycol, diethylene glycol, and propylene glycol.

When it is a hydrophilic polymer according to a preferred embodiment, examples may be made of polyethers, sulphonated polyesters, sulphonated polyamides or a mixture of these polymers. A preferred hydrophilic compound is a polyether, especially polyethylene oxide or polypropylene oxide.

Associative cationic polyurethanes of the formula RX- (P) n- [L- (Y) m] r-L '- (P') p-X'-R 'according to the invention are formed from diisocyanates and various compounds having functional groups with a mobile hydrogen atom. The functional groups with a mobile hydrogen atom may be alcohol, primary or secondary amine, or thiol groups, yielding, upon reaction with diisocyanate groups, polyurethanes, polyureas, and polythioureas, respectively. The term polyurethanes according to the present invention encompasses these three types of polymers, namely polyurethanes proper, polyureas and polythioureas and their copolymers.

The first type of compound involved in the formation of the polyurethane of the formula RX- (P) n- [L- (Y) m] r-L '- (P') p-X'-R 'is a compound containing at least one moiety with an amino group . The compound may be multifunctional, but preferably the compound is difunctional, that is, according to a preferred embodiment, the compound has two mobile hydrogen atoms, bonded, for example, to a hydroxyl group, a primary amine, a secondary amine, or a thiol. It is also possible to use a mixture of polyfunctional and difunctional compounds where there is a small percentage of polyfunctional compounds.

As previously indicated, this compound may contain more than one amino-functional moiety. It is then a polymer containing a repeat of an amine-functional moiety.

PL 206 730 B1

This type of relationship can be represented by one of the following formulas:

HZ- (P) n-ZH or

HZ- (P ') p-ZH wherein Z, P, P', n and p are as defined above.

As an example of an amino functional compound, N-methyldiethanolamine, N-tert-butyldiethanolamine, N-sulfoethyldiethanolamine can be mentioned.

The second compound involved in the production of the polyurethane of formula RX- (P) n- [L- (Y) m] r-L '- (P') p-X'-R 'is a diisocyanate corresponding to the formula:

O = C = N-R4-N = C = O wherein R4 is as defined above.

By way of example, mention may be made of methylenediphenyl diisocyanate, methylenecyclohexane diisocyanate, isophorone diisocyanate, toluene diisocyanate, naphthalene diisocyanate, butane diisocyanate, hexane diisocyanate.

The third compound involved in the formation of the polyurethane of formula RX- (P) n- [L- (Y) m] r-L '- (P') p-X'-R 'is a hydrophobic compound intended to form the hydrophobic end groups of the polymer of the formula RX- (P) n- [L- (Y) m] r-L '- (P') p-X'-R '.

The compound is formed from a hydrophobic group and a functional group with a mobile hydrogen, e.g. a hydroxyl group, a primary or secondary amine or a thiol.

For example, the compound may be a fatty alcohol, such as especially stearyl alcohol, dodecyl alcohol, decyl alcohol. When this compound contains a polymer chain, it can be e.g.

α-hydroxylated hydrogenated polybutadiene.

The hydrophobic group of a polyurethane of formula RX- (P) n- [L- (Y) m] r-L '- (P') p-X'-R 'may also arise from a tertiary amine quaternization reaction in a compound containing at least one tertiary amine. Thus, the hydrophobic group is introduced by a quaternizing agent. This quaternizing agent is a compound of the RQ or R'Q type where R and R 'are as defined above and Q is a leaving group like halide, sulfate etc.

The cationic associative polymer may further comprise a hydrophilic sequence. This sequence is contributed by the fourth type of compounds involved in making the polymer. This relationship can be multifunctional. It is preferably bi-functional. It can also be a mixture with a low percentage of multifunctional compound.

Functional groups with a mobile hydrogen atom are alcohol, primary or secondary amine, or thiol. This compound may be a polymer having one of these mobile hydrogen functional groups at its chain ends.

For example, when it is not a polymer, mention may be made of ethylene glycol, diethylene glycol, and propylene glycol.

When it is a hydrophilic polymer, for example polyethers, sulphonated polyesters, sulphonated polyamides or a mixture of these polymers can be mentioned. A preferred hydrophilic compound is a polyether, especially polyethylene oxide or polypropylene oxide.

The hydrophilic group named Y in the formula RX- (P) n- [L- (Y) m] r-L '- (P') p-X'-R 'is optional. Specifically, the quaternary or protonated amine functional moieties may be sufficient to impart the desired water solubility or dispersibility to this type of polymer in an aqueous solution. While the presence of a hydrophilic Y group is optional, cationic associative polyurethanes containing such a group are, however, preferred.

- (II) quaternary cellulose and polyacrylate derivatives with non-cyclic side amino groups.

Derivatives of quaternary cellulose are in particular:

- quaternized celluloses modified with groups containing at least one fatty chain, such as alkyl, arylalkyl, alkylaryl groups containing at least 8 carbon atoms or their mixtures,

- quaternary hydroxyethyl celluloses modified with groups containing at least one fatty chain, such as alkyl, aralkyl, alkylaryl groups containing at least 8 carbon atoms or mixtures thereof.

The alkyl groups derived from the above quaternized celluloses or hydroxyethyl celluloses preferably contain 8-30 carbon atoms. Aryl groups are preferably phenyl, benzyl, naphthyl or anthryl groups.

PL 206 730 B1

Examples include quaternized alkyl hydroxyethyl celluloses with C8-C30 fatty chains, Quatrisoft LM 200® products, Quatrisoft LM-X 529-18-A®, Quatrisoft LM-X 529-18B® (C12-containing alkyl) and Quatrisoft LM-K 529- 8® (C18-containing alkyl) sold by Amerchol and the products Crodacel QM®, Crodacel QL® (C12 alkyl) and Crodacel QS® (C18-containing alkyl) sold by Croda.

Amphoteric associative polymers

They are preferably selected from polymers containing at least one non-cyclic cationic moiety. Especially preferred are polymers made from or comprising 1-20% by mol of a monomer containing a fatty chain, preferably 1.5-15% by mol, and more preferably 1.5-6% by mol, based on the total number of moles of monomers.

The amphoteric associative polymers preferred according to the invention contain or are prepared by copolymerization:

1) at least one monomer of formula (23) or (24):

R-CH = CCZ- (C "H._2n)

RO r \₂

<img file="PL206730B1_D0008.tif" />

R —CH = C —CZ— (ChL) ii ii ' ⁿ ?ⁿ'

RO

Wherein R1 and R2, identical or different, represent a hydrogen atom or a methyl group, R3, R4 and R5, identical or different, represent a linear or branched alkyl group having 1-30 carbon atoms,

Z is an NH group or an oxygen atom, n is an integer 2-5,

A - an anion derived from an organic or inorganic acid, such as a methyl sulfate anion, or a halide, such as chloride or bromide;

2) at least one monomer of the formula:

R6-CH = CR7-COOH wherein R6 and R7, which may be identical or different, represent a hydrogen atom or a methyl group; and

3) at least one monomer of the formula:

R6-CH = CR7-COXR8 where R6 and R7, which are identical or different, represent a hydrogen atom or a methyl group, X is an oxygen or nitrogen atom, and R8 is a linear or branched alkyl group containing 1-30 carbon atoms, with at least one of the monomers of formula (23), (24) or R6-CH = CR7-COXR8 comprises at least one fatty chain.

The monomers of formula (23) and (24) according to the present invention are preferably selected from the group consisting of:

- dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate,

- diethylaminoethyl methacrylate, diethylaminoethyl acrylate,

- dimethylaminopropyl methacrylate, dimethylaminopropyl acrylate,

- dimethylaminopropyl methacrylamide, dimethylaminopropyl acrylamide, these monomers optionally being quaternized with e.g. C1-C4-alkyl halide or di (C1-C4) alkyl sulfate.

The monomer of formula (23) is especially selected from acrylamidopropyltrimethylammonium chloride and methacrylamidopropyltrimethylammonium chloride.

PL 206 730 B1

The monomers of formula R6-CH = CR7-COOH according to the present invention are preferably selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid and 2-methyl crotonic acid. First of all, the monomer of formula R6-CH = CR7-COOH is acrylic acid.

The monomers of the formula R6-CH = CR7-COXR8 according to the present invention are preferably selected from the group formed by C12-C22-alkyl acrylates or methacrylates, especially C16-C18-alkyl.

The fatty chain amphoteric polymer monomers of the present invention are preferably already neutralized and / or quaternized.

The number ratio of cationic charges / anionic charges is preferably about 1.

The associative amphoteric polymers of the invention preferably contain 1-10 mole% of a monomer comprising a fatty chain (monomer of formula (23), (24) or R6-CH = CR7-COXR8, preferably 1.5-6 mole%).

The weight average molecular weights of the amphoteric associative polymers of the invention may be in the range 500-50,000,000 and are preferably in the range 10,000-5,000,000.

The associative amphoteric polymers of the invention may also contain other monomers such as nonionic monomers, in particular C1-C4 alkyl acrylates or methacrylates.

The associative amphoteric polymers of the invention are e.g. described and prepared in WO 98/44012.

Among the amphoteric associative polymers of the invention, the acrylic acid / (meth) acrylamidopropyltrimethylammonium chloride / stearyl methacrylate terpolymers are preferred.

Associative polymers of non-ionic type

According to the invention, they are preferably selected from:

- (1) celluloses modified with groups containing at least one fatty chain; for example, the following can be mentioned:

- hydroxyethyl celluloses modified with groups containing at least one fatty chain, such as alkyl, arylalkyl, alkylaryl groups or mixtures thereof, in which the alkyl groups preferably contain C8-C22, such as the product Natrosol Plus Grade 330 CS® (C16 alkyls) sold by Aqualon or the product Bermocoll EHM 100® marketed by Berol Nobel;

celluloses modified with polyalkylene glycol alkylphenol ether groups, such as the product Amercell Polymer HM-1500® (polyethylene glycol (15) nonylphenol ether) sold by the company Amerchol;

- (2) hydroxypropyl guars modified with groups containing at least one fatty chain, such as Esaflor HM 22® (C22 containing alkyl chain) sold by Lamberti, RE210-18® (C14 containing alkyl chain) and RE205-1 (alkyl chain) containing C.₂₀) sold by the company Rhone-Poulenc;

- (3) copolymers of vinylpyrrolidone and fatty chain hydrophobic monomers, examples of which may be:

- Antaron V216® or Ganex V216® (vinylpyrrolidone / hexadecene copolymer) sold by ISP,

- Antaron V220® or Ganex V220® (vinylpyrrolidone / eikozen copolymer) sold by ISP,

- (4) C 1 -C 6 alkyl methacrylate or acrylate copolymers and amphiphilic monomers containing at least one fatty chain, such as, for example, methyl acrylate / ethoxylated stearyl acrylate copolymer sold by Goldschmidt under the name Antil 208®;

- (5) copolymers of hydrophilic methacrylates or acrylates and hydrophobic monomers containing at least one fatty chain, such as, for example, polyethylene glycol methacrylate / lauryl methacrylate copolymer.

- (6) polyether polyurethanes containing in their chain simultaneously hydrophilic sequences, most often polyoxyethylene in nature, and hydrophobic sequences, which may be aliphatic chains themselves and / or cycloaliphatic and / or aromatic chains;

- (7) polymers with an etheraminoplast backbone having at least one fatty chain, such as Pure Thix® compounds, sold by the company Sud-Chemie.

Preferably, the polyether polyurethanes contain at least two lipophilic hydrocarbon chains having 6-30 carbon atoms separated by one hydrophilic sequence, the hydrocarbon chains may be pendant chains or chains at the end of the hydrophilic sequence. In particular, one or more dangle chains can be provided. In addition, the polymer may contain a hydrocarbon chain at the end or both ends of the hydrophilic sequence.

PL 206 730 B1

The polyether polyurethanes can be multi-sequential, in particular in triblock form. The hydrophobic sequences can be at each end of the chain (e.g., a triblock copolymer with a central hydrophilic sequence) or distributed both at the ends and in the chain (e.g., a multi-sequence copolymer). The same polymers can also be grafted or star shaped.

The nonionic fatty chain polyether polyurethanes may be triblock copolymers in which the hydrophilic sequence is a polyoxyethylene chain containing 50-1000 oxyethylene groups. Non-ionic polyether polyurethanes have a urethane bond between the hydrophilic sequences, hence the origin of the name.

In a broader sense, among the nonionic fatty chain polyether polyurethanes there are also those in which the hydrophilic sequences are linked to the lipophilic sequences by other chemical bonds.

As examples of fatty chain nonionic polyether polyurethanes suitable for use in the invention, urea-grouped Rheolate 205® sold by the company Rheox or also Rheolates® 208, 204 or 212 and Acrysol RM184® can also be used.

Mention may also be made of the product Elfacos T210® with a C12-C14 alkyl chain and the product Elfacos T212® with a C18-containing alkyl chain from Akzo.

Alternatively, DW 1206B® from Rohm &amp; Haas with a C20-containing alkyl chain and urethane bond, 20% dry in water, can be used.

It is also possible to use solutions or dispersions of these polymers, especially in water or in a hydroalcoholic medium. Examples of such polymers are Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by the company Rheox. The product DW 1206F and DW 1206J, sold by the company Rohm &amp; Haas, can also be used.

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

Even more preferably according to the invention, a polyether polyurethane obtainable by polycondensation of at least three compounds is used, including (i) at least one polyethylene glycol containing 150-180 moles of ethylene oxide, (ii) stearyl alcohol or decyl alcohol, and (iii) at least one diisocyanate.

Such polyether polyurethanes are marketed by Rohm &amp; Haas under the names Aculyn 46® and Aculyn 44® [Aculyn 46® is a polyethylene glycol polycondensate with 150-180 moles of ethylene oxide, stearyl alcohol and methylenebis (4-cyclohexylisocyanate) (SMDI) with 15 wt. maltodextrin matrix (4%) and water (81%); Aculyn 44® is a polyethylene glycol polycondensate of 150-180 moles of ethylene oxide, decyl alcohol and methylenebis (4-cyclohexylisocyanate) (SMDI) 35 by weight in a mixture of propylene glycol (39%) and water (26%)].

The ready-to-use composition according to the invention may also contain at least one cationic or amphoteric polymer in the dye composition and / or the oxidizing composition.

Cationic polymers

For the purposes of the present invention, the expression "cationic polymer" means any polymer containing cationic groups and / or groups capable of being ionized into cationic groups.

Cationic polymers suitable for use in the present invention can be selected from all such polymers already known to improve the cosmetic properties of the hair, namely those described in particular in EP-A-337 354 and in French Patent Specifications FR No. 2,270,846, FR 2 383 660, FR 2 598 611, FR 2 470 596 and FR 2 519 863.

Preferred cationic polymers are selected from those containing groups containing primary, secondary, tertiary and / or quaternary amine groups which may either be part of the polymer backbone or be carried by a pendant substituent directly attached thereto.

The cationic polymers used have a generally number average molecular weight of from 500 to about 5x106, and preferably from 103 to about 3x106.

Among the cationic polymers, more particularly polymers of the polyamine, polyaminoamide and quaternary polyammonium types can be mentioned.

These are known products. They are described in particular in French patent specifications FR 2 505 348 or FR 2 542 997. Among these polymers, mention may be made of:

1) Homopolymers or copolymers of acrylic or methacrylic esters or amides containing at least one moiety of the following formulas (25), (26), (27) or (28):

PL 206 730 B1

<img file="PL206730B1_D0009.tif" />

in which:

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

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

R4, R5 and R6, which may be identical or different, represent an alkyl group having 1-18 carbon atoms or a benzyl group, preferably an alkyl group having 1-6 carbon atoms;

R1 and R2, which may be identical or different, represent a hydrogen atom or an alkyl group having 1-6 carbon atoms, preferably methyl or ethyl;

X is an anion derived from an inorganic or organic acid such as a methyl sulfate anion, or a halide such as chloride or bromide.

The polymers of the family (1) may also contain one or more comonomer derivatives which can be selected from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides, substituted at the nitrogen atom with lower C1-C4-alkyl groups of acrylic or methacrylic acids or their esters, vinyl lactams such as vinyl pyrrolidone or vinyl caprolactam, and vinyl esters.

Thus, among these polymers from family (1) the following can be mentioned:

- copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or dimethyl halide, such as those sold under the name Hercofloc® by the company Hercules,

- copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride described for example in patent application EP-A-080976 and sold under the name Bina Quat P 100® by the company Ciba Geigy;

- a copolymer of acrylamide and methacryloyloxyethyltrimethylammonium methyl sulfate sold under the name Reten® by the Hercules company,

- vinylpyrrolidone / acrylate or dialkylaminoalkyl methacrylate copolymers quaternized or nonquaternized, such as products sold under the name "Gafquat® by the ISP company, such as e.g." Gafquat® 734 or "Gafquat® 755, or possibly the products known as" Copolymer® 845, 958 " and 937. These polymers are described in detail in French Patent Nos. FR 2 077 143 and FR 2 393 573;

PL 206 730 B1

dimethylaminoethyl methacrylate / vinylcaprolactam / vinylpyrrolidone terpolymers, such as the product sold under the name Gaffix® VC 713 by the company ISP;

- vinylpyrrolidone / methacrylamidopropyl dimethylamine copolymers sold under the name

Styleze® CC 10 by ISP;

- and quaternary vinylpyrrolidone / dimethylaminopropyl methacrylamide copolymers, such as the product sold under the name "Gafquat® HS 100 by the company ISP."

2) Derivatives of cellulose ethers containing quaternary ammonium groups as described in French Patent No. FR 1 492 597, in particular polymers sold under the names "JR® (JR 400, JR 125, JR 30M) or" LR® (LR 400, LR 30M) by Union Carbide Corporation. These polymers are also defined in the CTFA dictionary as quaternary ammonium derivatives of hydroxyethyl cellulose reacted with a trimethylammonium substituted epoxide.

3) Cationic cellulose derivatives, such as copolymers of cellulose or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and described in particular in US Pat. , dimethyldiallylammonium.

Commercial products corresponding to this definition are in particular those sold under the names "Celquat® L 200 and" Celquat® H 100 by the company National Starch.

4) Cationic polysaccharides as described in particular in US Pat. Nos. 3,589 and 4,031,307, such as guar gums, containing cationic trialkylammonium groups. For example, guar gums modified with salt (e.g. chloride) of 2,3-epoxypropyltrimethylammonium are used.

Such products are especially sold under the trade names Jaguar® C13 S, Jaguar® C15, Jaguar® C17 or Jaguar® C162 by the company Meyhall.

5) Straight or branched chain polymers formed from piperazinyl groups and divalent alkylene or hydroxyalkylene groups, optionally interrupted by oxygen, sulfur, nitrogen or aromatic or heterocyclic rings, as well as oxidation and / or quaternization products of these polymers. Such polymers are described in particular in French patents FR 2 162 025 and FR 2 280 361.

6) Water-soluble polyaminoamides, especially prepared by polycondensation of an acid compound with a polyamine; these polyamino amides can be crosslinked with an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated, halohydrin, bisazetydynium, a bis, alkyl halide or alternatively with an oligomer resulting from the reaction of a difunctional compound which is reactive with a bis-halohydrin, bisazetydynium, a bis, alkyl halide, an epihalohydrin, a diepoxide or a bis-unsaturated derivative; the crosslinker is used in an amount of 0.025-0.35 mol per amino group of the polyaminoamide; these polyaminoamides can be alkylated or also quaternized if they contain one or more tertiary amine functions. Such polymers are described in particular in French Patent Nos. FR 2 252 840 and FR 2 368 508.

7) Polyaminoamide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids and subsequent alkylation with bifunctional agents. For example, adipic acid / dialkylaminohydroxyalkyldialkylene triamine polymers in which the alkyl group contains 1-4 carbon atoms and is preferably methyl, ethyl, propyl can be mentioned. Such polymers are described in particular in French Patent Specification FR 1 583 363.

Among these derivatives, mention may be made more particularly of the adipic acid / dimethylaminohydroxypropyl / diethylenetriamine polymers sold under the name "Cartaretine® F, F4 or F8 by the company Sandoz."

8) Polymers obtained by reacting a polyalkylene polyamine containing two primary amine groups and at least one secondary amine group with a dicarboxylic acid selected from diglycolic acid and aliphatic saturated dicarboxylic acids containing 3-8 carbon atoms. The molar ratio of polyalkylene polyamine and dicarboxylic acid is 0.8: 1 to 1.4: 1; wherein the resulting polyaminoamide is reacted with epichlorohydrin in a molar ratio of epichlorohydrin to the secondary amine group of the polyaminoamide ranging from 0.5: 1 to 1.8: 1. Such polymers are described in particular in US Pat. Nos. 3,227,615 and 2,961,347.

PL 206 730 B1

Polymers of this type are in particular sold under the name "Hercosett® 57 by the company Hercules Inc., or under the name" PD 170® or "Delsette® 101 by the company Hercules in the case of an adipic acid / epoxypropyl / diethylenetriamine copolymer.

9) Alkyl diallylamine or dialkyldiallylammonium cyclopolymers, such as homopolymers or copolymers having as their main chain constituent moieties according to formulas (29) or (30):

<img file="PL206730B1_D0010.tif" />

in which putty is equal to 0 or 1, with the sum of k + t equal to 1; R9 represents a hydrogen atom or a methyl group; R7 and R8 independently of each other represent an alkyl group having 1-6 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably has 1-5 carbon atoms, a lower amido (C1-C4) -alkyl group, or R7 and R8 may be together with the nitrogen atom to which they are attached a heterocyclic group such as piperidinyl or morpholinyl; R7 and R8, independently of each other, preferably represent an alkyl group having 1-4 carbon atoms; Y- is an anion like bromide, chloride, acetate, borate, citrate, tartrate, acid sulfate, acid sulfite, sulfate, phosphate. These polymers are described in particular in French patent specification FR 2 080 759 and in its additional certificate FR 2 190 406.

Among the polymers defined above, mention may be made more particularly of the dimethyldiallylammonium chloride homopolymer sold under the name "Merquat® 100 by the company Calgon (and its low average weight molar homologues) and the copolymers of diallyldimethylammonium chloride and acrylamide sold under the name" Merquat® 550.

10) Quaternary diammonium polymers containing repeating moieties according to formula (31):

- Ν + ^ Α, —Ν + χ-Β, X% X "in which formula (31):

R10; R11; R12 and R13, which may be identical or different, represent aliphatic, alicyclic or arylaliphatic groups containing 1-20 carbon atoms or lower aliphatic hydroxyalkyl groups, or else R10, R11, R12 and R13, together or separately, form with the nitrogen atoms to which they are attached , heterocyclic groups optionally containing a second heteroatom other than nitrogen, or else R10, R11, R12 and R13 are C1-C6-alkyl, linear or branched, substituted with nitrile, ester, acyl groups,

Amide or -CO-O-R14-D or -CO-NH-R14-D, where R14 is an alkylene group and D a quaternary ammonium group;

A1 and B1 are polymethylene groups containing 2-20 carbon atoms, which may be linear or branched, saturated or unsaturated, and may contain, linked or inserted into the backbone, one or more aromatic rings, or one or more oxygen, sulfur atoms, or sulfoxide, sulfone, disulfide, amine, alkylamino, hydroxyl, quaternary ammonium, ureido groups, amide or ester and X- is an anion derived from an inorganic or organic acid;

A1, R10 and R12 can form, with the two nitrogen atoms to which they are attached, a piperazine ring; in addition, if A1 is an alkylene or hydroxyalkylene group, linear or branched, saturated or unsaturated, B1 can also be - (CH2) n-CO-D-OC- (CH2) n- in which n is 1-100, preferably 1-50 and D is:

a) a glycol residue of the formula: -OZO-, where Z is a linear or branched hydrocarbon group, or a group corresponding to one of the following formulas:

- (CH2-CH2-O) x-CH2-CH2- (CH2-CH (CH3) -O] y-CH2-CH (CH3) where x and y are an integer 1-4 representing a specific and only degree of polymerization or any number 1-4, representing the average degree of polymerization;

b) a bis-secondary diamine residue such as a piperazine derivative;

c) the residue of the bis-primary diamine of the formula: -NH-Y-NH- where Y is a linear or branched hydrocarbon group or a divalent group

-CH2-CH2-SS-CH2-CH2-;

d) a ureylene group of the formula: -NH-CO-NH-.

Preferably X- is an anion such as chloride or bromide.

These polymers have a number average molecular weight of generally 1,000-100,000.

Polymers of this type are described in particular in French patents Nos. FR 2 320 330, FR 2 270 846, FR 2 316 271, FR 2 336 434 and FR 2 413 907 as well as in US patents 2 273 780, US 2 375 853, US 2,388,614, US 2,454,547, US 3,206,462, US 2,261,002, US 2,271,378, US 3,874,870, US 4,001,432, US 3,929,990, US 3,966,904, US 4,005,193, US 4,025,617, US 4,025,627, US 4,025,653, US 4,026,945 and US 4,027,020.

In particular, polymers which are formed of repeating moieties having the following formula (32) can be used:

<img file="PL206730B1_D0011.tif" />

(32) wherein R10, R11, R12 and R13, which are identical or different, represent an alkyl or hydroxyalkyl group containing about 1-4 carbon atoms, n and p are integers ranging from 2 to about 20, and X- is an anion derived from an inorganic acid or organic;

11) Quaternary polyammonium polymers formed from repeating moieties of formula (33):

<img file="PL206730B1_D0012.tif" />

(33)

Where p is an integer ranging from 1 to about 6, D may not exist or be a group - (CH2) r-CO-, in which r is a number equal to 4 or 7,

X- is an anion;

Such polymers can be produced according to the methods described in US 4,157,388, US 4,702,906, US 4,719,282. They are described in particular in EP-A-122,324.

Among these products, mention may be made, for example, of the products Mirapol A15, "Mirapol® AD1," Mirapol® AZ1 and "Mirapol® 175 sold by the company Miranol;

12) Quaternary polymers of vinylpyrrolidone and vinylimidazole, such as the products sold under the names Luviquat® FC 905, FC 550 and FC 370 by BASF;

13) Polyamines such as Polyquart® H sold by Henkel, listed in the CTFA dictionary under the name "Polyethyleneglycol (15) tallow polyamine;

14) Crosslinked polymers of methacryloyloxyalkyl (C 1 -C 4) trialkyl (C 1 -C 4) ammonium salts, such as polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride or by copolymerization of acrylamide with dimethylaminoethyl methacrylate followed by homopolymerization with methylaminoethyl chlorimethylation followed by homopolymerization with methylaminoethyl chloride. compound with olefinic unsaturated bond, in particular methylenebisacrylamide. A cross-linked acrylamide / methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion containing 50% by weight of the said copolymer in an inorganic oil can be used more particularly. This dispersion is sold under the name "Salcare® SC 92" by the company Allied Colloids. It is also possible to use a cross-linked methacryloyloxyethyltrimethylammonium chloride homopolymer containing about 50% by weight of the homopolymer in an inorganic oil or in a liquid ester. These dispersions are sold under the names "Salcare® SC 95 and" Salcare® SC 96 by the company Allied Colloids.

Other cationic polymers that can be used in the context of the invention are polyalkylenimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium groups, polyamine and epichlorohydrin condensates, quaternary polyureylenes and chitin derivatives.

Among all the cationic polymers that can be used in the present invention, it is preferable to use polymers from the family (1), (9), (10), (11), (12) and (14), and more preferably repeating polymers. with the following formulas (34) and (35):

<img file="PL206730B1_D0013.tif" />

especially those whose molecular weight is 9500-9900 as determined by gel permeation chromatography;

<img file="PL206730B1_D0014.tif" />

especially those where the molecular weight, as determined by gel permeation chromatography, is about 1200.

The concentration of the cationic polymer in the composition of the present invention may be 0.01-10% by weight based on the total weight of the composition, preferably 0.05-5%, even more preferably 0.1-3%.

PL 206 730 B1

Amphoteric polymers

Amphoteric polymers suitable for use in the present invention may be selected from polymers having K and M moieties distributed statistically throughout the polymer chain, where K is a moiety derived from a monomer having at least one basic nitrogen atom and M is a moiety derived from an acidic monomer having one or more carboxyl or sulfo groups, or else K and M may be groups derived from zwitterionic monomers carboxybetaines or sulfobetaines;

K and M may also be a cationic polymer chain containing primary, secondary, tertiary or quaternary amine groups wherein at least one amine group carries a carboxyl or sulfo group linked via a hydrocarbon group, or K and M are part of the polymer chain from ethylene-a, e-dicarboxylic group in which one of the carboxyl groups has reacted with the polyamine, containing one or more primary or secondary amine groups.

More particularly preferred amphoteric polymers as defined above are selected from the following polymers:

1) polymers resulting from the copolymerization of a monomer derived from a vinyl compound containing a carboxyl group, such as especially acrylic acid, methacrylic acid, maleic acid, α-chloroacrylic acid, and a basic monomer of a substituted vinyl compound containing at least one basic atom, such as especially dialkylaminoalkyl methacrylate and acrylate, dialkylaminoalkyl methacrylamide and acrylamide. Such compounds are described in US Patent No. 3,836,537.

Mention may also be made of the sodium acrylate / acrylamidopropyltrimethylammonium chloride copolymer sold under the name Polyquart® KE 3033 by the company Henkel.

The vinyl compound may also be a dialkyldiallylammonium salt such as dimethyldiallylammonium chloride. Copolymers of acrylic acid and the latter monomer are sold under the names Merquat® 280, Merquat® 295 and Merquat® Plus 3330 by the company Calgon;

2) Polymers containing moieties derived from:

a) from at least one monomer selected from acrylamides or methacrylamides substituted on the nitrogen atom with an alkyl group,

b) from at least one acid comonomer containing one or more reactive carboxyl groups,

c) and at least one basic comonomer, such as esters containing a primary, secondary, tertiary and quaternary amino group of acrylic and methacrylic acid and the product of quaternization of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.

More particularly preferred N-substituted acrylamides or methacrylamides according to the invention are groups in which the alkyl groups contain 2 to 12 carbon atoms, in particular N-ethyl acrylamide, N-tert-butylacrylamide, N-tert-octyloacrylamide, N-octyloacrylamide, N-decylacrylamide, N-dodecylacrylamide as well as the corresponding methacrylamides.

The acid comonomers are especially selected from acrylic, methacrylic, crotonic, itaconic, maleic, fumaric and alkyl monoesters having 1-4 carbon atoms and maleic or fumaric acid or anhydride.

The preferred basic comonomers are aminoethyl, butylaminoethyl, N, N'-dimethylaminoethyl, N-tert-butylaminoethyl methacrylamides.

Especially used are copolymers with the name CTFA (4th edition, 1991) Octylacrylamide / -acrylates / butylaminoethyl-methacrylate copolymer, such as those sold under the name Amphomer® or Lovocryl® 47 by the company National Starch.

3) cross-linked and partially or fully cross-linked polyaminoamides, derivatives of polyaminoamides of the general formula (36):

- [- CO-R19-CO-Z -] - (36) wherein R19 is a divalent group derived from a saturated dicarboxylic acid, an aliphatic mono- or dicarboxylic acid with an ethylene double bond, a lower alkanol ester containing 1-6 carbon atoms, and acids or a group derived from the addition of any of the acids mentioned with a bis (primary) or bis (secondary) amine and Z is a bis (primary), mono- or bis (secondary) polyalkylene polyamine group, and is preferably:

PL 206 730 B1

a) in an amount of 60-100 mol%, a group of formula (37):

<img file="PL206730B1_D0015.tif" />

where x = 2 and p = 2 or 3, or x = 3 and p = 2, this group being derived from diethylenetriamine, triethylenetetramine or dipropylenetriamine; b) in an amount of 0-40 mole%, the above group (37) where x = 2 and p = 1, derived from ethylenediamine, or a piperazine derivative group of formula (38):

<img file="PL206730B1_D0016.tif" />

c) in the amount of 0-20 mol%, the group -NH- (CH2) 6-NH-, a hexamethylenediamine derivative, these polyaminoamines being cross-linked by adding a bifunctional cross-linking agent selected from epihalohydrins, diepoxides, dianhydrides, bis-unsaturated derivatives, using 0.025-0.35 moles of crosslinker per amino group of the polyaminoamide and alkylated by treatment with acrylic acid, chloroacetic acid, or alkane sultone or their salts.

The saturated carboxylic acids are preferably selected from acids containing 6-10 carbon atoms, such as adipic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, terephthalic acid, and acids with a double ethylene bond, such as acrylic acid. , methacrylic, itaconic.

The alkane sultones used for the alkylation are preferably propane or butane sultone, the salts of the alkylating agents are preferably the sodium or potassium salts.

4) Polymers containing zwitterionic groups of formula (39):

<img file="PL206730B1_D0017.tif" />

wherein R20 is a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z are an integer of 1-3, R21 and R22 are hydrogen, methyl, ethyl or propyl, R23 and R24 are hydrogen or such an alkyl group that the sum of the carbon atoms in R23 and R24 does not exceed 10.

Polymers containing such moieties may also include derivative moieties of non-zwitterionic monomers such as dimethyl or diethylaminoethyl acrylate or methacrylate, or alkyl acrylates or methacrylates, acrylamides or methacrylamides, or vinyl acetate.

By way of example, mention may be made of a butyl methacrylate / dimethylcarboxymethylammonioethyl methacrylate copolymer such as the product sold under the name Diaformer® Z301 by the company Sandoz.

5) Polymers of chitosan derivatives containing monomeric groups corresponding to the following formulas (40), (41) and (42):

PL 206 730 B1

<img file="PL206730B1_D0018.tif" />

wherein moiety (40) is 0-30%, moiety (41) is 5-50% and moiety (42) is 30-90%, wherein said moiety of formula (42) is , R25 is a group of formula (43):

R₂7 ^R28

II ^r26-C - (O)_q-CH (43) where q = 0 or 1, if q = 0, each of R26, R27 and R28, identical or different, represents a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkylamino residue or a dialkylamino residue, optionally interrupted by one or more nitrogen atoms and / or optionally substituted with one or more amino, hydroxyl, carboxyl, alkylthio, sulfonic groups, an alkylthio residue in which the alkyl group carries an amino residue, wherein at least one of the groups R26, R27 and R28 in this case is a hydrogen atom;

or, if q = 1, each of R26, R27 and R28 is hydrogen, and the salts formed by these compounds with bases or acids;

6) Polymers derived from the N-carboxyalkylation of chitosan, such as N-carboxymethyl chitosan or N-carboxybutyl chitosan, sold under the name "Evalsan® by the company Jan Dekker;

7) Polymers according to general formula (44), such as e.g. described in French Patent Specification FR 1 400 366:

^ 29 (CH — CH_WITH)

<td></td><td colspan="3"></td><td colspan="3"> -|</td><td colspan="2"></td>

<td></td><td></td><td>DOOH</td><td></td><td>DOWN</td><td></td><td></td><td></td><td></td>

<td colspan="2"></td><td></td><td colspan="2">1 N— 1</td><td>'F30</td><td></td><td></td><td> (44)</td>

<td colspan="2"></td><td></td><td></td><td> ?33</td><td></td><td></td><td></td><td></td>

<td colspan="2"></td><td></td><td colspan="2">Ń—</td><td> ^32</td><td></td><td></td><td></td>

<td colspan="2"></td><td></td><td></td><td></td><td></td><td></td><td>r</td><td></td>

where R29 is hydrogen, CH3O, CH3CH2O, phenyl, R30 is hydrogen or lower alkyl like methyl, ethyl, R31 is hydrogen or lower alkyl like methyl, ethyl, R32 is lower alkyl like methyl, ethyl or a group corresponding to the formula -R33-N (R31) 2,

PL 206 730 B1 with R33 representing the group -CH2-CH2-, -CH2-CH2-CH2- or -CH2-CH (CH3) -, with R31 having the meanings mentioned above, and higher homologues of these groups, containing up to 6 atoms coal; r is such that the molecular weight is 500-6,000,000 and preferably 1,000-10,000,000;

8) Amphoteric polymers of the -DXDX- type, selected from:

a) polymers obtained by the action of chloroacetic acid or sodium chloroacetate on compounds containing at least one moiety of formula (45):

-DXDXD- (45) where D is a group of formula (38):

-ί / \ - \ _ / (38) and X represents the symbol E or E ', where E or E', identical or different, represent a divalent group which is a straight or branched alkylene group containing up to 7 carbon atoms in backbone, unsubstituted or substituted with hydroxyl groups, and which may further contain oxygen, nitrogen, sulfur, 1-3 aromatic and / or heterocyclic rings; wherein the oxygen, nitrogen and sulfur atoms are present in the form of an ether, thioether, sulfoxide, sulfone, sulfonium, alkylamino, alkenylamino, hydroxyl, benzylamino, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and / or urethane groups ;

b) polymers of formula (46):

-DXDX- (46) where D is the group (38):

-ί / \\ _ / (38) and X is the symbol E or E 'and at least one time E'; E is as defined above and E 'is a divalent group which is a straight or branched alkylene group containing up to 7 carbon backbone atoms unsubstituted or substituted by one or more hydroxyl groups and containing one or more nitrogen atoms, the nitrogen atom being is substituted with an alkyl chain optionally interrupted by an oxygen atom and containing necessarily one or more carboxyl groups or one or more hydroxyl groups, transformed into betaine by reaction with chloroacetic acid or sodium chloroacetate;

9) Alkyl (C1-C5) vinyl ether / maleic anhydride copolymers modified partially by semi-amination with N, N-dialkylaminoalkylamine such as N, N-dimethylaminopropylamine or by semi-esterification with N, N-dialkanolamine. These copolymers can also contain other vinyl comonomers, such as vinylcaprolactam.

Particularly preferred amphoteric polymers according to the invention are those of the family (1).

According to the invention, the amphoteric polymer (s) may be present in an amount of 0.01-10% by weight, preferably 0.05-5% by weight, more preferably 0.1-3% by weight, based on the total weight of the composition.

Environment (substrate)

The dye composition medium which is suitable for dyeing is preferably an aqueous medium made of water and may advantageously contain cosmetically acceptable organic solvents, of which, in particular, alcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol and phenylethyl alcohol or glycols. or glycol ethers, such as ethylene glycol monomethyl, monoethyl and monobutyl ether, propylene glycol or its ethers, such as e.g. propylene glycol monomethyl ether, butylene glycol, dipropylene glycol and

Diethylene glycol alkyl ethers, such as, for example, diethylene glycol monoethyl or monobutyl ether. The solvents may therefore be present in concentrations ranging from about 0.5 to 20% and preferably from about 2 to 10% by weight based on the total weight of the composition.

The dye composition according to the invention may also contain unsaturated fatty alcohols including especially oleyl alcohol in an amount in the range 0.5-15%, preferably approximately 1-10% of the total weight of the composition.

Other adjuvants

The dyeing composition according to the invention may also contain an effective amount of other agents known previously in oxidative dyeing, such as various conventional adjuvants, in particular masking agents such as EDTA and etidronic acid, UV filters, waxes, volatile or non-volatile silicones, cyclic, linear or branched, modified with organic groups (especially with amino groups) or unmodified, preservatives, ceramides, pseudoceramides, vegetable, inorganic or synthetic oils, vitamins or provitamins such as panthenol, confectioners, etc.

Said composition may also contain reducing agents or antioxidants. They can be selected in particular from sodium sulphite, thioglycolic acid, thiolactic acid, sodium acid sulphite, dehydroascorbic acid, hydroquinone, 2-methylhydroquinone, tert-butylhydroquinone and homogentisic acid. They are generally present in an amount of about 0.05-3% by weight based on the total weight of the composition.

In any case, one skilled in the art will take care to select any optional complementary compound or compounds such that the advantageous properties associated with the oxidative dye composition according to the invention are not deteriorated, or at least not substantially, with the additive or additives concerned.

Oxidizer

In the oxidizing composition, the oxidant is preferably selected from hydrogen peroxide, urea peroxide, bromates or ferricyanides, persalts such as perborates and persulfates. The use of hydrogen peroxide is particularly preferred. This oxidant is preferably formed from a hydrogen peroxide solution, the titer of which may be in the range of especially about 1-40 volumes, more preferably about 5-40.

One or more redox reaction enzymes such as laccases, peroxidases and 2-electron oxidoreductases (such as uricases) may also be used as the oxidant, optionally in the presence of a suitable donor or cofactor thereof.

The ready-to-use composition and applied to the keratin fibers [the composition resulting from the blending of the dye composition and the oxidizing composition] has a pH generally from 3 to 12, limits included. Preferably, it is from 8.5 to 11 limits, limits included, and can be adjusted to the desired value by acidifying or basifying agents well known in the art for dyeing keratin fibers.

Among the alkalizing agents, there may be mentioned, for example, ammonia water, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, ethoxylated and / or propoxylated hydroxyalkylamines and ethylenediamines, sodium or potassium hydroxide and compounds of the following formula (47):

<img file="PL206730B1_D0019.tif" />

wherein R is a propylene residue optionally substituted with hydroxyl or C1-C4-alkyl; R38, R39, R40 and R41, which may be identical or different, represent a hydrogen atom, a C1-C4-alkyl group or a hydroxy-C1-C4-alkyl group.

Acidifying agents are usually, for example, inorganic or organic acids, e.g. hydrochloric acid, orthophosphoric acid, carboxylic acids, e.g. acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.

The dyeing process according to the invention preferably comprises the application of a ready-to-use, ready-to-use composition from the dye composition and the oxidizing composition.

To wet or dry keratin fibers, and allowing the composition to act for an exposure time of preferably 1-60 minutes, even more preferably 1-45 minutes, rinsing the fibers, and then shampooing them if necessary, then again. rinsing and drying.

A specific example illustrating the invention is given below, but is not intended to limit it in nature. Example 1

The following dyeing composition was prepared:

Dyeing composition:

(expressed in grams of active substance)

<td>Etherolauryl carboxylic acid 4.5 EO (Akypo® RLM 45 marketed by Chem Y) ........</td><td> 3,6</td>

<td>Glycerol 1.5 Lauryl Alcohol (Chimexane® NV distributed by Chimex) ...........</td><td> 6,5</td>

<td>Decyl alcohol 5 EO (Empilan® KA-5/90-FL sold by Albright &amp; Wilson) ...................</td><td> 5</td>

<td>Oleyl alcohol .................</td><td> 1</td>

<td>Carboxylic acid etheralkyl (C13 / C15) monoethanolamide, containing 2 moles of ethylene oxide ..............</td><td> 5</td>

<td>Cationic associative polymer (Quatrisoft LM200® marketed by Amerchol) ...............</td><td> 0,2</td>

<td>Monoethanolamine</td><td> 2</td>

<td>Cationic polymer [Poliquaternium 6 (Merquat® 100 marketed by Calgon)] ..............</td><td> 1,36</td>

<td>Ethanol..............</td><td> 11</td>

<td>Propylene glycol .............</td><td> 5</td>

<td>Dipropylene glycol ..........</td><td> 5</td>

<td>1,3-Dihydroxybenzene (resorcinol) ..........</td><td> 0,36</td>

<td>p-Phenylenediamine .............</td><td> 2</td>

<td>N, N-bis (P-hydroxyethyl) -p-phenylenediamine sulfate ...</td><td> 0,38</td>

<td>2,4-Diamino-1- (P-hydroxyethyloxy) benzene dihydrochloride ............</td><td> 0,31</td>

<td>N, N-bis (P-hydroxyethyl) -N, N'-bis (4'aminophenyl) -1,3-diamino-2-propanol tetrahydrochloride</td><td> 0,036</td>

<td>3-Aminophenol ............</td><td> 0,69</td>

<td>Reducing agents, antioxidants ...........</td><td>qs</td>

<td>Masking agent .............</td><td>qs</td>

<td>Aroma..............</td><td>qs</td>

<td>Aqueous ammonia solution (containing 25% ammonia) .....</td><td> 1,6</td>

<td>Demineralized water ............. qs .........</td><td> 100</td>

The dye composition was mixed for 2 minutes just before use in a plastic bowl with the oxidizing composition containing 20 volumes of aqueous hydrogen peroxide solution at a rate of 1 part of the dye composition to 1.5 parts of the oxidizing composition.

The resulting mixture was applied to a lock of hair containing 90% gray hair and left to act for 30 minutes.

Then the strands were rinsed with water, washed with shampoo, rinsed again with water, then dried and combed out.

Thus, a black shade was obtained.

Example 2

The following dyeing composition was prepared:

PL 206 730 B1

Dyeing composition:

(expressed in grams of active substance)

<td>Glycerol (C12) alkyl ether (1.5 mol)</td><td> 5,0</td>

<td>Oleyl alcohol</td><td> 1</td>

<td>Diurethane (HMDI) alcohols (C.₁₆/ C₁₈) ethoxylated (66 OE) and propoxylated (14 OP)</td><td> 1</td>

<td>Lauryl ether carboxylic acid 4.5 OE</td><td> 6,0</td>

<td>Decyl alcohol ethoxylate (3 OE)</td><td> 6,0</td>

<td>Rapeseed acid amide ethoxylated (4 OE)</td><td> 7</td>

<td>Tetramethylhexamethylenediamine / 1,3-dichloropropylene polycondensate in aqueous solution</td><td> 0,9</td>

<td>Propylene glycol</td><td> 6</td>

<td>96 ° denatured ethyl alcohol</td><td> 13</td>

<td>Hexylene glycol (2-methyl-2,4-pentanediol)</td><td> 3</td>

<td>3-Methyl-1-phenyl-5-pyrazolone</td><td> 0,15</td>

<td>1-e-hydroxyethyloxy-2,4-diaminobenzene dihydrochloride</td><td> 0,29</td>

<td>1,3-bis [(4-aminophenyl) (2-hydroxyethyl) amino] -2-propanol tetrahydrochloride</td><td> 0,05</td>

<td>1,4-Diaminobenzene</td><td> 1,6</td>

<td>1-Hydroxy-3-aminobenzene</td><td> 1,24</td>

<td>1,3-Dihydroxybenzene (resorcinol)</td><td> 0,41</td>

<td>N, N-bis (2-hydroxyethyl) -p-phenylenediamine sulfate 1H2O</td><td> 0,3</td>

<td>Ethylenediaminetetraacetic acid</td><td> 0,2</td>

<td>Pure monoethanolamine</td><td> 0,8</td>

<td>Ammonium thiolactate in 58% aqueous solution (50% thiolactic acid)</td><td> 0,8</td>

<td>Terrbic acid (i.e. d-isoascorbic acid)</td><td> 0,31</td>

<td>Fragrance</td><td> 0,75</td>

<td>Ammonia water (20% stock concentration)</td><td> 10</td>

<td>Deionized water qsad</td><td> 100</td>

The dye composition was mixed at the time of use in a plastic cup for 2 minutes with the oxidizing composition titrated to 20 volumes of hydrogen peroxide at the rate of 1 part of the coloring composition to 1.5 parts of the oxidizing composition.

The resulting mixture was applied to a lock of hair that was 90% white and left for 30 minutes.

Then, the strands were rinsed with water, washed with shampoo, rinsed again with water, then dried and combed out. The shade of black was then obtained.