Composition for oxidative coloring keratin fibers comprising rape seed oil fatty acid oxyethylenated amide

FIELD: cosmetics.

SUBSTANCE: invention relates to compositions used in oxidative coloring keratin fibers, in particular, human keratin fibers and more specifically to hair coloring. The process is carried out in medium suitable for coloring comprising at least one oxidative dye and at least one oxyethylenated fatty acid amide from rape seeds oil taken in the amount above 5% of the composition weight, and to a method for coloring and a set. Invention provides improving rheological properties of the composition as compared with compositions of the prior art, namely, increasing its viscosity and/or stability, in particular, after mixing with the oxidative composition the invention provides preparing multiple chromatic shades of good stability.

EFFECT: improved and valuable properties of composition.

30 cl, 2 ex

 

The present invention relates to compositions for oxidative dyeing of keratin fibers, particularly keratin fibers and more specifically hair, containing in a medium suitable for dyeing, at least one oxidation dye and, in addition, at least one acetyltyrosine amide fatty acids of rapeseed oil.

The invention relates also to methods and devices for dyeing, using the specified composition.

Known dyeing keratin fibres, in particular human hair, coloring compositions containing precursors of oxidation dyes, usually referred to as "oxidized bases, in particular ortho - or para-phenylenediamine, ortho - or para-aminophenols and heterocyclic bases.

Precursors of oxidation dyes are compounds, originally little painted or completely unpainted, showing their ink effect within the hair in the presence of oxidizing agents, leading to the formation of colored compounds. The formation of these colored compounds occurs as a result of either oxidative condensation of the "oxidized bases themselves or the oxidative condensation of the "oxidizable reason" connection-modifiers staining, or "actual pigment components, to the which are usually present in the dye compositions used in oxidation dyeing and presents more specifically, metaphenylenediamine, meaningfully and metaliterary, and certain heterocyclic compounds.

The variety of molecules used, which are, on the one hand, "oxidized bases" and, on the other hand, "the actual pigment components, allows to obtain a very rich palette of colors.

These oxidized bases and actual pigment components must be in carriers or bases, which makes possible their application to the keratin fibers after mixing with the oxidizing agent.

These carriers are usually water, and to an ink composition flowed across the face when applied, they usually contain a thickener.

To obtain compositions for oxidative dyeing, light in applying to the hair and not flowing outside the areas to be painted, have used amides of fatty acids and, in particular, coconut oil, such as diethanolamide coconut oil acids or monoisopropanolamine acids of coconut oil, or monoethanolamide allyloxycarbonyl acid, ethoxylated with 2 mol of ethylene oxide.

These amides of fatty acids lead to compositions for oxidative dyeing with very good rheological properties, which, however, may be the more superior.

Thus, after numerous studies conducted on this issue, it has been unexpectedly discovered that it is possible to obtain a composition for the oxidation dyeing, in which the conditions of application of improved compared to previous compositions of the prior art, due to the use of acetylaminophenol amide fatty acids of rapeseed oil at a certain concentration.

Compositions for the oxidative dyeing containing acetyltyrosine amide fatty acids of rapeseed oil are thus much better rheological properties compared to compositions of the prior art with other inorganic salts of fatty acids (increased viscosity and/or stability), in particular, after mixing with an oxidizing composition.

They allow, in addition to get numerous colour shades with good durability.

Thus, an object of the present invention is a composition for the oxidative dyeing of keratin fibers, particularly keratin fibers and more specifically hair, containing in a medium suitable for dyeing, at least one oxidation dye and containing, in addition, more than 5% by weight of the composition of at least one acetylaminophenol amide fatty acids of rapeseed oil.

Another object of the invention is the ready-to-use composition for oxidation dyeing keratin fibers, which contains a medium suitable for dyeing, at least one composition such as described above, and at least one oxidizing agent.

Under the composition ready for use, in the spirit of the present invention understand the composition is intended for direct application to keratin fibers, meaning it can be stored in the warehouse tel Quel to use or be obtained by mixing two or more compositions immediately prior to use.

The invention also relates to a method for oxidative dyeing of keratin fibers, particularly keratin fibers in humans, such as the hair, which consists in applying to the fibers ink composition containing in a medium suitable for dyeing, at least one oxidation dye and more than 5% by weight of the composition of at least one acetylaminophenol amide fatty acids of rapeseed oil, and color show at alkaline, neutral or acidic pH using an oxidizing composition containing, in a medium suitable for dyeing, at least one oxidizing agent, which is added to the ink composition directly at the time of application or you put after it, without intermediate rinsing.

The object of the invention is also a device for dyeing from several departments or the set is for the oxidative dyeing of keratin fibers, in particular keratin fibers and more specifically hair, which includes the branch containing the ink composition comprising in a medium suitable for dyeing, at least one oxidation dye and more than 5% by weight of the composition of at least one acetylaminophenol amide fatty acids of rapeseed oil, and another compartment containing an oxidizing composition comprising in a medium suitable for dyeing, an oxidizing agent.

Other characteristics, aspects, objectives and advantages of the invention will become clearer after reading the following description and examples.

Acetyltyrosine amides of fatty acids of rapeseed oil, which are suitable according to the present invention contain, in particular, on average, from 1 to 20 mol of ethylene oxide, preferably from 1 to 10 mol of ethylene oxide, and more specifically from 1 to 5 moles of ethylene oxide.

Preferably amide corresponds to the following formula:

in which R is derived fatty acids derived from rapeseed, n is an average number from 1 to 20, preferably from 1 to 10, more preferably from 1 to 5.

These amides can be called a commercial product l®N, manufactured by the company CHEM Y, which is Amida fatty acid rapeseed oil containing 4 mol of ethylene oxide.

As specified is earlier, acetyltyrosine amide or amides of fatty acids of rapeseed oil contains more than 5% by weight of the composition.

According to one private variant of the invention, the proportion acetylaminophenol amide fatty acids of rapeseed oil is at least 5.5 wt.%, more specifically, at least 6 wt.% song.

At the same time, the share acetylaminophenol amide fatty acids of rapeseed oil is up to 20 wt.% of the composition, preferably less than 10 wt.% of the composition. It should be noted that the composition does not include an oxidant.

Oxidative dyes

Oxidative dyes, which can be used according to the invention, selected from oxidized bases and/or the actual pigment components.

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

Oxidized bases, which can be used in the framework of the present invention is selected from a regular bases, known in oxidation dyeing, among which, in particular, called ortho - and para-phenylendiamine, double bases, ortho - and para-aminophenols, the following heterocyclic bases, and their salts joining with acid.

In particular, it is possible to call:

(I) paraphenylenediamine the following formula (I) and their salts accession acid:

in which:

R1represents a hydrogen atom, an alkyl radical C1-C4monohydroxyethyl C1-C4polyhydroxyethyl C2-C4, alkoxy(C1-C4)alkyl(C1-C4), alkyl (C1-C4substituted nitrogen-containing group, phenyl or 4'-AMINOPHENYL;

R2represents a hydrogen atom, an alkyl radical C1-C4monohydroxyethyl C1-C4or polyhydroxyethyl C2-C4, alkoxy(C1-C4)alkyl(C1-C4) or alkyl (C1-C4substituted nitrogen-containing group;

R1and R2can also form with the nitrogen atom to which they relate, contain nitrogen a heterocycle with 5 or 6 links, possibly substituted by one or more alkyl, hydroxyl or ureido groups;

R3represents a hydrogen atom, a halogen atom such as a chlorine atom, an alkyl radical C1-C4sulfo, carboxy, monohydroxyethyl C1-C4or hydroxyalkoxy C1-C4acetylaminobenzoic C1-C4methylaminorex C1-C4or carbamoylphenoxy C1-C4,

R4represents a hydrogen atom, halogen or alkyl radical C1-C4.

Of the nitrogen-containing groups in the formula (I) can, in particular, to call R dicale amino, mono(C1-C4)alkylamino, di(C1-C4)alkylamino, three(C1-C4)alkylamino, monohydroxy(C1-C4)alkylamino, imidazolinium and ammonium.

From paraphenylenediamine formula (I) can in particular be called paraphenylenediamine, paratoluidine, 2-chloro-paraphenylenediamine, 2,3-dimethyl-paraphenylenediamine, 2,6-dimethyl-paraphenylenediamine, 2,6-diethyl-paraphenylenediamine, 2,5-dimethyl-paraphenylenediamine, N,N-dimethyl-paraphenylenediamine, N,N-diethyl-paraphenylenediamine, N,N-dipropyl-paraphenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis-(β-hydroxyethyl)-paraphenylenediamine, 4-N,N-bis-(β-hydroxyethyl)amino-2-methyl-aniline, 4-N,N-bis-(β-hydroxyethyl)-amino-2-chloro-aniline, 2-β-hydroxyethyl-paraphenylenediamine, 2-fluoro-paraphenylenediamine, 2-isopropyl-paraphenylenediamine, N-(β-hydroxypropyl)-paraphenylenediamine, 2-hydroxymethyl-paraphenylenediamine, N,N-dimethyl-3-methyl-paraphenylenediamine, N,N-(ethyl β-hydroxyethyl)-paraphenylenediamine, N-(β,γ-dihydroxypropyl)-paraphenylenediamine, N-(4'-AMINOPHENYL)-paraphenylenediamine, N-phenyl-paraphenylenediamine, 2-β-hydroxyethyloxy-paraphenylenediamine, 2-β-acetylamino-ethyloxy-paraphenylenediamine, N-(β-methoxyethyl)-paraphenylenediamine, 2-methyl-1-N-β-hydroxyethyl-paraphenylenediamine, N-(4-AMINOPHENYL)-3-hydroxypyrrolidine and their salts joining with acid.

From what areferendum formula (I) are preferred in particular, paraphenylenediamine, paratoluidine, 2-isopropyl-paraphenylenediamine, 2-β-hydroxyethyl-paraphenylenediamine, 2-β-hydroxy-ethoxypropylamine, 2,6-dimethyl-paraphenylenediamine, 2,6-diethyltoluenediamine, 2,3-dimethyl-paraphenylenediamine, N,N-bis-(β-hydroxyethyl)-paraphenylenediamine, 2-chloro-paraphenylenediamine, and their salts joining with acid.

-(II) According to the invention under the double bases understand compounds containing at least two aromatic nuclei, which are amino and/or hydroxy-group.

From the double bases which can be used as oxidized bases in the dye compositions corresponding to the invention can, in particular, include compounds corresponding to the following formula (II), and their salts accession acid:

in which:

- Z1and Z2identical or different, represent a hydroxyl radical or-NH2that can be a substituted alkyl radical C1-C4or by a bridge Y;

- the bridge Y is an alkylenes chain containing from 1 to 14 carbon atoms, linear or branched, which may be interrupted or terminated by one or more nitrogen-containing groups and/or one or more heteroatoms such as oxygen atoms, sulfur is whether nitrogen, possibly substituted by one or more hydroxyl or C1-C6alkoxy radicals;

- R5and R6represent a hydrogen atom or a halogen, an alkyl radical C1-C4monohydroxyethyl C1-C4polyhydroxyethyl C2-C4aminoalkyl C1-C4or bridging group Y;

- R7, R8, R9, R10, R11and R12identical or different, represent a hydrogen atom, the bridge Y or alkyl radical C1-C4;

provided that the compounds of formula (II) contain only one bridge group Y in the molecule.

Of the nitrogenous groups of formula (II) can in particular be called radicals of amino, mono(C1-C4)alkylamino, di(C1-C4)alkylamino, three(C1-C4)alkylamino, monohydroxy(C1-C4)alkylamino, imidazolinium and ammonium.

From the double bases of formula (II), can more specifically be called N,N'-bis-(β-hydroxyethyl)-N,N'-bis-(4'-AMINOPHENYL)-1,3-diamino-propanol, N,N'-bis-(β-hydroxyethyl)-N,N'-bis-(4'-AMINOPHENYL)-Ethylenediamine, N,N'-bis-(4-AMINOPHENYL)-tetramethylaniline, N,N'bis-(β-hydroxyethyl)-N,N'-bis-(4-AMINOPHENYL)-tetramethylaniline, N,N'-bis-(4-methyl-AMINOPHENYL)-tetramethylaniline, N,N'-bis-(ethyl)-N,N'-bis-(4'-amino-3'-were)-Ethylenediamine, 1,8-bis(2,5-diaminophenoxy)for 3,5-dioxaoctyl, and with whom do join with acid.

Among these double bases of formula (II) is particularly preferred N,N'-bis-(β-hydroxyethyl)-N,N'-bis-(4'-AMINOPHENYL)-1,3-diaminopropanol, 1,8-bis(2,5-diaminophenoxy)for 3,5-dioxaoctyl or one of their salts joining with acid.

(III) the para-aminophenols that meets the following formula (III), and their salts accession acid:

in which:

R13represents a hydrogen atom, a halogen atom, such as fluorine, alkyl radical C1-C4monohydroxyethyl C1-C4, alkoxy(C1-C4)alkyl(C1-C4or aminoalkyl C1-C4or hydroxyalkyl(C1-C4)aminoalkyl C1-C4.

R14represents a hydrogen atom or halogen atom such as fluorine, alkyl (C1-C4, monohydrocalcite C1-C4, polyhydroxyalkane C2-C4, aminoalkyl C1-C4, cyanoaniline C1-C4or alkoxy(C1-C4)alkyl, C1-C4the radical.

From para-aminophenols of formula (III) can more specifically be called para-aminophenol, 4-amino-3-METHYLPHENOL, 4-amino-3-terfenol, 4-amino-3-hydroxymethylene, 4-amino-2-METHYLPHENOL, 4-amino-2-hydroxymethylene, 4-amino-2-methoxymethanol, 4-amino-2-aminomethylphenol, 4-amino-2-(β-hydroxyethyl-aminomethyl)-phenol, and their salts Pris is unity with acid.

(IV) ortho-aminophenols that may be used as oxidized bases in the framework 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 salts joining with acid.

(V) Of the heterocyclic bases which can be used as oxidized bases in the dye compositions corresponding to the invention can more specifically be called a derivative of pyridine, pyrimidine derivatives, pyrazole derivatives and their salts joining with acid.

From pyridine derivatives can more specifically be called compounds described, for example, in patents GB 1026978 and GB 1153196, such as 2,5-diamino-pyridine, 2-(4-methoxyphenyl)amino-3-amino-pyridine, 2,3-diamino-6-methoxy-pyridine, 2-(β-methoxyethyl)amino-3-amino-6-methoxypyridine, 3,4-diamino-pyridine and its salts joining with acid.

Of pyrimidine derivatives can more specifically be called compounds described, for example, in German patent DE 2359399 or Japanese patents JP 88-169571 and JP 91-10659 or in the patent applications WO 96/15765, such as 2,4,5,6-Tetra-aminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopirimidina, 2,5,6-triaminopyrimidine, and pyrazolo-pyrimidine derivatives, such as providing outie in the patent application FR-A-2750048, of which can be called pyrazolo-[1,5-a]-pyrimidine-3,7-diamine; 2,5-dimethyl-pyrazolo-[1,5-a]-pyrimidine-3,7-diamine; pyrazolo-[1,5-a]-pyrimidine-3,5-diamine; 2,7-dimethyl-pyrazolo-[1,5-a]-pyrimidine-3,5-diamine; 3-amino-pyrazolo-[1,5-a]-pyrimidine-7-ol; 3-amino-pyrazolo-[1,5-a]-pyrimidine-5-ol; 2-(3-amino-pyrazolo-[1,5-a]-pyrimidine-7-yl-amino)-ethanol; 2-(7-amino-pyrazolo-[1,5-a]pyrimidine-3-yl-amino)-ethanol; 2-[(3-amino-pyrazolo[1,5-a]pyrimidine-7-yl)-(2-hydroxyethyl)-amino]-ethanol; 2-[(7-amino-pyrazolo[1,5-a]pyrimidine-3-yl)-(2-hydroxyethyl)-amino]-ethanol; 5,6-dimethyl-pyrazolo-[1,5-a]-pyrimidine-3,7-diamine; 2,6-dimethyl-pyrazolo-[1,5-a]-pyrimidine-3,7-diamine; 2,5,N7,N7-tetramethyl-pyrazolo-[1,5-a]-pyrimidine-3,7-diamine; 3-amino-5-methyl-7-imidazolidinone-pyrazolo-[1,5-a]-pyrimidine; and their salts accession, and their tautomeric forms, when there is a tautomeric equilibrium, and their salts joining with acid.

Of the derivatives of pyrazole can more specifically be called compounds described in patents DE 3843892, DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2733749 and DE 19543988, such as 4,5-diamino-1-methyl-pyrazole, 3,4-diamino-pyrazole, 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-phenylpyrazol, 4-amino-1,3-dimethyl-5-hydrazinophenyl, 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-diamine is-1-(β -hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)-pyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)-pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethyluracil, 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'-amino-ethyl)amino-1,3-dimethylpyrazole, 3,4,5-diaminophenol, 1-methyl-3,4,5-diaminophenol, 3,5-diamino-1-methyl-4-methylaminophenol, 3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole, and their salts joining with acid.

According to the present invention oxidizable base amount, preferably from about 0.0005 to 12% wt. the total weight of the composition (not containing an oxidizing agent) and even more preferably about 0.005 to 8 wt.% from this weight.

The actual pigment components, which can be used in the ink compositions according to the invention, are components that are commonly used in compositions for oxidative dyeing, that is, meta-aminophenols, meta-phenylenediamine, metaliterary, Naftali and the heterocyclic actual pigment component such as, for example, indole derivatives, derivatives indoline, sesamol and its derivatives, derivatives of pyridine, derivatives of pyrazolo-triazole, pyrazolones, indazols, benzimidazole, benzothiazole, benzoxazole, 13-benzodioxole, the quinoline and their salts joining with acid.

These actual pigment components, in particular chosen from 2,4-diamino-1-(β-hydroxyethyloxy)-benzene, 2-methyl-5-aminophenol, 5-N-(β-hydroxyethyl)amino-2-METHYLPHENOL, 3-aminophenol, 1,3-dihydroxy-benzene, 1,3-dihydroxy-2-methyl-benzene, 4-chloro-1,3-dihydroxybenzene, 2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis-(2,4-diaminophenoxy)-propane, sesamol, 1-amino-2-methoxy-4,5-methylenedioxybenzene, α-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-β-hydroxyethylidene, 6-hydroxy-indoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazole-5-it, 1-phenyl-3-methyl-pyrazole-5-on, 2-amino-3-hydroxypyridine, 3,6-dimethyl-pyrazolo-[3,2-c]-1,2,4-triazole, 2,6-dimethyl-pyrazolo-[1,5-b]-1,2,4-triazole and their salts joining with acid.

If they are present, the actual pigment components are preferably approximately from 0.0001 to 10 wt.% the total weight of the composition (not containing an oxidizing agent) and even more preferably about 0.005 to 5 wt.%.

Usually salt accession acid, oxidized bases and the actual pigment component is selected in particular from hydrochloride, hydrobromide, sulfates and tartratami, lactates and acetates.

Ink composition conforming to the invention may also include one or more direct the dyes, in particular, to change the colors, enriching them with a glare. These direct dyes may in particular be selected from microcrustacea, azo dyes or antrahinonovye dyes, neutral, cationic or anionic, commonly used or those that are described in particular in patent applications FR-2782450, 2782451, 2782452 and EP-1025834, in a weight proportion of from about 0.001 to 20%, preferably from 0.01 to 10% of the total weight of the composition.

Ink composition conforming to the invention may in addition contain at least one surfactant of anionic, nonionic, cationic or amphoteric nature in the amount of 0.01 to 40%, preferably from 0.1 to 30 wt.% the total weight of the composition.

Of the surfactants of the anionic type are preferably used according to the invention weakly anionic surfactants, which can be called more specifically oxyalkylation hydroxycarboxylic acids and their salts having the following formula (I):

in which:

R represents a radical C8-C22alkyl or alkenyl, linear or branched or a mixture thereof, the radical alkyl(C8-C9)phenyl, radical R CONH-CH2-CH2-, where R' is alkyl or alkanniny radical C11-C21linear or branched,

n is an integer or Dematic the second fraction from 2 to 24,

p is an integer or decimal from 0 to 6,

A denotes a hydrogen atom or Na, K, Li, 1/2 Mg or the rest of monoethanolamine, ammonium or triethanolamine.

Oxyalkylation hydroxycarboxylic acids or their salts, preferably used according to the present invention is selected from compounds of formula (I)in which R means a radical or mixture of radicals) alkyl(C12-C14), oleyl, cetyl, stearyl; nonylphenolic or octylphenyl radical, A denotes the hydrogen atom or sodium, p=0, and n is from 2 to 20, preferably from 2 to 10.

Even more preferable to use the compounds of formula (I)in which R means an alkyl radical C12, A denotes the hydrogen atom or sodium, p=0, and n is from 2 to 10.

Commercial products can be preferable to use products manufactured by the company 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=Octylphenol, n=4, p=0, A=H);

AKYPO® OP 80 (R=Octylphenol, n=8, p=0, A=H);

AKYPO® OP 190 (R=Octylphenol, 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);

KYPO® 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 160 NV (R=alkyl(C12-C14), n=16, p=0, A=Na);

AKYPO® RO 20 (R=oleyl, n=2, p=0, A=H);

AKYPO® RO 90 (R=oleyl, n=9, p=0, A=H);

AKYPO® RCS 60 (R=Cecil/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=oleyl, n=5, p=0, A=H),

or by the company SANDOZ under the names:

SANDOPAN ACA-48 (R=Cecil/stearyl, n=24, p=0, A=H);

SANDOPAN DTC Acid (R=alkyl(Cl3), n=6, p=0, A=H);

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

SANDOPAN LS-24 (R=alkyl(C12-Cl4), n=12, p=0, A=Na);

SANDOPAN JA 36 (R=alkyl(C13), n=18, p=0, A=H),

and, in particular, the 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.

Oxyalkylation hydroxycarboxylic acids or their salts comprise from about 2 to 15%, preferably from about 3 to 10% of the total weight of the composition.

Of the non-ionic surface-active substances, which themselves are well known compounds (see, in particular, in this respect "Handbook of Surfactants" M.R.PORTER, publisher Blackie&Son (Glasgow and London), 1991, p. 116-178), can be called (partial list) alcohols, alpha-diols, polyethoxysiloxane or polipropilenovyie ALKYLPHENOLS, there is the following fatty chain, containing, for example, from 8 to 22 carbon atoms, and the number of groups of ethylene oxide or propylene oxide can be from 1 to 50. You can also call copolymers of ethylene oxide and propylene oxide condensates of ethylene and propylene with fatty alcohols; mono - or polyglycerins aliphatic alcohols containing on average from 1 to 30 groups of glycerol; acetyltyrosine esters sorbitan and fatty acids having from 2 to 30 mol ethylene oxide; fatty acid esters and sucrose esters of fatty acids and of polyethylene glycol, alkylpolyglycoside derived N-alkylamine, amine oxides, such as oxides, alkyl(C10-C14)amines or oxides N-allmenareliars.

According to the invention is preferably used:

1) fatty alcohols containing from 8 to 22 carbon atoms, acetyltyrosine 1-10 mol of ethylene oxide. Of them can be called more specifically lauric alcohol 2 OE, lauric alcohol 3 OE, decroly alcohol 3 OE and decroly alcohol 5 OE.

2) mono - or polyglycerins aliphatic alcohols, which can be represented by the following formula (II):

in which:

R represents a saturated or unsaturated radical, linear or branched, containing from 8 to 40 carbon atoms, and preferably from 10 to 30 carbon atoms;

m is a number of 1 to 0, preferably from 1 to 10.

As compounds of this type can be called lauric alcohol with 4 moles of glycerol (INCI name: POLYGLYCERYL-4 LAURIC ETHER), lauric alcohol with 1.5 mol of glycerol, alerby alcohol with 4 moles of glycerol (INCI name: POLYGLYCERYL-4 ALERBY ETHER), alerby alcohol with 2 mol of glycerol (INCI name: POLYGLYCERYL-2 ALERBY ETHER), Cetearyl alcohol with 2 mol of glycerol, Cetearyl alcohol with 6 mol of glycerol, ileocecectomy alcohol with 6 mol of glycerol, and octadecanol with 6 mol of glycerol.

The aliphatic alcohol may be a mixture of aliphatic alcohols, as well as the m-value is a statistical value, which means that in a commercial product can co-exist several types of aliphatic polyglycerins alcohols in the mixture.

From mono - or polyglycerins aliphatic alcohols preferably used, in particular, alcohol C8/C10with 1 mol of glycerine, alcohol C10/C12with 1 mol of glycerine and alcohol C12with 1.5 mol of glycerol.

Non-ionic(e) the surfactant is(are) about 2 to 40 wt.% and preferably from about 4 to 20% of the total weight of the composition.

Ready-to-use composition according to the invention can also contain in the ink composition and/or in the oxidizing composition, cationic or amphoteric polymers, such as described below, and other Agay is you control the rheology, such as cellulosic thickeners (hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose and the like), guar gum and its derivatives (hydroxypropanoic and the like), gums of microbial origin (xanthan gum resin, resin scleroglucan etc.), crosslinked homopolymers of acrylic acid or acrylamidophenylboronic acid and associative polymers, such as described below.

Preferably according to the invention coloring part contains at least one cationic or amphoteric polymer and at least one associative polymer.

Cationic polymers

From the point of view of the present invention, the expression "cationic polymer" means any polymer containing cationic groups and/or groups that can ionize with the formation of cationic groups.

Cationic polymers that may be used in accordance with the present invention, can be selected from among all the cationic polymers which are already known as polymers that improve the cosmetic properties of the hair, namely, in particular those described in patent application EP 337354 and in French patents FR 2270846, 2383660, 2598611, 2470596 and 2519863.

Preferred cationic polymers are chosen from polymers which contain units having primary, secondary, tertiary and/or Quaternary amino groups, which can be either cha is part of the main polymer chain, either the sideways Deputy immediately connected with it.

Used cationic polymers are usually srednekamennogo molecular weight of from about 500 to 5·106and preferably from about 103up to 3·106.

From cationic polymers can more specifically be called such polymers, as polyamine, polyaminoamide and poly(Quaternary ammonium).

This is a known products. They are described in particular in patents FR 2505348 or FR 2542997. Of these polymers can be called:

(1) homopolymers or copolymers derived from esters or amides of acrylic or methacrylic acid containing at least one of the links of the following formulas (V), (VI), (VII) or (VIII):

in which:

R3identical or different, denote a hydrogen atom or the radical CH3;

A, same or different, represent an alkyl group, linear or branched, containing from 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms, or hydroxyalkyl group with 1-4 carbon atoms;

R4, R5, R6identical or different, represent an alkyl group containing from 1 to 18 carbon atoms, or a benzyl radical, preferably an alkyl group containing from 1 to 6 carbon atoms;

R1and R2the same is or different, represent a hydrogen or alkyl group containing from 1 to 6 carbon atoms, preferably methyl or ethyl;

X represents an anion derived from an inorganic or organic acid, such as anion methosulphate or halide, such as chloride or bromide.

The polymers of family (1) can also contain one or more parts formed from the comonomers which may be chosen from the family of acrylamides, methacrylamides, diacetonitrile, acrylamido and methacrylamido, substituted on the nitrogen by lower alkilani (C1-C4), acrylic or methacrylic acids or their esters, vinylacetate, such as vinyl pyrrolidone or vinylcaprolactam, vinyl esters.

So, of polymers of family (1) can be called:

copolymers of acrylamide and dimethylaminoethylmethacrylate, quaternionic dimethylsulfate or dimethylselenide, such as sold under the name HERCOFLOC® HERCULES,

copolymers of acrylamide and methacryloyloxyethyl-ameriglide described, for example, in patent application EP-A-080976 and sold under the name BINA QUAT P 100® the company CIBA GEIGY,

copolymer of acrylamide and methacryloyloxyethyl-ammonium methosulfate, sold under the name RETEN® HERCULES,

copolymers of vinylpyrrolidone with dialkylaminoalkyl the om or methacrylate, quaternion or not, such as the products sold under the name "GAFQUAT®" by the company ISP, such as, for example, "GAFQUAT® 734" or "GAFQUAT® 755", or also products called "COPOLYMER® 845, 958 and 937". These polymers are described in patents FR 2.077.143 and FR 2.393.573,

triple copolymers dimethylaminoethylmethacrylate, vinylcaprolactam and vinylpyrrolidone, such as the product sold under the name GAFFIX® VC 713 by the company ISP,

copolymers of vinylpyrrolidone and methacrylamidoethylene produced, in particular under the name STYLEZE® CC 10 by ISP company,

and quaternion copolymers of vinylpyrrolidone and dimethylaminoethylmethacrylate, such as the product sold under the name "GAFQUAT® HS 100" by the company ISP.

(2) simple Derivatives of cellulose ethers containing Quaternary ammonium group, described in the French patent 1492597, and in particular the polymers sold under the names "JR®" (JR 400, JR 125, JR 30M) or "LR®" (LR 400, LR 30M) by the company Union Carbide Corporation. These polymers are also defined in the CTFA dictionary as derived Quaternary ammonium and hydroxyethyl cellulose reacted with the epoxy resin is replaced with a trimethylammonium group.

(3) Cationic cellulose derivatives such as copolymers of cellulose or cellulose derivatives grafted water-soluble monomer quarter of the aqueous ammonium and described, in particular, in patent US 4131576, such as hydroxyethylcellulose, for example hydroxymethyl-, hydroxyethyl - or hydroxypropylcellulose, grafted, in particular, the salt of methacryloxypropyltrimethoxysilane, methacrylamidoethylene, dimethyldiallylammonium.

The commercial products corresponding to this definition are, in particular, the products sold under the name "Celquat® L 200" and "Celquat® H 100" by the company National Starch.

(4) the Cationic polysaccharides described in particular in patents US 3589578 and 4031307, such as guar gums containing cationic groups of trialkylamine. Use, for example, guar gum, modified salt (e.g., chloride) of 2,3-epoxypropyltrimethylammonium.

Such products are, in particular, under the trade names JAGUAR® C13 S, JAGUAR® C 15, JAGUAR® C 17 or JAGUAR® C162 by the company MEYHALL.

(5) Polymers containing units of piperazinil and divalent alkylene or hydroxyethylene radical with a linear or branched chain, which may have at the end atoms of oxygen, sulfur, nitrogen or aromatic cycles or heterocycles, and the products of oxidation and/or quaternization of these polymers. Such polymers are described in particular in patents FR 2162025 and 2280361.

(6) water-Soluble polyaminoamide obtained, in particular by polycondensation of an acid compound with what Eminem; these polyaminoamide can be crosslinked epichlorhydrine, diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-gelegenheden, bis-azetidine, bis-halogenosilanes, bis-alkylhalogenide or oligomer formed by the reaction of bifunctional compounds that are active against bis-gelegenheden, bis-azetidine, bis-halogenosilanes, bis-alkylhalogenide, epichlorhydrine, diepoxide or bis-unsaturated compounds; and a crosslinking agent is used in concentrations of constituents from 0.025 to 0.35 mol per amino group polyaminoamide; these polyaminoamide can be alkylated or, if they contain one or more tertiary amino groups, quaternidinum. Such polymers are described in particular in patents FR 2252840 and FR 2368508.

(7) Derivative polyaminoamide obtained by condensation of polyalkyleneglycol with polycarboxylic acids followed by alkylation of bifunctional agents. Can be called, for example, polymers of adipic acid and dialkylaminoalkylsubstituted, in which the alkyl radical contains from 1 to 4 carbon atoms, and means preferably methyl, ethyl, propyl. Such polymers are described in particular in patent FR 1583363.

Of these derivatives can be called more specifically, the polymers of adipic acid, dimethylamine is hydroxypropyl and Diethylenetriamine, manufactured under the name "Cartaretine ®F, F4 or F8" by the company Sandoz.

(8) Polymers obtained by reaction of polyallylamine containing two primary amino groups and at least one secondary amino group, with a dicarboxylic acid selected from diglycolic acid and saturated aliphatic dicarboxylic acids containing from 3 to 8 carbon atoms. When this molar ratio of polyallylamine to the dicarboxylic acid ranges from 0.8:1 to 1.4:1; and the resulting polyaminoamide enter into reaction with epichlorohydrin in a molar ratio of epichlorohydrin to secondary amine groups polyaminoamide average of from 0.5:1 to 1.8:1. Such polymers are described in particular in patents US 3227615 and US 2961347.

Polymers of this type are produced, in particular under the name "Hercosett® 57" by the company Hercules Inc. or also under the name "PD 170®" or "Delsette® 101" by the company Hercules in the case of a copolymer of adipic acid, epoxypropyl and Diethylenetriamine.

(9) Cyclopolymer of alkyldiethanolamine or dialkyldimethylammonium, such as the homopolymers or copolymers containing as a main component circuit units corresponding to formula (IX) or (X)

the formula in which k and t are equal to 0 or 1, the sum k+t being equal to 1; R9means a hydrogen atom or a methyl radical; R7and R8independently on the UGA mean alkyl group, containing from 1 to 6 carbon atoms, a hydroxyalkyl group in which the alkyl part contains preferably from 1 to 5 carbon atoms, a group of lower aminoalkyl (C1-C4), or R7and R8can denote, together with the nitrogen atom to which they are attached, heterocyclic groups such as piperidinyl or morpholinyl; preferably R7and R8independently from each other represent 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, phosphate. These polymers are described in particular in patent FR 2080759 and additional testimony to it n°2190406.

Of the polymers defined above, can be called more specifically, a homopolymer of dimethyldiallylammonium, manufactured under the name "Merquat® 100" by the company Calgon (and its homologues of low srednevekovoi molecular mass) and copolymers of diallyldimethylammoniumchloride and of acrylamide, sold under the name "MERQUAT® 550".

(10) the Polymer of Quaternary diammonium containing recurring units corresponding to the formula (XI)

in which:

R10, R11, R12and R13identical or different, represent aliphatic, alicyclic or arylaliphatic radicals, with the holding from 1 to 20 carbon atoms, or lower hydroxyacylglutathione radicals, or R10, R11, R12and R13together or separately, constitute, with the nitrogen atoms to which they are linked, a heterocycle possibly containing a second heteroatom other than nitrogen, or R10, R11, R12and R13represent an alkyl radical With1-C6linear or branched, substituted nitrile, ester, acyl, amide group, or-CO-O-R14-D or-CO-NH-R14-D, where R14is alkylene, and D is a Quaternary ammonium group;

A1and B1are polymethene group containing from 2 to 20 carbon atoms which may be linear or branched, saturated or unsaturated, and may contain connected with the main circuit or included in one or more aromatic cycles or one or more oxygen atoms, sulfur or sulfoxide, sulfo - disulfide, amino, alkylamino-, hydroxyl groups, Quaternary ammonium, ureido, aminogroup or group of ester, and

X-means anion formed from organic or inorganic acids;

A1, R10and R12can form with the two nitrogen atoms to which they are linked, pieperazinove cycle; in addition, if A1means alkilinity and the and hydroxyalkyloxy radical, linear or branched, saturated or unsaturated, B1can also mean a group -(CH2)n-CO-D-OC-(CH2)n-, in which D means:

a) a glycol residue of formula: -O-Z-O-, where Z denotes a hydrocarbon radical, linear or branched, or a group that meets one of the following formulas:

where x and y denote an integer from 1 to 4, representing a defined unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization;

b) the remainder of bis-secondary diamine such as piperazine derivative;

c) the remainder of bis-primary diamine of the formula: -NH-Y-NH-, where Y denotes a hydrocarbon radical, linear or branched, or a divalent radical

-CH2-CH2-S-S-CH2-CH2-;

d) ureylene group of the formula

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

These polymers have srednekamennogo molecular weight component usually from 1000 to 100000.

Polymers of this type are described in particular in French patents 2320330, 2270846, 2316271, 2336434 and 2413907 and US patents 2273780, 2375853, 2388614, 2454547, 3206462, 2261002, 2271378, 3874870, 4001432, 3929990, 3966904, 4005193, 4025617, 4025627, 4025653, 4026945 and 4027020.

Can be used, in particular, polymers of this type, which contain repeat ausina links meets the following formula (XII):

in which R10, R11, R12and R13identical or different, denote an alkyl or hydroxyalkyl radical containing from about 1 to 4 carbon atoms, n and p are integers, components from about 2 to 20 and X-is an anion derived from an organic or inorganic acid.

(11) Polymers of poly(Quaternary ammonium)containing the repeating unit of the formula (XIII)

in which p is an integer from about 1 to 6, D may be absent or may indicate a group -(CH2)r-CO-in which r denotes a number equal to 4 or 7, X-is an anion.

Such polymers can be obtained according to the methods described in patents US 4157388, US 4702906, US 4719282. They are described in particular in patent application EP 122324. One can, for example, as the products "Mirapol® A 15", "Mirapol® AD1", "Mirapol® AZ1" and "Mirapol® 175", manufactured by the company Miranol.

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

(13) Polyamine, such as Polyquart® H, manufactured by HENKEL, referred to as POLYETHYLENEGLYCOL(15) TALLOW POLYAMINE" (polyethylene glycol(15) fatty polyamine in the CTFA dictionary.

(14) Crosslinked polymer is salts methacryloyloxyethyl(C 1-C4) trialkyl(C1-C4)ammonium, such as the polymers obtained by homopolymerization of dimethylaminoethylmethacrylate, quaternionic with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethylmethacrylate, quaternions the methyl chloride, and for the Homo - or copolymerization followed by cross-linking with the aid of connection with the olefinic unsaturation, in particular methylene-bis-acrylamide. It is possible, in particular, to use cross-linked copolymer of acrylamide and methacryloxypropyltrimethoxysilane (20/80 by weight) in the form of a dispersion containing 50 wt.% the specified copolymer in mineral oil. This variance is released under the name "SALCARE® SC 92" by the company ALLIED COLLOIDS. You can also use cross-linked homopolymer of methacryloxypropyltrimethoxysilane containing about 50 wt.% homopolymer in mineral oil or in a liquid ether complex. These dispersions are produced under the name "SALCARE® SC 95 and SALCARE® SC 96" by the company ALLIED COLLOIDS.

Other cationic polymers that may be used within the invention are polyalkylene, in particular polyethylenimine, polymers containing units of vinylpyridine or vinylpyridine, condensates of polyamines and of epichlorohydrin, quaternion polyproylene and derivatives of chitin.

Among all the cationic polymers suitable for used the I in the framework of the present invention, it is preferable to use polymers families(1), (9), (10), (11), (12) and (14), and even more preferably polymers with repeating units of the following formulae (W) and (U):

and, in particular, such a molecular weight, determined by gel permeation chromatography, ranges from 9500 to 9900;

and, in particular, such a molecular weight, determined by gel permeation chromatography, is about 1200.

The concentration of cationic polymer in the composition according to the present invention may range from 0.01 to 10 wt.% the total weight of the composition, preferably from 0.05 to 5% and even more preferably from 0.1 to 3%.

Amphoteric polymers

Amphoteric polymers that may be used in accordance with the present invention may be selected from polymers containing units K and M, statistically distributed in the polymer chain, where K means the link is formed from monomer containing at least one basic nitrogen atom and M denotes a link formed from an acid monomer containing one or more carboxy or sulfo groups, or K and M may denote groups derived from zwitterionic monomers of carboxylation or sulfobetaine;

K and M may also denote a cationic polymer chain that contains asuu primary, secondary, tertiary or Quaternary amino groups, in which at least one of the amine groups carries a carboxyl or sulfo group attached through an intermediate hydrocarbon radical, or K and M form part of a polymer chain with ethylene-α,β-dicarboxylic links, where one of the carboxyl groups was aminirovanie when reacted with polyamines containing one or more primary or secondary amino groups.

Amphoteric polymers that meet the definition given above, in particular, preferably selected from the following polymers:

(1) Polymers obtained by copolymerization of monomer formed from a vinyl compound carrying a carboxyl group, such in particular as acrylic acid, methacrylic acid, maleic acid, alpha-goracinova acid, and a basic monomer formed from a substituted vinyl compound containing at least one basic atom, such as, in particular, dialkylaminoalkyl and-acrylate, dialkylaminoalkyl and-acrylamide. Such compounds are described in patent US 3836537. You can also call the copolymer of sodium acrylate and acrylamidophenylboronic, manufactured under the name POLYQUART® KE 3033 by the company HENKEL.

The vinyl compound may also be a salt of dialkyldimethylammonium, such as Dima is ideallylocated. Copolymers of acrylic acid and of the latter monomer are offered under the names MERQUAT® 280, MERQUAT® 295 and MERQUAT® PLUS 3330 by the company CALGON.

(2) Polymers containing units formed from:

a) at least one monomer selected from acrylamides or methacrylamides, substituted by nitrogen alkyl radical,

b) at least one acid co monomer containing one or more reactive carboxylic groups, and

c) at least one primary co monomer, such as esters of acrylic and methacrylic acids having as substituents primary, secondary, tertiary and Quaternary amino groups, and the product of quaternization of dimethylaminoethylmethacrylate with dimethyl or diethylsulfate.

N-substituted acrylamide or methacrylamide, especially preferred according to the invention, are compounds in which the alkyl radicals contain from 2 to 12 carbon atoms and, in particular, N-ethylacetamide, N-tert-butylacrylamide, N-tert-octylacrylamide, N-octylacrylamide, N-declariation, N-dodecylammonium, as well as relevant methacrylamide.

The acidic comonomers are selected in particular from acrylic, methacrylic, crotonic, takenaway, maleic, fumaric acids, and containing from 1 to 4 carbon atoms of alkylamidoamines maleine is Oh or fumaric acid or their anhydrides.

Preferred basic comonomers are aminoethyl, butylaminoethyl-, N,N'-dimethylaminoethyl-, N-tert-butylmethacrylate.

Use, in particular, copolymers, referred to in the CTFA (4th ed., 1991), the copolymer of octylacrylamide/acrylates/butylaminoethyl, such as the products sold under the name AMPHOMER® or LOVOCRYL® 47 by the company NATIONAL STARCH.

(3) Crosslinked polyaminoamide, fully or partially alkylated formed from polyaminoamide General formula

in which R19is a divalent radical formed from a saturated dicarboxylic acid, aliphatic mono - or dicarboxylic acid with ethylene double bond of ester lowest alkanol containing from 1 to 6 carbon atoms of these acids or a radical obtained by adding to any of these acid bis-primary or bis-secondary amine, and Z denotes a radical of bis-primary, mono - or bis-secondary polyalkylene-polyamine and preferably represents:

a) in an amount of from 60 to 100 mol.%, radical

where x=2 and p=2 or 3, or x=3 and p=2

moreover, this radical is derived from Diethylenetriamine, triethylene-tetraamine or dipropylenetriamine;

b) in an amount of from 0 to 40 mol.%, radical (XV), in which

x=2 and p=1, and which is brasovan of Ethylenediamine, or a radical formed from piperazine

c) in an amount of from 0 to 20 mol.%, the radical-NH-(CH2)6-NH-, derived from diamine, and these polyamidoamine crosslinked by adding a bifunctional crosslinking agent chosen from epichlorhydrine, diepoxides, dianhydrides, bis-unsaturated derivatives, at a ratio of from 0.025 to 0.35 mol of crosslinking agent to the amino group polyaminoamide, and alkylated by the action of acrylic acid, Chloroacetic acid or alonzolerone or their salts.

The saturated carboxylic acids are preferably chosen from acids containing from 6 to 10 carbon atoms, such as adipic, 2,2,4-trimethyl-adipic and 2,4,4-trimethyl-adipic, terephthalic acid, acids with ethylene double bond, such as, for example, acrylic, methacrylic, taconova acid.

Alkanesulfonyl used in the alkylation are preferably propane or butanesultone, salt alkylation agents are preferably salts of sodium or potassium.

(4) Polymers containing zwitterionic units of the formula

in which R20means polymerized unsaturated group, such as acrylate, methacrylate, acrylamide or methacrylamide, y and z represent an integer from 1 is about 3, R21and R22represent a hydrogen atom, methyl, ethyl or propyl, R23and R24represent a hydrogen atom or an alkyl radical, so that the sum of carbon atoms in R23and R24not more than 10.

Polymers containing such links may include links formed not from zwitterionic monomers, such as dimethyl - or diethylaminoethylamine or - methacrylate, or alkylacrylate or-methacrylates, acrylamide or methacrylamide or vinyl acetate.

As example can be mentioned a copolymer of methyl methacrylate and dimethylcarbamodithioato, such as the product sold under the name DIAFORMER® Z301 by the company SANDOZ.

(5) polymers derived from chitosan containing monomer units that meet the following formulae (XVII), (XVIII) (XIX):

moreover, the link (XVII) is present in an amount of from 0 to 30%, a link (XVIII) in an amount of 5 to 50%, and a link (XIX) in an amount of from 30 to 90%, provided that the link (XIX) R25is a radical of the formula

in which q is zero or 1;

if q=0, R26, R27and R28identical or different, represent each a hydrogen atom, methyl, hydroxyl, acetoxy group or amino group, the rest of monoalkylamines or the rest of dialkylamino may, p is ermany one or more nitrogen atoms and/or may substituted by one or more amino-, hydroxy-, carboxy-, alkylthio, sulfo groups, alkylthio, the alkyl part of which carries the amino group, and at least one of the radicals R26, R27and R28is in this case a hydrogen atom;

or if q=1, R26, R27and R28each represents a hydrogen atom, and salts formed by these compounds with bases or acids.

6) Polymers obtained N-carboxyethylgermanium chitosan, such as N-carboxymethylchitosan or N-carboxymethylchitin, manufactured under the name "EVALSAN®" the company JAN DEKKER.

(7) Polymers corresponding to General formula (XX), such as described, for example, in French patent 1400366

in which R29is a hydrogen atom, radical, CH3O, CH3CH2O-phenyl, R30means hydrogen or a lower alkyl radical, such as methyl, ethyl, R31means hydrogen or a lower alkyl radical, such as methyl, ethyl, R32means a lower alkyl radical, such as methyl, ethyl, or a radical corresponding to the formula: -R33-N(R31)2and R33is a group-CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH(CH3)-, and R31has the values listed above,

as well as the higher homologues of these RA is Ikhlov, containing up to 6 carbon atoms,

r is such that the molecular weight ranges from 500 to 6000000, preferably from 1000 to 1000000.

(8) Amphoteric polymers of the type-D-X-D-X-, is selected from:

a) polymers obtained by the action of Chloroacetic acid or chloracetate of sodium compounds containing at least one unit of formula

where D denotes the radical

and X is the symbol E or E', E or E', equal or different, denote a divalent radical which is alkilinity radical with a linear or branched chain containing up to 7 carbon atoms in the main chain, unsubstituted or substituted with hydroxyl groups and which may also contain atoms of oxygen, nitrogen, sulfur, 1 to 3 aromatic cycles and/or heterocycles; the atoms of oxygen, nitrogen and sulfur are present in the form of groups of ordinary ether, tiefer, sulfoxides, sulfonic, sulfonato, alkylamino, alkenylamine groups, hydroxyl, benzylamine groups, groups, amine oxide, Quaternary ammonium, amide, imide, of alcohol, of ester and/or urethane;

b) polymers of formula

where D denotes the radical

and X is the symbol E or E' and at least once E'; E has the meaning indicated above, and E' is a divalent radical, which is alkilinity radical with a linear or branched chain having up to 7 carbon atoms in the main chain, is unsubstituted or substituted by one or more hydroxyl radicals and containing one or more nitrogen atoms, the nitrogen atom is substituted by one alkyl chain possibly containing in-chain oxygen atom and necessarily containing one or more carboxyl groups or one or more hydroxyl groups and butanesulfonyl reaction with Chloroacetic acid or sodium CHLOROACETATE.

(9) the Copolymers of alkyl(C1-C5)-vinyl ether and maleic anhydride, partially modified by polyamidoamine with N,N-dialkylaminoalkyl, such as N,N-dimethylaminopropylamine or polieterefikatsii. N,N-dialkanolamine. These copolymers may also contain other vinyl comonomers, such as vinylcaprolactam.

Amphoteric polymers, especially preferred according to the invention are polymers of family (1).

Associative polymers that may be used according to the invention

Associative polymers are water-soluble polymers capable in the aquatic environment reversible associated with themselves or with other molecules.

Their chemical structure includes hydrof the global zones and hydrophobic zones, having at least one fatty chain.

Associative polymers according to the invention can be polymers of anionic, cationic, amphoteric type and preferably non-ionic or cationic.

Associative anionic polymers of the type:

Of them can be called:

(I) polymers containing at least one hydrophilic element and at least one link allyl ester with a fatty chain, more specifically polymers, hydrophilic element which is formed unsaturated anionic ethylene monomer, more specifically, vinylcarbazole acid and very specifically acrylic acid or methacrylic acid or their mixture, in which the link allyl ether of a fatty chain corresponds to the monomer of following formula (I):

in which R' denotes H or CH3B means ethylenoxy radical, n is zero or denotes an integer from 1 to 100, R denotes a hydrocarbon radical selected from alkyl, arylalkyl, aryl, alcylaryl, cycloalkyl radicals containing from 8 to 30 carbon atoms, preferably from 10 to 24, and more particularly from 12 to 18 carbon atoms. Link formula (I) preferably is a link in which R' denotes H, n is equal to 10, and R means sterelny radical (C18).

Anionic associative polymers of this type of description which are prepared by the method of emulsion polymerization, in the patent EP-0216479.

Of the anionic associative polymers are preferred, in particular, according to the invention the polymers formed from 20 to 60 wt.% acrylic acid and/or methacrylic acid, 5-60 wt.% the lower alkyl(meth)acrylate, 2-50 wt.% allyl ether of a fatty chain of formula (I), and 0-1 wt.% cross-linking agent, which is a well-known copolymerizable unsaturated polyethylene monomer, such as diallylphthalate, allyl(meth)acrylate, divinylbenzene, (poly)etilenglikolevykh, and methylene-bis-acrylamide.

Of these the latter is preferable, in particular, the triple cross-linked copolymers of methacrylic acid, ethyl acrylate, ether of stearyl alcohol and of polyethylene glycol (10 OE) (Steareth 10), in particular produced by the company ALLIED COLLOIDS under the names SALCARE SC 80® and SALCARE an sc90®, which are aqueous 30%-tion triple emulsions of crosslinked copolymer of methacrylic acid, ethyl acrylate and steareth-10-allyl ether (40/50/10).

- (II) polymers containing at least one hydrophilic element type of unsaturated olefinic carboxylic acid and at least one hydrophobic link type Olkiluoto (C10-C30) ester of unsaturated carboxylic acid.

Preferably these polymers selected from polymers have hydrophilic link type unsaturated olefinic carboxylic acid corresponding to the monomer of the following formula (II):

in which R1means H, CH3or C2H5then there are the parts of acrylic acid, methacrylic acid or metacrilato acid, and in which the hydrophobic link type Olkiluoto (C10-C30) ester of unsaturated carboxylic acid corresponds to the monomer of following formula (III):

in which R2means H, CH3or C2H5(that is, links of acrylates, methacrylates or ethacrylate) and preferably H (acrylate units) or CH3(methacrylate units), and R3means an alkyl radical C10-C30preferably C12-C22.

Alkalemia (C10-C30) esters of unsaturated carboxylic acids corresponding to the invention, include, for example, laurelcrest, stearylamine, dellaquila, isodecyladipate, dodecylamine and the corresponding methacrylates: laurenmarie, sterilisability, decylmethacrylate, isabellemadelinet and dodecylmercaptan.

Anionic polymers of this type are described and prepared, for example, according to the US patents 3915921 and US 4509949.

This type of associative anionic polymers are used, in particular, polymers formed from a mixture of monomers containing:

(i) mainly acrylic acid,

(ii) an ester of formula (III), opisaniya, in which R2means H or CH3and R3means an alkyl radical having from 12 to 22 carbon atoms,

(iii) and a crosslinking agent, which is a well-known unsaturated polyethylene monomer capable of copolymerizate, such as diallylphthalate, allyl(meth)acrylate, divinylbenzene, (poly)etilenglikolevykh, and methylene-bis-acrylamide.

This type anionic associative polymers are used, in particular, polymers containing from 95 to 60 wt.% acrylic acid (hydrophilic group), from 4 to 40 wt.% alkylacrylate C10-C30(hydrophobic group) and from 0 to 6 wt.% the polymerized crosslinking monomer, or a polymer containing from 98 to 96 wt.% acrylic acid (hydrophilic group), 1 to 4 wt.% alkylacrylate C10-C30(hydrophobic group) and from 0.1 to 0.6 wt.% the polymerized crosslinking monomer, such as the monomers described previously.

Of the above polymers are particularly preferred according to the present invention the products manufactured by the company GOODRICH under the trade names PEMULEN TR1®, PEMULEN TR2®, CARBOPOL 1382®and even more preferably PEMULEN TR1® and the product produced by the firm S.E.P.P.I.C. under the name COATEX SX®.

(III) ternary copolymers of maleic anhydride, α-olefin C30-C38and alkylsulphate, such as the product (copolymer of m is leinbaugh anhydride, α-olefin C30-C38and isopropylmalate), sold under the name PERFORMA V 1608® the company NEWPHASE TECHNOLOGIES.

(IV) triple acrylic copolymers containing:

(a) from about 20% to 70 wt.% carboxylic acids with α,β-monoethylene the unsaturation,

(b) from about 20 to 80 wt.% not surface-active monomer with α,β-monoethylene the unsaturation other than (a)

(c) from about 0.5 to 60 wt.% non-ionic monourethane, which is the reaction product of the surface-active monohydride with monoisocyanates with monoethanol the unsaturation,

such as described in patent application EP-A-0173109 and, more specifically described in example 3, namely ternary copolymer of methacrylic acid, methyl acrylate and diethylmethylbenzenediamine ethoxylated (40 OE) BeginInvoke alcohol, in an aqueous 25%dispersion.

(V) copolymers, in which the number of form of their monomers include carboxylic acid with α,β-monoethylene the unsaturation, ether carboxylic acids with α,β-monoethylene the unsaturated and aliphatic oxyalkylation alcohol.

Preferably, these compounds also contain as monomer ether carboxylic acid with α,β-monoethylene the unsaturation and an alcohol (C1-C4.

As an example of this type of compounds can aswat ACULYN 22® manufactured by ROHM and HAAS, which is a ternary copolymer of methacrylic acid, ethyl acrylate and oxyalkylation of sterilisability.

Associative polymers of cationic type

Of them can be called:

(I) cationic associative polyurethanes, the collection of which was described by the applicant in French patent N°-0009609; it can be represented by the following General formula (Ia):

in which:

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

X and X', equal or different, represent a group containing an amino group, associated or not associated with a hydrophobic group, or a group L";

L, L' and L"are the same or different, represents a group formed from a diisocyanate;

P and P', equal or different, represent a group containing an amino group, associated or not with a hydrophobic group;

Y represents a hydrophilic group;

r is an integer from 1 to 100, preferably from 1 to 50 and in particular from 1 to 25,

n, m and p are equal to each, independently, a number from 0 to 1000;

the molecule contains at least one amino group, protonated or quaternion, and at least one hydrophobic group.

In the preferred method of preparation of these polyur tanov the only hydrophobic groups are the groups R and R' on the ends of the chain.

A preferred family of cationic associative polyurethanes is the collection corresponding to the above formula (Ia)in which:

R and R' are both, independently, a hydrophobic group,

X, X' each represent a group L",

n and p equal to the number from 1 to 1000 and

L, L', L", P, P', Y and m have the meanings specified above.

Another preferred family of cationic associative polyurethanes is the collection corresponding to the formula (Ia)in which:

R and R' both independently represent a hydrophobic group, X and X' each represent a group L", n and p are 0, and L, L', L", Y and m have the meanings specified above.

The fact that n and p are equal to 0, means that these polymers do not contain links formed from a monomer with an amino group introduced into the polymer by the polycondensation. Protonated amino groups of these polyurethanes result from the hydrolysis of isocyanate groups, with an excess, at the end of the chain, and subsequent alkylation of the formed primary amine groups by alkylation agents with a hydrophobic group, i.e. compounds of the type RQ or R Q, where R and R' are such as defined above, and Q means a removable group, such as halide, sulfate, etc.

Another preferred family of cationic associative polyurethanes is the collection corresponding to the formula (Ia), in which the nd:

R and R' both independently represent a hydrophobic group,

X and X' both independently represent a group containing a Quaternary amine,

n and p are zero, and

L, L', Y and m have the meanings specified above.

Srednekislye molecular mass of the cationic associative polyurethanes is preferably from 400 to 500,000, in particular from 1000 to 400,000 and ideally from 1000 to 300000.

Under hydrophobic group understand the radical or polymer with a hydrocarbon chain, saturated or not, linear or branched, which may contain one or more heteroatoms such as P, O, N, S, or a radical with perfluorinated or silicone chain. When the hydrophobic group means a hydrocarbon radical, it contains at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferably from 18 to 30 carbon atoms.

Preferably the hydrocarbon group is derived from monofunctional compounds.

As an example, the hydrophobic group may be derived from aliphatic alcohol such as stearyl alcohol, dodecyloxy alcohol, decroly alcohol. It can also mean a hydrocarbon polymer, such as, for example, polybutadiene.

When X and/or X' means a group containing a tertiary or Quaternary amine, X and/or X' could the t to represent one of the following formulas:

in which:

R2represents alkalinity radical containing from 1 to 20 carbon atoms, linear or branched, containing or not containing a saturated or unsaturated cycle or Allenby radical, where one or more carbon atoms can be replaced by a heteroatom selected from N, S, O, P;

R1and R3identical or different, denote alkyl or alkanniny radical With1-C30linear or branched, aryl radical, and 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 a group of the formula

in which:

Z represents-O-, -S - or-NH-; and

R4represents alkalinity radical containing from 1 to 20 carbon atoms, linear or branched, containing or not containing a saturated or unsaturated cycle, Allenby radical, where one or more carbon atoms can be replaced by a heteroatom selected from N, S, O and P.

The groups P and P'that contains the amino group may represent at least one of the following formulas:

in which:

R5and R7have the same the values, and R2defined previously;

R6, R8and R9are the same values that R1and R3defined previously;

R10represents alkylenes group, linear or branched, unsaturated possible, which may contain one or more heteroatoms selected from N, O, S and P,

and A-is a physiologically acceptable counterion.

As for the value of Y, under hydrophilic group understand water-soluble group, the polymer or not.

As examples, when the group Y is not a polymer, ethylene glycol, diethylene glycol and propylene glycol.

When in accordance with the preferred method of implementation, the group Y is a hydrophilic polymer include, for example, polyethers, polysulfonamide, polysulfonamide, or a mixture of these polymers. Preferably the hydrophilic compound is a simple polyester and, in particular, polyethylene oxide or polypropyleneoxide.

Cationic associative polyurethanes of formula (Ia) according to the invention formed from diisocyanates and from various compounds containing the group rolling hydrogen. Group rolling hydrogen can be alcohol groups, primary or secondary amino groups or thiol groups, giving, after reaction with diisocyanate groups is respectively polyurethanes, polycarbamide and politimotion. The term "polyurethanes" in the present invention covers all three types of polymers, namely the actual polyurethane, polycarbamide and politimotion, and their copolymers.

The first type of compounds involved in obtaining the polyurethane of formula (Ia)is a compound containing at least one link with the amino group. This compound may be multifunctional, but preferably this connection bifunktionalno, i.e. according to a preferred variant implementation of this compound contains two movable hydrogen atom, which carries, for example, one hydroxyl group, primary or secondary amino group or tighrope. You can also use a mixture of multifunctional and bifunctional compounds, in which the percentage of multifunctional compounds is small.

As indicated previously, this compound may contain more than one link with the amino group. In this case, the specified connection is a polymer having a repeating unit with the amino group.

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

or

in which Z, P, P', n and p are such as defined above.

As examples of compounds with amino group can be called N-methyldiethanolamine, N-tert-butalbita is alamin, N-sulfoaildenafil.

A second connection involved in obtaining the polyurethane of formula (Ia)is a diisocyanate corresponding to the formula

in which R4defined above.

As an example we can mention methylenediphenyl-diisocyanate, methyltrichlorosilane, isophorondiisocyanate, colorvision, naphthalenedisulfonate, potentisation, exanguination.

The third connection is involved in obtaining the polyurethane of formula (Ia)is a hydrophobic compound that is intended for the formation of hydrophobic end groups of the polymer of formula (Ia).

This compound contains a hydrophobic group and rolling of hydrogen, such as hydroxyl group, primary or secondary amino group, or a thiol group.

An example of this connection may be the limiting alcohol, such as, in particular, stearyl alcohol, dodecyloxy alcohol, decroly alcohol. When this compound contains the polymer chain, it can represent, for example, hydrogenated polybutadiene with α-hydroxyl group.

The hydrophobic group of the polyurethane of formula (Ia) can also be obtained by the reaction of quaternization of the tertiary amine compounds containing at least one link of the tertiary amine. Thus, the hydrophobic group is introduced Agay is the quaternization. This quaternization agent is a compound of the type RQ or R Q, where R and R' are such as defined above, and Q means a removable group, such as halogen, sulfate, etc.

Cationic associative polyurethane may also contain hydrophilic sequence. This sequence is entered the fourth type of compounds involved in the production of polymer. This compound may be multifunctional. Preferably it bifunktionalno. You can also use a mixture with a minor proportion of a multifunctional compound.

Group rolling hydrogen are alcohol groups, primary and secondary amino groups or thiol groups. This compound may be a polymer, having at the ends of the chains one of these groups is hydrogen rolling.

As an example, can be called when the specified connection is not a polymer, ethylene glycol, diethylene glycol and propylene glycol.

When it is a hydrophilic polymer include, for example, polyesters, polysulfonamide, polysulfonamide or a mixture of these polymers. Preferably the hydrophilic compound is a polyester and, in particular, polyoxyethylene or polyoxypropylene.

Hydrophilic group, denoted by Y in the formula (Ia), optional. Indeed, links with Quaternary or protonirovannoi what monography may be sufficient to obtain the solubility or dispersive ability of the pigment, necessary for this type of polymer in aqueous solution. Although the presence of a hydrophilic group Y is optional, preferred, however, the cationic associative polyurethanes containing such a group.

-(II) derivatives quaternionic pulp and acyclic polyacrylates with lateral amino groups.

Derivatives quaternionic cellulose, are, in particular,

- quaternionic cellulose, modified by groups containing at least one fatty chain, such as alkyl, arylalkyl, alcylaryl group containing at least 8 carbon atoms, or mixtures thereof,

- quaternionic the hydroxyethyl cellulose modified with groups containing at least one fatty chain, such as alkyl, arylalkyl, alcylaryl group containing at least 8 carbon atoms, or mixtures thereof.

Alkyl radicals, which are quaternion cellulose or hydroxyethylcellulose, above, contain preferably from 8 to 30 carbon atoms. Aryl radicals means preferably phenyl, benzyl, raftiline or antennae group.

As examples quaternionic alkylhydroxylamines with fatty chains8-C30you can specify the products QUATRISOFT LM 200®, QUATRISOFT LM-X 529-18A®, QUATRISOFT LM-X 529-18B® (alkyl (C12and QUARISOFT LM-X 529-8® (alkyl (C18)manufactured by the company AMERCHOL and the products CRODACEL QM®, CRODACEL QL® (alkyl (C12) and CRODACEL QS® (alkyl (C18), manufactured by CRODA.

(III) Cationic polyvinylacetate, the family described by the applicant in French patent application N°-0101106.

These polymers contain:

a) at least one monomer of type vinylacetate or alkalineearth;

b) at least one monomer of the following structures (I) or (II):

in which:

X means an oxygen atom or a radical NR6,

R1and R6signify, independently from each other, a hydrogen atom or an alkyl radical C1-C5linear or branched,

R2means an alkyl radical C1-C4linear or branched,

R3, R4and R5signify, independently from each other, a hydrogen atom, an alkyl radical C1-C30linear or branched, or a radical of the formula (III):

Y, Y1and Y2signify, independently from each other, alkalinity radical C2-C16linear or branched,

R7means a hydrogen atom, or an alkyl radical C1-C4linear or branched, or hydroxyalkyl radical of C1-C4that line is or branched,

R8means a hydrogen atom or an alkyl radical With1-C30linear or branched,

p, q and r denote, independently from each other, either zero or 1,

m and n denote, independently of one another, an integer from 0 to 100,

x represents an integer from 1 to 100,

Z denotes the anion of an organic or inorganic acid,

provided that:

at least one of the substituents R3, R4, R5or R8means an alkyl radical C9-C30linear or branched,

- if m or n is different from zero, then q is 1,

- if m or n is zero, then p or q is 0.

Cationic polyvinylacetate according to the invention can be made or to be unstitched and can also be block copolymers.

Preferably the counterion Z-monomers of formula (I) selected from halogen ions, phosphate ions, ion methosulfate, ion tosilata.

Preferably R3, R4and R5signify, independently from each other, a hydrogen atom or an alkyl radical With1-C30linear or branched.

More preferably, the monomer (b) is a monomer of the formula (I), in which even more preferably m and n are equal to zero.

The monomer winlactat or alkylphenolate is preferably a compound of structure (IV)

in which:

s about the mean integer from 3 to 6,

R9means a hydrogen atom or an alkyl radical With1-C5,

R10means a hydrogen atom or an alkyl radical With1-C5,

provided that at least one of the radicals R9and R10means a hydrogen atom.

Even more preferably the monomer (IV) is vinyl pyrrolidone.

Cationic polyvinylacetate according to the invention may also contain one or more additional monomers, preferably cationic or non-ionic.

As compounds preferred according to the invention, it is possible to name the following ternary copolymers containing at least:

a) one monomer of formula (IV)

b) one monomer of formula (I)in which p=1, q=0, R3and R4signify, independently from each other, a hydrogen atom or an alkyl radical C1-C5and R5means an alkyl radical C9-C24and

c) one monomer of formula (II)in which R3and R4signify, independently from each other, a hydrogen atom or an alkyl radical C1-C5.

Even more preferably used triple copolymers containing, by weight, 40 to 95% of monomer (a), from 0.1 to 55% of monomer (c) and from 0.25 to 50% of monomer (b). Such polymers are described in patent application WO-00/68282, the contents of which is an integral part of the present invention.

As a researcher is as cationic polyvinylacetate according to the invention is used, in particular, ternary copolymers of vinylpyrrolidone, dimethylaminoethylmethacrylate and didecyldimethylammoniumchloride, ternary copolymers of vinylpyrrolidone, dimethylaminoethylmethacrylate and calidatetimeformatter.h, ternary copolymers of vinylpyrrolidone, dimethylaminoethylmethacrylate and lauryldimethylamine-tosilata or chloride.

Srednevekovaja molecular weight cationic polyvinylacetate according to the present invention is preferably from 500 to 20000000. More specifically, it is to 200,000 up to 2,000,000 and more preferably from 400000 to 800000.

Associative amphoteric polymers

They are preferably selected from polymers containing at least one non-cyclic cationic unit. More specifically, the preferred polymers have been derived from or containing from 1 to 20 mol.% monomer containing one fatty chain, and preferably from 1.5 to 15 mol.% and even more specifically from 1.5 to 6 mol.%, from the total number of moles of monomers.

Associative amphoteric polymers preferred according to the invention, contain, or otherwise obtained by copolymerization of:

1) at least one monomer of formula (Ia) or (Ib):

in which R1and R2the same or different, represent a hydrogen atom or a methyl radical, R3, R4and R5identical or different, represent an alkyl radical, linear or branched, containing from 1 to 30 carbon atoms,

Z is an NH group or an oxygen atom

n is an integer from 2 to 5

A-is the anion of an organic or inorganic acid, such as anion methosulphate or halide, such as chloride or bromide;

2) at least one monomer of formula (II)

in which R6and R7identical or different, represent a hydrogen atom or a methyl radical; and

3) at least one monomer of formula (III):

in which R6and R7identical or different, represent a hydrogen atom or a methyl radical, X represents an oxygen atom or nitrogen and R8means an alkyl radical, linear or branched, containing from 1 to 30 carbon atoms;

moreover, at least one of the monomers of formulas (Ia), (Ib) or (III) contains at least one fatty chain.

The monomers of formula (Ia) and (Ib) according to the present invention is preferably selected from the group formed by:

- dimethylaminoethylmethacrylate, dimethylaminoethylacrylate,

- diethylaminoethylmethacrylate, diethyl what menatelecom,

- dimethylaminoethylmethacrylate, dimethylaminopropylamine,

- dimethylaminopropionitrile, dimethylaminopropylamine,

moreover, these monomers may quaternity, for example, alkylhalogenide C1-C4or diallylsulfide C1-C4.

More specifically, the monomer of formula (Ia) selected from acrylamidophenylboronic and metallicametallicametall.

The monomers of formula (II) according to the present invention is preferably selected from the group formed by acrylic acid, methacrylic acid, crotonic acid and methyl-2-crotonic acid. More specifically, the monomer of formula (II) is an acrylic acid.

The monomers of formula (III) according to the present invention is preferably selected from the group formed by alkylacrylate or - methacrylates C12-C22and, in particular, C16-C18.

The monomers that form amphoteric polymers with fatty chain, according to the invention preferably already neutralized and/or quaternion.

The numerical ratio of the cationic charges to the anionic charges is preferably approximately equal to 1.

Associative amphoteric polymers according to the invention contain preferably from 1 to 10 mol.% monomer containing a fatty chain (monomer of formula (Ia), (Ib) or (III)), and preferably from 1.5 is about 6 mol.%.

Srednevekovye molecular weight amphoteric associative polymers according to the invention can be from 500 to 50000000 and preferably ranges from 10,000 to 5000000.

Associative amphoteric polymers according to the invention can also contain other monomers, such as non-ionic monomers and, in particular, such as C1-C4alkylacrylate or methacrylates.

Associative amphoteric polymers according to the invention described and obtained, for example, in the patent application WO 9844012.

Of the amphoteric associative polymers according to the invention the preferred ternary copolymers of acrylic acid, (meth)acrylamidophenylboronic and sterilisability.

Associative polymers are non-ionic type

According to the invention they are preferably chosen from:

- (1) the cellulose modified with groups containing at least one fatty chain;

You can call, for example:

- hydroxyethyl cellulose modified with groups containing at least one fatty chain, such as alkyl, arylalkyl, alcylaryl group, or mixtures thereof, and in which the alkyl groups are preferably C8-C22such as the product NATROSOL PLUS GRADE 330 CS® (alkali C16)manufactured by the company AQUALON, or the product BERMOCOLL EHM 100®manufactured by the company BEROL NOBEL,

- hidroxiethile the vine, modified groups polyalkyleneglycol ether, such as product AMERCELL POLYMER HM-1500® (polyethylene glycol(15) Nonylphenol ether), produced by the company AMERCHOL.

- (2) hydroxypropanoate modified with groups containing at least one fatty chain, such as product ESAFLOR HM 22® (alkyl chain C22)manufactured by the company LAMBERTI, and the products RE210-18® (alkyl chain C14) and RE205-1® (alkyl chain C20), manufactured by RHODIA.

- (3) copolymers of vinylpyrrolidone and of hydrophobic monomers with a fatty chain, which may be called, for example:

products ANTARON V216® or GANEX V216® (copolymer of vinylpyrrolidone and hexadecane)manufactured by the company I.S.P.

products ANTARON V220® or GANEX V220® (copolymer of vinylpyrrolidone and eicosene)manufactured by the company I.S.P.

- (4) copolymers of alkyl(C1-C6) methacrylates or acrylates and of amphiphilic monomers containing at least one fatty chain, such as, for example, a copolymer of methyl acrylate and ethoxylated stearylamine manufactured by the company GOLDSCHMIDT under the name ANTIL 208®.

(5) copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers containing at least one fatty chain, such as, for example, a copolymer of polietilenglikolsuktsinata and lauriemittiet.

- (6) poliafico urethane, containing in their chain simultaneously hydrophilic sequence, often polyoxyethylene, and a hydrophobic sequence, which can only be aliphatic sequences and/or cycloaliphatic and/or aromatic sequences.

- (7) polymers with main chain ester aminoplast containing at least one fatty chain, such as connections PURE THIX®offered by the company SUD-CHEMIE.

Preferably politicomilitary contain at least two lipophilic hydrocarbon chains containing from 6 to 30 carbon atoms, separated by a hydrophilic sequence, and the hydrocarbon chain may be suspended by chains or chains at the end of the hydrophilic sequence. In particular, it is possible to provide one or more dangling chains. In addition, the polymer may contain a hydrocarbon chain at one or two ends of a hydrophilic sequence.

Politicomilitary can have mnogoobrazny form, in particular of Tremblant. Hydrophobic sequences can be at each end of the chain (for example: three-block copolymer with a Central hydrophilic sequence), or to accommodate both at the ends and inside the chain (for example, a copolymer with multiple sequences). These polymers can also be in icymi or stellate.

Non-ionic politicomilitary with fatty chain can be three-block copolymers, hydrophilic sequence which is polyoxyethylene chain containing from 50 to 1000 ethoxylated groups. Non-ionic politicomilitary contain one urethane bond between the hydrophilic sequences, whence comes the name.

In a broad sense, the non-ionic politicaleconomy with fatty chains called also those in which the hydrophilic sequence connected with lipophilic sequences of other chemical bonds.

As examples of nonionic politicalization with fatty chains that may be used in the invention can also be used Rhéolate 205® with carbamide group, produced by the company RHEOX, or Rhéolate® 208, 204 or 212, and also Acrysol RM 184®.

You can also call the product ELFACOS T210® with alkyl chain C12-C14and the product ELFACOS T212® with alkyl chain C18from AKZO.

You can also use the product DW 1206B® from ROHM & HAAS with alkyl chain C20and urethane bond, in the form of a 20% solids in water.

You can also use solutions or dispersions of these polymers, in particular, in water or in aqueous-alcoholic medium. As examples of such polymers can be called Rhéolate® 255, Rhéolate® 278 and Rhé olate® 244 manufactured by the company RHEOX.

You can also use the product DW 1206F and DW 1206J offered by the company ROHM & HAAS.

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

More particularly according to the invention, it is preferable to use polyetherpolyols, which can be obtained by polycondensation of at least three compounds containing (i) at least one glycol containing from 150 to 180 mol of ethylene oxide, (ii) stearyl alcohol or decroly alcohol and (iii) at least one diisocyanate.

Such politicomilitary produced, in particular, by the company ROHM & HAAS under the names Aculyn 46® and Aculyn 44® [ACULYN 46® is polycondensate of polyethylene glycol with 150 or 180 mol of ethylene oxide, stearyl alcohol and methylene-bis(4-cyclohexylsulfamate) (SMDI), at a concentration of 15 wt.% in a matrix of maltodextrin (4%) and water (81%); ACULYN 44® is polycondensate of polyethylene glycol with 150 or 180 mol of ethylene oxide, delovogo alcohol and methylene-bis(4-cyclohexylsulfamate) (SMDI) at a concentration of 35 wt.% in a mixture of propylene glycol (39%) and water (26%)].

Cationic polymers and amphoteric polymers can range from about 0.01 to 10 wt.%, preferably from 0.05 to 5 wt.% and even more preferably is from 0.1 to 3 wt.% the total weight of the composition. Associative polymers can range from about 0.01 to 10% of the total weight of the composition and preferably from 0.1 to 5 wt.% the total weight of the composition.

Environment

Medium ink composition suitable for dyeing is preferably an aqueous medium, formed by water, which may preferably contain one or more organic solvents that are acceptable in cosmetic terms, in particular monohydroxy alcohols or diols, linear or branched, preferably saturated, containing from 2 to 10 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexyleneglycol (2-methyl-2,4-pentanediol), neopentylglycol and 3-methyl-1,5-pentanediol; aromatic alcohols such as benzyl alcohol, phenethyl alcohol; glycols or glycol ethers, such as for example, onomatology, monotropy and monobutyl ethers of ethylene glycol, propylene glycol or its ethers such as, for example, onomatology ether of propylene glycol, butyleneglycol, dipropyleneglycol; and alkalemia(C1-C4) ethers of diethylene glycol such as, for example, monotropy or monobutyl ether of diethylene glycol, individually or in a mixture.

In this case, the solvents may be present, each in concentrations that constitute from 0.5 to 20 wt.% the total weight of the composition. More specifically, the amount of solvent which is at least 2 wt.%, preferably at least 5 wt.% the total weight of the composition. At the same time, it may be preferably equal to or less than 20 wt.%, more preferably less than or equal to 15 wt.% the total weight of the composition.

Other additives

The ink composition according to the invention may contain an effective amount of other agents, also previously known in oxidation dyeing, such as various conventional additives such as complexing compounds such as EDTA, heteronomy acid, UV filters, waxes, volatile or nonvolatile silicone compounds, cyclic, linear or branched, organomodified (in particular, amino groups) or not, preservatives, ceramides, pseudoceramides, vitamins or provitamins such as panthenol, matting agent, etc.

According to one feature of the invention the composition may contain at least one fatty substance chosen in particular from saturated aliphatic alcohols, linear or branched, containing at least 10 carbon atoms; oils or waxes, saturated vegetable origin, hydrocarbon. Preferably, if such compounds are present, their content is below or equal to 10 wt.% by weight of the composition.

This composition may also contain reducing agents or antioxidants. It may be selected, in particular from sodium sulphite, thioglycolic, timelocal acid, sodium bisulfite, dehydroascorbic acid, hydroquinone, 2-methylhydroquinone, tert-butylhydroquinone and homogentisic acid, and they are in this case usually present in amounts comprising from about 0.05 to 3 wt.% the total weight of the composition.

Ink composition conforming to the invention may in addition contain unsaturated aliphatic alcohols, such as alerby alcohol in a weight proportion of from 0.5 to 15% of the total weight of the ink composition.

Of course, the specialist must choose the optional additional compound(I)mentioned above, so that beneficial properties inherent in the ready-to-use composition according to the invention would not be changed or materially modified the proposed additive or additives.

In accordance with one specific embodiment of the invention, the composition prior to mixing with an oxidizing composition is in liquid form at 25°C and atmospheric pressure.

Preferably, the liquid has a viscosity of not more than 150 centipoise, measured by the rheometer RhéoStress 1, the degree of shift 200-1at 25°C.

The oxidizing agent

In the oxidizing composition, the oxidizing agent preferably selected from hydrogen peroxide, urea peroxide, bromato Il is ferricyanide alkali metals, persona, such as perborates and persulfates. The use of hydrogen peroxide is particularly preferable. The oxidant is preferably formed by a hydrogen peroxide solution, the title of which may vary, in particular, about 1 to 40 volumes, and even more preferably from about 5 to 40.

Can also be used as an oxidizing agent one or more redox enzymes, such as laccase, peroxidase and an oxidoreductase with 2 electrons (such as uricase), optionally in the presence of the donor or of the corresponding cofactor.

the pH of the ready-to-use composition applied to the keratin fibers [composition obtained by mixing the ink composition and the oxidizing composition], typically has a value from 3 to 12 inclusive. It is preferably from 8.5 to 11, inclusive, and may be set to the desired value with the help of pagkikita or podslushivaet, well known in the prior art in the dyeing of keratin fibers.

From podslushivaet can be called, for example, ammonium hydroxide, carbonates of alkali metals, alkanolamines, such as mono-, di - and triethanolamines and their derivatives, hydroxyethylamine and acetyltyrosine and/or oxypropylene ethylendiamine, hydroxides of sodium or potassium hydroxide and the compounds of the following formulas is:

in which R is a propylene residue, possibly substituted by a hydroxyl group, or an alkyl radical C1-C4; R38, R39, R40and R41identical or different, represent a hydrogen atom, an alkyl radical C1-C4or hydroxyalkyl C1-C4.

Podnikatel usually are, for example, inorganic or organic acids, such as hydrochloric acid, orthophosphoric acid, carboxylic acids such as tartaric acid, citric acid, lactic acid, or sulphonic acids.

The method of colouring according to the invention is preferably in applying the ready-to-use composition, prepared at the time of application of ink and oxidizing composition described above, to wet or dry keratin fibers, in impact over time of about 1 to 60 minutes, more preferably from about 10 to 45 minutes, rinsing the fibers, and then, if necessary, washing them with shampoo, then repeat rinsing and drying.

The following is a specific example illustrating the invention and without limiting character.

Example 1

Was prepared following the ink composition:

Ink composition:

(expressed in grams of active the substances)

Lauralanthalasa acid 4,5 OE (Akypo® RLM 45, manufactured by CHEM Y)7
Lauric alcohol 2 OE (Dehydol®LS-2-DEO-N, manufactured by COGNIS)4
Decroly alcohol 5 OE (Empilan®KA-5/90-FL, manufactured by ALBRIGHT & WILSON)8
Alerby alcohol3
Amide fatty acids of rapeseed oil with 4 mol ethylene oxide (l®N, manufactured by CHEM Y)7
Associative nonionic polymer (Dapral® T212 produced AKZQ)1
Monoethanolamine2
Polyquaternium 6 (Merquat® 100, manufactured by CALGON)1,5
Ethanol11
Propylene glycol5
Dipropyleneglycol5
1,3-dihydroxybenzene (resorcinol)0,3
Paraphenylenediamine0,3
Reducing agents, antioxidantsdost. Qty
Complexing agentdost. Qty
Perfumedost. Qty
Ammonium hydroxide (ammonia 20,5%)1,6
Demineralized the ode, sufficient quantity to100

The ink composition was mixed with an oxidizing composition before application, in a plastic Cup for 2 minutes, tetroe hydrogen peroxide fortress 20 volumes at the rate of 1 part of dye composition per 1.5 parts of oxidizing composition.

The resulting mixture was applied to strands of hair graying at 90% and left for 30 minutes.

Then the strands were rinsed with water, wash it with shampoo, again rinsed with water, then dried and combed.

Got a greenish-brown hue.

Example 2

Was prepared following coloring composition:

Coloring composition:

(the content expressed in grams of active substance)

Composition A according to the inventionComposition B comparative
Propylene glycol55
Ethoxylated amide acid rapeseed oil (4 OE)73
Lauralanthalasa acid (4,5 OE)4,54,5
Decroly alcohol acetyltyrosine (3 OE)8,08,0
Alerby alcohol11
Lauric alcohol acetyltyrosine (2 OE 44
Diuretin (HMDI) acetyltyrosine (66 OE) and oxyprogesterone (OP 14) alcohols (C16/C18)0,10,1
1,3-dihydroxybenzene (resorcinol)0,30,3
1,4-diaminobenzene0,30,3
Monoethanolamine net22
ethylenediaminetetraacetic acid0,20,2
Erythropenia acid (or D-isoascorbic acid)0,310,31
A homopolymer of dimethyldiallylammonium-chloride in 40% aqueous solution1,51,5
Perfume0,950,95
Dipropyleneglycol55
Thiolactam ammonium 58% aqueous solution (50% timelocal acid)0,80,8
Ammonium hydroxide (theoretical concentration 20%)88
Ethyl alcohol 96°, denatured11,011,0
Deionized waterDost. Qty 100dost. Qty 100

The ink composition was mixed in point Prim is in with an oxidizing composition, citrua hydrogen peroxide fortress 20 volumes at the rate of 1 part of dye composition per 1.5 parts of oxidizing composition.

The resulting mixture was applied on half of the head 10 different models (one half of the head with A composition mixed with an oxidizing composition, and the other half of the head with composition B, mixed with the same oxidizing composition).

The difference in application between the two bases was noted on a scale from 1 to 5, in particular:

- adherence to the roots (1: bad grip - 5: very good adhesion)

- consistency on the head (1: low - 5: very dense)

Using 10 trials, in which the evaluation was conducted by the group of experts (evaluators in each trial varied), were obtained the following average results:

GripConsistency
ABAB
3,352,252,951,95

Composition A according to the invention, which contains 7% Aminol N, shows a much better grip with roots and is more dense on the head (deviations significant)than the comparative composition B, which contains only 3% of Aminol N.

1. The composition for oxidative okresu is of keratin fibers, in particular keratin fibers and more specifically hair, containing in a medium suitable for dyeing, at least one oxidation dye, characterized in that it contains more than 5% by weight of the composition of at least one acetyltyrosine amide fatty acids of rapeseed oil.

2. The composition according to claim 1, characterized in that acetyltyrosine amide fatty acids of rapeseed oil selected from the group formed such inorganic salts containing from 1 to 20 mol of ethylene oxide.

3. The composition according to claim 1, characterized in that the content acetylaminophenol amide fatty acids of rapeseed oil is up to 20% by weight of the composition, preferably less than 10% by weight of the composition.

4. The composition according to claim 1, characterized in that the content of the amide is at least 5,5%, in particular at least 6%, by weight of the composition.

5. The composition according to claim 1, characterized in that it contains at least one oxidizable base or its salts accession acid selected from hydrochloride, hydrobromide, sulfates, tartratami, lactates and acetates.

6. The composition according to claim 5, characterized in that the oxidized bases are chosen from ortho - or paraphenylenediamine, double bases, ortho - or paraaminophenol and heterocyclic bases, and salts of the Association of these compounds with CIS who Auteuil.

7. The composition according to claim 6, characterized in that paraphenylenediamine selected from compounds of the following formula (I):

in which R1represents a hydrogen atom, an alkyl radical C1-C4monohydroxyethyl C1-C4polyhydroxyethyl2-C4, alkoxy (C1-C4) alkyl (C1-C4), alkyl (C1-C4substituted nitrogen-containing group selected from amino, monoalkyl (C1-C4) amino, dialkyl (C1-C4) amino, trialkyl (C1-C4) amino, monohydroxyethyl (C1-C4) amino radicals, imidazoline and ammonium, phenyl or 4'-AMINOPHENYL;

R2represents a hydrogen atom, an alkyl radical C1-C4monohydroxyethyl C1-C4or polyhydroxyethyl2-C4, alkoxy (C1-C4) alkyl (C1-C4) or alkyl (C1-C4substituted nitrogen-containing group;

R1and R2can also form with the nitrogen atom to which they relate, contain nitrogen a heterocycle with 5 or 6 links, possibly substituted by one or more alkyl, hydroxyl or ureidopropionic;

R3represents a hydrogen atom, halogen atom, alkyl radical C1-C4alphagroup, carboxyl, managed oxyalkyl or hydroxyalkoxy C 1-C4acetylaminobenzoic C1-C4methylaminorex C1-C4or carbamoylphenoxy C1-C4,

R4represents a hydrogen atom, halogen or alkyl radical C1-C4.

8. The composition according to claim 6, wherein the double bases are chosen from compounds of the following structure (II):

in which Z1and Z2identical or different, represent a hydroxyl radical or-NH2that can be a substituted alkyl radical C1-C4or by a bridge Y;

the bridge Y is an alkylenes chain containing from 1 to 14 carbon atoms, linear or branched, which may be interrupted or terminated by one or more nitrogen-containing groups selected from amino, monoalkyl (C1-C4) amino, dialkyl (C1-C4) amino, trialkyl (C1-C4) amino, monohydroxyethyl (C1-C4) aminosalicylic, imidazoline and ammonium and/or one or more heteroatoms such as oxygen atoms, sulfur or nitrogen, possibly substituted by one or more hydroxyl or C1-C6alkoxyalkane;

R5and R6represent a hydrogen atom or a halogen, an alkyl radical C1-C4monog taxiarchis C 1-C4polyhydroxyethyl2-C4aminoalkyl C1-C4or bridging group Y;

R7, R8, R9, R10, R11and R12identical or different, represent a hydrogen atom, the bridge Y or alkyl radical C1-C4provided that the compounds of formula (II) contain only one bridge group Y in the molecule.

9. The composition according to claim 6, characterized in that paraaminophenol selected from compounds of the following structure (III):

in which R13represents a hydrogen atom, halogen atom, alkyl radical C1-C4monohydroxyethyl C1-C4, alkoxy (C1-C4) alkyl (C1-C4), or aminoalkyl C1-C4or hydroxyalkyl (C1-C4) aminoalkyl C1-C4;

R14represents a hydrogen atom or a halogen atom, an alkyl, C1-C4monohydrocalcite C1-C4, polyhydroxyalkane2-C4, aminoalkyl C1-C4, cyanoaniline C1-C4or alkoxy (C1-C4) alkyl, C1-C4the radical.

10. The composition according to claim 6, wherein said heterocyclic bases are chosen from pyridine derivatives, pyrimidine derivatives, including pyrazolopyrimidines, the derivatives of pyrazole.

11. The composition according to claim 6, characterized in that the oxidized bases are present in concentrations of from 0.0005 to 12% and preferably 0.005 to 8% of the total weight of the composition.

12. The composition according to claim 1, characterized in that the actual pigment components selected from metaphenylenediamine, melaninogenica, Matadepera, the heterocyclic actual pigment components and salts of the Association of these compounds with an acid, selected their hydrochloride, hydrobromides, sulfates, tartratami, lactates and acetates.

13. The composition according to item 12, wherein the actual pigment components are present in concentrations of from 0.0001 to 10%, preferably 0.005 to 5% of the total weight of the composition.

14. Composition according to one of the preceding paragraphs, characterized in that it further comprises a direct dye, the weight proportion of which is from 0.001 to 20%, preferably from 0.01 to 10% of the total weight of the composition.

15. The composition according to claim 1, characterized in that it further contains at least one reducing agent or an antioxidant in an amount of from 0.05 to 3% of the total weight of the composition.

16. The composition according to claim 1, characterized in that it contains at least one surfactant selected from anionic, cationic, nonionic or amphoteric surface-active substances.

17. The composition according to item 16, characterized in that she will win at least one anionic surfactant type acetylaminophenol (C 8-C30) alkyloxy carboxylic acid or one of its salts.

18. The composition according to item 16, characterized in that it contains at least one non-ionic surfactant, oxyalkylene or mono - or paliperidonesee.

19. The composition according to claim 1, characterized in that the surfactant is from 0.01 to 40%, preferably from 0.1 to 30% of the total weight of the composition.

20. The composition according to claim 1, characterized in that it contains at least one associative polymer is non-ionic, anionic, cationic or amphoteric type in the amount of from 0.01 to 10% of the total weight of the composition.

21. The composition according to claim 1, characterized in that it contains at least one cationic or amphoteric polymer in an amount of from 0.01 to 10% of the total weight of the composition.

22. The composition according to claim 1, characterized in that it contains at least one unsaturated aliphatic alcohol in an amount of from 0.5 to 15% of the total weight of the composition.

23. The composition according to claim 1, characterized in that it contains water, at least one solvent selected from monohydroxy alcohols or diols, linear or branched, preferably saturated, containing from 2 to 10 carbon atoms; aromatic alcohols; glycols, ethers, glycol, simple alilovic ethers of diethylene glycol individually or in a mixture.

24. The composition according to item 23, wherein the solvent or solvents are present each in concentrations that constitute from 0.5 to 20% of the total weight of the composition.

25. The composition according to claim 1, characterized in that it is in liquid form.

26. Ready-to-use composition for the oxidation dyeing of keratin fibers, particularly keratin fibers person, such as hair, characterized in that it is obtained by mixing the ink composition, such as defined in one of claims 1 to 25, and an oxidizing composition comprising at least one oxidizing agent.

27. The composition according to p. 25, characterized in that the oxidizing agent chosen from hydrogen peroxide, urea peroxide, bromato or ferricyanides alkali metals, persona, redox enzymes, such as laccase, peroxidase and an oxidoreductase with two electrons, optionally in the presence of the donor or of the corresponding cofactor.

28. A method of coloring keratin fibers, particularly keratin fibers and more specifically the hair, characterized in that it consists in applying to the fibers at least one ink composition containing in a medium suitable for dyeing, at least one oxidation dye and more than 5% by weight of the composition of at least one acetyltyrosine amide LM is Noah acid rapeseed oil, and color show at alkaline, neutral or acidic pH using an oxidizing composition containing, in a medium suitable for dyeing, at least one oxidizing agent, which are mixed immediately before use with an ink composition or which is applied thereafter, without intermediate rinsing.

29. The method according to p, characterized in that it consists in applying to wet or dry keratin fibers ready-to-use composition, prepared immediately before use of ink and oxidizing compositions, in effect during the period of time of about 1 to 60 minutes, preferably from 10 to 45 minutes, rinsing the fibers, and then, if necessary, washing them with shampoo, then repeat rinsing and drying.

30. Kit for dyeing keratin fibers, more specifically the hair, characterized in that at least one branch includes the ink composition comprising in a medium suitable for dyeing, at least one oxidation dye and more than 5% by weight of the composition of at least one acetylaminophenol amide fatty acids of rapeseed oil, and that the other compartment comprises an oxidizing composition comprising in a medium suitable for dyeing, an oxidizing agent.



 

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