DE20120050U1 - New oxidation dyes with 2,4-dichloro-3-aminophenol - Google Patents

Description

Henkel KGaA

Dr. May/ES
07.12.2001

Utility model application H 5449

"New oxidation dyes with 2,4-dichloro-3-aminophenol"

The present invention relates to agents for dyeing keratin fibers which contain 2,4-dichloro-3-aminophenol as a coupler component in combination with at least one other specific dye precursor.

Keratin fibers, especially human hair, are now treated in a variety of ways with hair cosmetic preparations. These include cleaning the hair with shampoos, caring for and regenerating it with conditioners and treatments, and bleaching, coloring and shaping the hair with dyes, tints, perming products and styling products. Products for changing or nuanced the color of the hair play a prominent role.

For temporary coloring, dyes or tints are usually used that contain so-called direct dyes as the coloring component. These are dye molecules that are absorbed directly into the hair and do not require an oxidative process to form the color. One of these dyes is henna, which has been known since ancient times for coloring the body and hair. These dyes are generally sensitive to shampooing, so that an often undesirable shift in shade or even visible "discoloration" can occur.

So-called oxidation dyes are used for permanent, intensive coloring with corresponding fastness properties. Such dyes usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidation agents or atmospheric oxygen, or by coupling with one or more coupler components. The oxidation dyes are characterized by excellent, long-lasting coloring results.

H5449 2

Good oxidation dye precursors should primarily meet the following requirements: They must produce the desired color nuances with sufficient intensity and authenticity during oxidative coupling. They must also have good absorption properties on the fiber, whereby in the case of human hair in particular there must be no noticeable differences between damaged and newly grown hair (leveling properties). They should be resistant to light, heat, sweat, friction and the influence of chemical reducing agents, e.g. permanent wave liquids. Finally, if they are used as hair dyes, they should not stain the scalp too much and, above all, they should be harmless from a toxicological and dermatological point of view. Furthermore, the color achieved should be easy to remove from the hair by bleaching if it does not meet the individual's wishes and needs to be reversed.

A developer component or a special coupler/developer combination alone is generally not sufficient to achieve a color shade that looks natural on the hair. In practice, combinations of different developers and/or coupler components are therefore usually used. There is therefore a constant need for new, improved dye components, in particular to achieve the widest possible coverage of the entire color palette.

It has now surprisingly been found that particularly intensive dyeings with excellent fastness properties and extraordinarily good toxicological properties can be obtained when dyeing agents are used which contain a special combination of 2,4-dichloro-3-aminophenol and at least one other special dye precursor.

A first object of the present invention is therefore an agent for dyeing keratin fibers, which contains in a medium suitable for dyeing as oxidation dye precursors a combination of

a) 2,4-dichloro-3-aminophenol and

b) at least one further dye precursor selected from l-(2'-hydroxyethyl)-4,5-diaminopyrazole, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4,5,6-

• » ♦ Si ·· *

Tetraaminopyrimidine, 1 -(2'-Hydroxyeihyl)-2,5-diaminobenzene, p-toluenediamine, bis-(2-hydroxy-5-aminophenyl)-methane and 3-methyl-4-aminophenol,
and the physiologically acceptable salts of these compounds.

According to the invention, keratin fibres are understood to mean fur, wool, feathers and in particular human hair.

Examples of physiologically acceptable salts of the compounds according to the invention are the hydrochlorides, hydrobromides, sulfates, phosphates, acetates, propionates, citrates and lactates.

The color-changing agents according to the invention can contain at least one further dye precursor in addition to the dye combination according to the invention.

The present invention is not subject to any restrictions with regard to the dye precursors that can be used in the agents according to the invention. The agents according to the invention can be used as dye precursors

, oxidation dye precursors of the developer and coupler type, and

• Precursors of natural-analogous dyes, such as indole and indoline derivatives,

as well as mixtures of representatives of these groups.

Primary aromatic amines with an additional free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives are usually used as developer components.

According to the invention, it may be preferred to use a p-phenylenediamine derivative or one of its physiologically acceptable salts as the developer component. Particularly preferred are p-phenylenediamine derivatives of the formula (I)

NG ¹ G ²

(I)

_NH2

G ¹ represents a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, a C 1 - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C 8 -polyhydroxyalkyl radical, a (C ₁ - to C ₄ )-alkyloxy-(C ₁ - to C ₄ )-alkyl radical, a 4'-aminophenyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;

G ² represents a hydrogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C 8 polyhydroxyalkyl radical, a (C ₁ to C ₄ )-alkyloxy-(C ₁ to C ₄ )-alkyl radical or a C ₁ to C ₄ alkyl radical substituted by a nitrogen-containing group;

G ³ represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₁ to C ₄ hydroxyalkoxy radical, a C ₁ to C ₄ acetylaminoalkoxy radical, a C ₁ to C ₄ mesylaminoalkoxy radical or a C ₁ to C ₄ carbamoylaminoalkoxy radical;

G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ to C ₄ alkyl radical or

When G ³ and G ⁴ are in the ortho position to each other, they can together form a bridging α,ω-alkylenedioxo group, such as an ethylenedioxy group.

Examples of the C ₁ - to C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ - to C ₄ -alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, preferred examples of a C ₁ - to C ₄ -hydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly

preferred. Examples of halogen atoms according to the invention are F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used according to the invention are derived from the definitions given here. Examples of nitrogen-containing groups of the formula (II) are in particular the amino groups, C ₁ - to C ₄ -monoalkylamino groups, C 1 - to C ₄ -dialkylamino groups, C ₁ - to C ₄ -trialkylammonium groups, C ₁ - to C ₄ -monohydroxyalkylamino groups, imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (I) are selected from p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine, N,N-dipropyl-p-phenylenediamine, 4-amino-3-methyl-(N,N-diethyl)-aniline, N,N-bis-(ß>Hydr _0X yethyl)-pphenylenediamine, 4-N,N-bis-(ß. _Hy droxyethyl)amino-2-methylaniline, 4-N,N-bis-(ß-hydroxyethyl)amino-2-chloroaniline, 2-( _a ß.Dihydroxyethyl)-p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N-(ß_pjy _< i _rox yp _rO pyn-p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, NjN-dimethyl-S-methyl-p-phenylenediamine, N,N-(ethyl,ß-hydroxyethyl)-PP ^hen y ^lendiamm , N-(ß,r ^Dih y ^drox yP ^ro Py ¹ )"P"P ^hen y ^lendiamine 'N-(4'-aminophenyl)-p-phenylenediamine, N-phenyl-p-phenylenediamine, 2-(ß.

Hydroxyethyloxy)-p-phenylenediamine, 2-(ß_acet ^{yl ammoet} hyloxy)-p-phenylenediamine, N-(ß-methoxyethyl)"P'phenylenediamine and 5,8-diaminobenzo-l,4-dioxane and their physiologically acceptable salts.

According to the invention, particularly preferred p-phenylenediamine derivatives of the formula (I) are p-phenylenediamine and N,N-bis-(ß-hydroxymethyl)phenylenediamine.

Furthermore, it may be preferred according to the invention to use another p-aminophenol derivative or one of its physiologically acceptable salts as the developer component. Particularly preferred are p-aminophenol derivatives of the formula (II)

&agr;&idigr;)

^NHG1

where:

G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C^monohydroxyalkyl radical, a C ₂ - to C ₆ -polyhydroxyalkyl radical, a (C ₁ - to C ₄ )-alkoxy-(C ₁ - to C ₄ )-alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical, a hydroxy-(C,- to C ₄ )-alkylamino radical, a C ₁ - to C ₄ -hydroxyalkoxy radical, a C ₁ - to C ₄ -hydroxyalkyl-(Cj- to C ₄ )-aminoalkyl radical or a (di-C ₁ - to C ₄ -alkylamino)-(C ₁ - to C ₄ )-alkyl radical, and

G ¹⁴ represents a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a C 1 - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₆ -polyhydroxyalkyl radical, a (C ₁ - to C ₄ )-alkoxy-(C 1 - to C ₄ )-alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a C ₁ - to C ₄ -cyanoalkyl radical,

G ¹⁵ represents hydrogen, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₆ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and

G ¹⁶ stands for hydrogen or a halogen atom.

The substituents used in formula (II) are defined according to the invention analogously to the above statements.

Preferred p-aminophenols of the formula (II) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methyl-phenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-(ßhydroxyethoxy)-phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino-2-aminomethylphenol, 4-amino-2-(ßhydroxyethyl-aminomethyl)-phenol, 4-amino-2-( _α ,β-dihydroxyethyl)-phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2-(diethylaminomethyl)-phenol and their physiologically acceptable salts.

H5449

Very particularly preferred compounds of the formula (II) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(α,β-dihydroxyethyl)phenol and 4-amino-2-(diethylaminomethyl)phenol.

Furthermore, the developer component can be selected from o-aminophenol and its derivatives, such as 2-amino-4-methylphenol or 2-amino-4-chlorophenol.

Furthermore, the developer component can be selected from heterocyclic developer components, such as pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiologically acceptable salts.

Preferred pyridine derivatives are in particular the compounds described in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine, 2-(ß-methoxyethyl)amino-3-amino-6-methoxypyridine and 3,4-diaminopyridine.

Preferred pyrimidine derivatives are in particular the compounds described in German patent DE 2 359 399, Japanese laid-open specification JP 02019576 A2 or in laid-open specification WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.

Preferred pyrazole derivatives are in particular the compounds described in the patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740931 and DE 195 43 988, such as 4,5-diamino-1-methylpyrazole, 4,5-diamino-l-(ß-hydroxyethyl)pyrazole, 3,4-diaminopyrazole, 4,5-diamino-l-(4'-chlorobenzyl)pyrazole, 4,5-diamino-l,3-dimethylpyrazole, 4,5-diamino-3-methyl-l-phenylpyrazole, 4,5-diamino-1 -methyl-3-phenylpyrazole, 4-amino-1,S-dimethyl-S-hydrazinopyrazole, 1 Benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(ß-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-l-ethyl-3-methylpyrazole, 4,5-diamino -l-ethyl-3-(4'-methoxyphenyl)-pyrazole, 4,5-diamino-1 -ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1 -methyl-

. a

pyrazole, 4,5-diamino-3-hydroxymethyl-l-isopropylpyrazole, 4,5-diamino-3-methyl-lisopropylpyrazole, 4-amino-5-(2'-amioethyl)amino-l,3-dimethylpyrazole, 3, 4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4(ß-hydroxyethyl)amino-l-methylpyrazole.

Preferred pyrazole-pyrimidine derivatives are in particular the derivatives of pyrazole-[1,5-a]-pyrimidine of the following formula (III) and its tautomeric forms, provided that a tautomeric equilibrium exists:

-[NG ¹⁷ G ¹⁸ Jp

-[NG ¹⁹ G ²⁰ Ic

(III)

where:

G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a C 1 - to C ₄ -alkyl radical, an aryl radical, a C 1 - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a (C 1 - to C ₄ )-alkoxy-(C 1 - to C ₄ )-alkyl radical, a C 1 - to C ₄ -aminoalkyl radical, which may optionally be protected by an acetyl-ureide or sulfonyl radical, a (C 1 - to C ₄ )-alkylamino-(C 1 - to C ₄ )-alkyl radical, a di-[(C 1 - to C ₄ )-alkyl]-(C 1 - to C ₄ )-aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain members, a C 1 - to C ₄ -hydroxyalkyl- or a di-(Ci- to C ₄ )-[hydroxyalkyl]-(Ci- to C ₄ )-aminoalkyl radical,

the X radicals independently represent a hydrogen atom, a C1 to C4 _alkyl radical, an aryl radical, a Cp to _C4 hydroxyalkyl radical, a _C2 to C4 _{polyhydroxyalkyl} radical, a C1 to Q aminoalkyl radical, a (Cp to _C4 ) alkylamino (Cp to _C4 ) alkyl radical, a di[(Cp to _C4 ) alkyl] (Cp to C4) aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain members, a Cp to C4 hydroxyalkyl or a di(Cj to _C4 hydroxyalkyl) aminoalkyl radical, an amino radical, a Cp to _C4 alkyl or di(Cp to _C4 hydroxyalkyl) amino radical, a halogen atom, a carboxylic acid group or a sulfonic acid group,

i has the value 0, 1,2 or 3,

· t

&rgr; has the value O or 1,

q has the value 0 or 1 and

&eegr; has the value 0 or 1,
provided that

the sum of &rgr; + q is not equal to 0,

if &rgr; + q is 2, &eegr; has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7);

if ρ + q is 1, η has the value 1, and the groups NG ¹⁷ G ¹⁸ (or NGI9G20) and the group OH occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7);

The substituents used in formula (III) are defined according to the invention analogously to the above statements.

If the pyrazole-[l,5-a]-pyrimidine of the above formula (III) contains a hydroxy group at one of the positions 2, 5 or 7 of the ring system, a tautomeric equilibrium exists, which is shown, for example, in the following scheme:

NG ¹⁷ G ¹⁸

Among the pyrazole-[l,5-a]-pyrimidines of the above formula (III) one can mention in particular:

pyrazole-[1,5-a]-pyrimidine-3,7-diamine;

2,5-Dimethylpyrazole-[l,5-a]-pyrimidine-3,7-diamine;

pyrazole-(1,5-a]-pyrimidine-3,5-diarnine;

2,7-Dimethylpyrazole-[l,5-a]-pyrimidine-3,5-diamine;

3-Aminopyrazole-[l,5-a]-pyrimidin-7-ol;

3-Amino pvrazole-[l,5-a]-pyrimidin-5-ol;

2-(3-Aminopyrazole-[1,5-a]-pyrimidin-7-ylamino)-ethanol;

2-(7-Aminopyrazole-[l,5-a]-pyrimidin-3-ylamino)-ethanol;

2-[(3-Aminopyrazole-[1,5-a]-pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol;

H5449 10

2-[(7-Aminopyrazole-[1,5-a]-pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol;

5,6-Dimethylpyrazole-[l,5-a]-pyrimidine-3,7-diamine;

2,6-Dimethylpyrazole-[l,5-a]-pyrimidine-3,7-diamine;

2,5, N7, N7-Tetramethylpyrazole-[l,5-a]-pyrimidine-3,7-diamine;

as well as their physiologically acceptable salts and their tautomeric forms, if a tautomeric equilibrium exists.

The pyrazole-[l,5-a]-pyrimidines of the above formula (III) can be prepared by cyclization starting from an aminopyrazole or from hydrazine as described in the literature.

According to the invention, particularly preferred developer components are selected from p-phenylenediamine, 2-( _α ,β-dihydroxyethyl)-p-phenylenediamine, N,N-bis-(β-hydroxy ^em yl)-p-phenylenediamine, N,N'-bis-(β_hydroxyethyl)-N,N'-bis-(4'-aminophenyl)-1,3 -diaminopropan-2-ol, N,N'-bis-(4'-aminophenyl)-1,4-diazacycloheptane, 1,1O-bis-(2',5'-

diaminophenyl)-1,4,7,10-tetraoxadecane, p-aminophenol, 4-amino-2-aminomethylphenol, 4-amino-2-( _a ,ß-dihydroxyethyl)-phenol, 4-amino-2-(diethyl- aminomethyl)-phenol, 2-amino-4-methylphenol, 2-amino-5-methylphenol, 2-amino-4-chlorophenol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine , 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, 4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole, 4 ,5-Diamino-l-(4'-chlorobenzyl)pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,S-dimethyl- S-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tertbutyl-3-methylpyrazole, 4 ,5-Diamino-l-(ß-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-l-ethyl-3-(4'-methoxyphenyl)- pyrazole, 4,5-diaminol-ethyl-3-hydroxymethylpyrazole, 4,5-Diamino-3-hydroxymethyl-l-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1 -isopropylpyrazole, 4,5-diamino-3-methyl-1 -isopropylpyrazole, 4-amino-5-(ß -aminoethyl)-amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5 -Diami no-1 -methyl-4-methylaminopyrazole, 3,5 -Diamino-4-(ßhydroxyethyl)-amino-l-methylpyrazole, pyrazole-[l,5-a]-pyrimidine-3,7-diamine, 2,5-dimethyl-pyrazole-[l,5-a]-pyrimidine -3,7-diamine, pyrazole-[l,5-a]-pyrimidine-3,5-diamine, 2,7-Dimethyl-pyrazole-[l,5-a]-pyrimidin-3,5-diamine, 3-aminopyrazole-[l,5-a]-pyrimidin-7-ol,

H5449 11

3-Aminopyrazole-[l,5-a]-pyrimidin-5-ol, 2-(3-aminopyrazole-[l,5-a]-pyrimidin-7-ylamino)-ethanol, 2-(7-aminopyrazole-[ 1,5-a]-pyrimidin-3-ylamino)-ethanol, 2-[(3-aminopyrazole-[1,5-a]-pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]- ethanol, 2-[(7-aminopyrazole-[1,5-a]-pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol, 5,6-dimethylpyrazole-[1,5-a ]-pyrimidine-3,7-diamine, 2,6-dimethylpyrazole-[l,5-a]-pyrimidine-3,7-diamine, 3-Amino-7-dimethylamino-2,5-dimethylpyrazole-[l,5-a]-pyrimidine and the physiologically tolerable salts of these compounds.

As coupler components, m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are usually used.

Coupler components preferred according to the invention are:

- m-Aminophenol and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 3-trifluoroacetylamino^- chloro-o-methylphenol, 5 - amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5-(2'-hydroxyethyl)-amino-2-methylphenol, 3-(diethylamino) -phenol, 1,3-dihydroxy-5-(methylamino)-benzql, 3-ethylamino-4-methylphenol and 2,4-dichloro-3-aminophenol,
o-Aminophenol and its derivatives,

m-Diaminobenzene and its derivatives such as 2,4-diaminophenoxyethanol, 1,3-bis-(2',4'-diaminophenoxy)-propane, 1,3-bis-(2',4'-diaminophenyl)-propane, 2,6-bis-(2'-hydroxyethylamino)-l-methylbenzene and 1-amino-3-bis-(2'-hydroxyethyl)-aminobenzene,

o-Diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-l-methylbenzene,

Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6 -methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,

H5449

Naphthalene derivatives such as 1-naphthol, 2-methyl-l-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1 ,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,

Moφholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorphoiin,

Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,
Pyrazole derivatives such as l-phenyl-3-methylpyrazol-5-one,
Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,

- Pyrimidine derivatives, such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino -4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or

Methylenedioxybenzene derivatives such as l-hydroxy-3,4-

methylenedioxybenzene, l-amino-3,4-methylenedioxybenzene and l-(2'-hydroxyethyl)-amino-3,4-methylenedioxy-benzene.

Particularly preferred further coupler components are 2,4-diaminophenoxyethanol, 1,3-bis-(2',4'-diaminophenoxy)-propane, 2,6-bis-(2'-hydroxyethylamino)-toluene, 3,4-dioxymethylphenol, 1-naphthol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chorresorcinol, 2- Chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresocine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 3-Amino-2-methylamino-6-methoxypyridine, l,3-bis-(2,4-diaminophenoxylpropane, 2,4-diaminophenoxyethanol, 2-amino-4-(2'-hydroxyethyl)amino-amide and the physiologically acceptable salts of these compounds.

It is not necessary for the oxidation dye precursors or the direct dyes to be uniform compounds. Rather, the hair dyes according to the invention may contain other components in minor amounts, depending on the manufacturing processes for the individual dyes.

provided that they do not adversely affect the staining result or must be excluded for other reasons, e.g. toxicological reasons.

With regard to the dyes that can be used in the hair dyes and tints according to the invention, express reference is also made to the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250; direct dyes) and Chapter 8, pages 264-267; oxidation dye precursors), published as Volume 7 of the series "Dermatology" (ed.: Ch., Culnan and H. Maibach), published by Marcel Dekker Inc., New York, Basel, 1986, and the "European Inventory of Cosmetic Raw Materials", published by the European Community, available in diskette form from the Federal Association of German Industrial and Commercial Companies for Pharmaceuticals, Health Foods and Personal Care Products e.V., Mannheim.

The developer components are preferably contained in the agents according to the invention in amounts of 0.005 to 20% by weight, preferably 0.1 to 5% by weight, and the coupler components are preferably contained in amounts of 0.005 to 20% by weight, preferably 0.1 to 5% by weight, in each case based on the total agent.

Indoles and indolines which have at least one hydroxy or amino group, preferably as a substituent on the six-membered ring, are preferably used as precursors of nature-analogous dyes. These groups can carry further substituents, e.g. in the form of an etherification or esterification of the hydroxy group or an alkylation of the amino group.

Particularly suitable as precursors of natural hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (IV),

R ⁵ -O

in which independently

(IV)

H5449 14

R ¹ represents hydrogen, a Ci^-alkyl group or a Ci-C ₄ -hydroxyalkyl group,

R ² represents hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically acceptable cation,

R ³ represents hydrogen or a Ci-C ₄ alkyl group,

R ⁴ represents hydrogen, a Ci-C ₄ alkyl group or a group -CO-R ⁶ , in which

R ⁶ represents a Ci-C ₄ alkyl group, and

R ⁵ represents one of the groups mentioned under R ⁴ ,

as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid as well as 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

Particularly noteworthy within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5,6-dihydroxyindoline.

Derivatives of 5,6-dihydroxyindole of formula (V) are also excellently suited as precursors of natural hair dyes,

(V)
R
in which independently

R ¹ represents hydrogen, a Ci-C4-alkyl group or a Cj-C ₄ -hydroxyalkyl-

group,

R ² represents hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically acceptable cation,

R ³ represents hydrogen or a Cj -C ₄ -alkyl group,

&EEgr;5449 15

R ⁴ represents hydrogen, a Ci-C ₄ alkyl group or a group -CO-R ⁶ , in which

R ⁶ represents a Ci-C^alkyl group, and

R ⁵ represents one of the groups mentioned under R ⁴ ,

as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.

Within this group, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and especially 5,6-dihydroxyindole are noteworthy.

The indoline and indole derivatives can be used in the dyes used in the process according to the invention both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, e.g. the hydrochlorides, sulfates and hydrobromides. The indole or indoline derivatives are usually contained in these in amounts of 0.05-10% by weight, preferably 0.2-5% by weight.

Particularly when using dye precursors of the indoline or indole type, it has proven advantageous to use an amino acid and/or an oligopeptide as an alkalizing agent.

In addition to the dye precursors, the agents according to the invention can contain direct dyes for further shading. These are usually selected from nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred direct dyes are those known under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 13, HC Red BN, Basic Red 76, HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue

·

H5449 16 *

7, Basic Blue 26, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Basic Violet 2, Basic Violet 14, Acid Violet 43, Disperse Black 9, Acid Black 52, Basic Brown 16 and Basic Brown 17 as well as l,4-bis-(ß-hydroxyethyl)-amino-2-nitrobenzene, 3-nitro-4-(ß-hydroxyethyl)-aminophenol, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, hydroxyethyl-2-nitro-toluidine, picramic acid, 2-amino-6-chloro-4-nitrophenol, A- ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-l-hydroxy-4-nitΓobenzene. The agents according to the invention according to this embodiment preferably contain the direct dyes in an amount of 0.01 to 20% by weight, based on the total colorant.

Furthermore, the preparations according to the invention can also contain naturally occurring dyes such as henna red, henna neutral, henna black, chamomile blossom, sandalwood, black tea, buckthorn bark, sage, logwood, madder root, catechu, sedre and alkanet root.

The agents according to the invention preferably contain dye precursors in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose of hair coloring, such carriers are, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations that are suitable for application to the hair. However, it is also conceivable to integrate the dye precursors into a powder or tablet-shaped formulation.

For the purposes of the present invention, aqueous-alcoholic solutions are understood to mean aqueous solutions containing 3 to 70% by weight of a C1-C4 alcohol, in particular ethanol or isopropanol. The agents according to the invention can additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. Preference is given to all water-soluble organic solvents.

The actual oxidative dyeing of the fibers can in principle be carried out with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, especially

■ ■ ··

H5449 17

when, in addition to coloring, a lightening effect on human hair is desired. Possible oxidizing agents are persulfates, chlorites and in particular hydrogen peroxide or its addition products with urea, melamine and sodium borate. However, the oxidation colorants can also be applied to the hair together with a catalyst which activates the oxidation of the dye precursors, e.g. Such catalysts are, for example, transition metal compounds, iodides, quinones or certain enzymes. Suitable enzymes are, for example, peroxidases, which can significantly increase the effect of small amounts of hydrogen peroxide. Also suitable according to the invention are enzymes which directly oxidize the oxidation dye precursors with the help of atmospheric oxygen, such as, for example, laccases, or which generate small amounts of hydrogen peroxide in situ and in this way biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates for this, e.g. b.

Pyranose oxidase and e.g. D-glucose or galactose,

Glucose oxidase and D-glucose,

Glycerol oxidase and glycerol,

Pyruvate oxidase and benzoic acid or their salts,
- Alcohol oxidase and alcohol (MeOH, EtOH),

Lactate oxidase and lactic acid and their salts,

Tyrosinase oxidase and tyrosine,

Uricase and uric acid or their salts,

Choline oxidase and choline,

Amino acid oxidase and amino acids.

The actual hair dye is expediently prepared immediately before use by mixing the preparation of the oxidizing agent with the preparation containing the dye precursors. The resulting ready-to-use hair dye preparation should preferably have a pH value in the range of 6 to 12. It is particularly preferred to use the hair dye in a slightly alkaline environment. The application temperatures can be in a range between 15 and 40 ⁰ C. After an exposure time of 5 to 45 minutes, the hair dye is removed by rinsing out

H5449 18

from the hair to be colored. There is no need to wash the hair with a shampoo if a carrier with a high surfactant content, e.g. a coloring shampoo, was used.

The agents according to the invention can also contain all active ingredients, additives and auxiliary substances known for such preparations. In many cases, these agents contain at least one surfactant, whereby in principle both anionic and zwitterionic, ampholytic, non-ionic and cationic surfactants are suitable. In many cases, however, it has proven advantageous to select the surfactants from anionic, zwitterionic or non-ionic surfactants.

All anionic surface-active substances suitable for use on the human body are suitable as anionic surfactants in preparations according to the invention. These are characterized by a water-solubilizing anionic group such as a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 C atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups as well as hydroxyl groups. Examples of suitable anionic surfactants are, each in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 or 3 C atoms in the alkanol group,

linear fatty acids with 10 to 22 C atoms (soaps),

Ethercarboxylic acids of the formula RO-(CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group having 10 to 22 C atoms and X = O or 1 to 16,

Acylsarcosides with 10 to 18 C atoms in the acyl group,

Acyltaurides with 10 to 18 C atoms in the acyl group,

Acyl isethionates with 10 to 18 C atoms in the acyl group,

Sulfosuccinic acid mono- and dialkyl esters with 8 to 18 C atoms in the alkyl group and sulfosuccinic acid mono-alkylpolyoxyethyl esters with 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups,

linear alkanesulfonates with 12 to 18 C atoms,

linear alpha-olefin sulfonates with 12 to 18 C atoms,

Alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 C atoms,

H5449

- alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO(CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group having 10 to 18 C atoms and x = O or 1 to 12,

Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
sulfated hydroxyalkylpolyethylene and/or hydroxyalkylenepropylene glycol ethers according to DE-A-37 23 354,

Sulfonates of unsaturated fatty acids with 12 to 24 C atoms and 1 to 6 double bonds according to DE-A-39 26 344,

Esters of tartaric acid and citric acid with alcohols, which are addition products of about 2-15 molecules of ethylene oxide and/or propylene oxide with fatty alcohols with 8 to 22 C atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule and in particular salts of saturated and in particular unsaturated Cg-C22 carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.

Non-ionic surfactants contain a hydrophilic group such as a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such compounds are, for example,

Addition products of 2 to 30 moles of ethylene oxide and/or 0 to 5 moles of propylene oxide with linear fatty alcohols having 8 to 22 C atoms, with fatty acids having 12 to 22 C atoms and with alkylphenols having 8 to 15 C atoms in the alkyl group,
C|2-C ₂ 2-fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol,

C8-C22 alkyl mono- and oligoglycosides and their ethoxylated analogues and
Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil.

Preferred nonionic surfactants are alkyl polyglycosides of the general formula R ¹ O-(Z) _x . These compounds are characterized by the following parameters.

H5449 20

The alkyl radical R ¹ contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear and 2-methyl-branched aliphatic radicals are preferred. Examples of such alkyl radicals are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl and 1-myristyl. When using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The alkyl polyglycosides that can be used according to the invention can, for example, contain only one specific alkyl radical R ^1. However, these compounds are usually prepared from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the respective processing of these compounds.

Particularly preferred are those alkyl polyglycosides in which R ¹
essentially consisting of Cs and Qo alkyl groups,
essentially consisting of C12 and Cn alkyl groups,
consisting essentially of Cs to Ci6 alkyl groups or
consists essentially of C12 to C16 alkyl groups.

Any mono- or oligosaccharide can be used as the sugar building block Z. Sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are usually used. Such sugars are, for example, glucose, fructose, ^^ galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose,

Talose and sucrose. Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain on average 1.1 to 5 sugar units. Alkyl polyglycosides with x values of 1.1 to 1.6 are preferred. Alkyl glycosides in which x is 1.1 to 1.4 are very particularly preferred.
In addition to their surfactant effect, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. The expert will therefore take into account the fact that the perfume oil has an effect on the hair that extends beyond the duration of the hair treatment.

H5449 21

the hair is desired, preferably this class of substance is used as a further ingredient of the preparations according to the invention.

The alkoxylated homologues of the alkyl polyglycosides mentioned can also be used according to the invention. These homologues can contain on average up to 10 ethylene oxide and/or propylene oxide units per alkyl glycoside unit.
Furthermore, zwitterionic surfactants can be used, particularly as co-surfactants. Zwitterionic surfactants are surface-active compounds which have at least one quaternary ammonium group and at least one COO ^W or -SO3 ^H group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-NjN-dimethylammonium glycinates, for example cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-NjN-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each with 8 to 18 C atoms in the alkyl or acyl group, as well as cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants are also particularly suitable as co-surfactants. Ampholytic surfactants are understood to be surface-active compounds which, in addition to a Cs-Ci 8 alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SOaH group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids, each with about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C12-18 acylsarcosine.

According to the invention, the cationic surfactants used are in particular those of the quaternary ammonium compound, esterquat and amidoamine type.

H5449 22

Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

Esterquats are known substances that contain at least one ester function and at least one quaternary ammonium group as a structural element. Preferred esterquats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are sold, for example, under the trademarks Stepantex®, Dehyquart® and Armocare®. The products Armocare® VGH-70, an N,N-bis(2-palmitoyloxyethyl)dimethylammonium chloride, as well as Dehyquart® F-75 and Dehyquart® AU-35 are examples of such esterquats.

The alkylamidoamines are usually produced by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. A particularly suitable compound from this group of substances according to the invention is stearamidopropyldimethylamine, which is commercially available under the name Tegoamid® S 18.

Other cationic surfactants that can be used according to the invention are the quaternized protein hydrolysates.

Also suitable according to the invention are cationic silicone oils such as the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 Emulsion (containing a hydroxylamino-modified silicone, also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat

H5449 23

3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

An example of a quaternary sugar derivative that can be used as a cationic surfactant is the commercial product Glucquat®100, which according to INCI nomenclature is a "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

The compounds with alkyl groups used as surfactants can each be uniform substances. However, it is generally preferred to start from native plant or animal raw materials when producing these substances, so that mixtures of substances with different alkyl chain lengths, depending on the respective raw material, are obtained.

In the case of surfactants which are addition products of ethylene and/or propylene oxide to fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. "Normal" homolog distribution refers to mixtures of homologs which are obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alkoxides as catalysts. Narrowed homolog distributions, on the other hand, are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alkoxides are used as catalysts. The use of products with a narrow homolog distribution can be preferred.

Furthermore, the agents according to the invention can preferably also contain a conditioning active ingredient selected from the group consisting of cationic surfactants, cationic polymers, alkylamidoamines, paraffin oils, vegetable oils and synthetic oils.

Cationic polymers may be preferred as conditioning agents. These are usually polymers that contain a quaternary nitrogen atom, for example in the form of an ammonium group.

·

H5449 24

Preferred cationic polymers are, for example,

quaternized cellulose derivatives, such as those commercially available under the names Celquat® and Polymer JR®. The compounds Celquat® H 100, Celquat® L 200 and Polymer JR®400 are preferred quaternized cellulose derivatives.
polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid as well as esters and amides of acrylic acid and methacrylic acid. The products commercially available under the names Merquat®100 (poly(dimethyldiallylammonium chloride)), Merquat®550 (dimethyldiallylammonium chloride-acrylamide copolymer) and Merquat® 280 (dimethyldiallylammonium chloride-acrylic acid copolymer) are examples of such cationic polymers.

Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat®734 and Gafquat®755.
Vinylpyrrolidone-methoimidazolinium chloride copolymers, such as those sold under the name Luviquat®,
quaternized polyvinyl alcohol
as well as those under the designations
Polyquaternium 2,
Polyquaternium 17,
Polyquatemium 18 and

Polyquaternium 27 known polymers with quaternary nitrogen atoms in the polymer main chain.

Cationic polymers of the first four groups are particularly preferred, with Polyquaternium-2, Polyquaternium-10 and Polyquaternium-22 being very particularly preferred.

Silicone oils, especially dialkyl and alkylaryl siloxanes, such as dimethylpolysiloxane and methylphenylpolysiloxane, as well as their alkoxylated and quaternized analogues, are also suitable as conditioning agents. Examples of such silicones are the products sold by Dow Corning under the names DC 190, DC 200, DC 344, DC 345 and DC 1401 as well as the commercial products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning® 929 Emulsion

H5449 25

(containing a hydroxyl-amino-modified silicone, also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

Paraffin oils, synthetically produced oligomeric alkenes and vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil and peach kernel oil can also be used as conditioning agents.

Also suitable hair conditioning compounds are phospholipids, such as soy lecithin, egg lecithin and cephalins.

Other active ingredients, excipients and additives include

non-ionic polymers such as vinylpyrrolidone/vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone/vinyl acetate copolymers and polysiloxanes,

zwitterionic and amphoteric polymers such as acrylamidopropyl trimethylammonium chloride/acrylate copolymers and octylacrylamide/methyl methacrylate/tert-butylaminoethyl methacrylate^-hydroxypropyl methacrylate copolymers,

anionic polymers such as polyacrylic acids, cross-linked polyacrylic acids, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and acrylic acid/ethyl acrylate/N-tert-butyl acrylamide terpolymers,

Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives such as methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as bentonite or fully synthetic hydrocolloids such as.

Polyvinyl alcohol,

Structurants such as maleic acid and lactic acid,

hair conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins,

H5449 26

Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates,

Perfume oils, dimethylisosorbide and cyclodextrins,

Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol,

fibre structure-improving agents, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, fruit sugar and lactose,

quaternized amines such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate

Defoamers such as silicones,

Dyes for coloring the product,

Anti-dandruff ingredients such as Piroctone Olamine, Zinc Omadine and Climbazole,

Sunscreens, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,

Substances for adjusting the pH value, such as common acids, especially food acids and bases,

Active ingredients such as allantoin, pyrrolidonecarboxylic acids and their salts as well as bisabolol,

Vitamins, provitamins and vitamin precursors, especially those of groups A, B3, B ₅ , B ₆ , C, E, F and H,

Plant extracts such as extracts from green tea, oak bark, stinging nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden blossom, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lemon, wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, wild thyme, yarrow, thyme, lemon balm, restharrow, coltsfoot, marshmallow, meristem, ginseng and ginger root.

Cholesterol,

Consistency agents such as sugar esters, polyol esters or polyol alkyl ethers,

Fats and waxes such as spermaceti, beeswax, montan wax and paraffins,

Fatty acid alkanolamides,

Complexing agents such as EDTA, NTA, ß-alaninediacetic acid and phosphonic acids,

Swelling and penetrating agents such as glycerin, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

- Opacifiers such as latex, styrene/PVP and styrene/acrylamide copolymers, pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate, pigments,

Stabilizers for hydrogen peroxide and other oxidizing agents, propellants such as propane-butane mixtures, N2O, dimethyl ether, CO2 and air, antioxidants.

With regard to further optional components and the amounts of these components used, express reference is made to the relevant manuals known to the person skilled in the art, e.g. Kh. Schrader, Grundlagen und Rezepturen der Kosmetika, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.

The following examples are intended to illustrate the subject matter of the present application without, however, limiting it thereto.

H5449

Examples of implementation i. Composition of the colouring cream

Partial Mixture A

HydrenolV 8.5 g

Lorol®techn. ² 2.0 g

Eumulgin®B2 ³ 0.75 g

Texapon®NSO ⁴ 20.0 g

Dehyton®K ⁵ 12.5 g Distilled water 30.0 g

¹ Ciö-ig fatty alcohol (INCI name: Cetearyl alcohol) (Cognis)

² C^-is fatty alcohol (INCI name: Coconut alcohol) (Cognis)

³ Cetylstearyl alcohol with approx. 20 mol EO (INCI name: Ceteareth-20) (Cognis)

⁴ Sodium lauryl ether sulfate (approx. 28% active ingredient; INCI name: Sodium Laureth Sulfate) (Cognis)

⁵ Fatty acid amide derivative with betaine structure of the formula R-CONH(CH ₂ )3N ⁺ (CH3)2CH ₂ COO· (approx. 30 % active substance; INCI name: Cocoamidopropyl Betaine) (Cognis)

The substances Hydrenol®D, Lorol® and Eumulgin®B2 were tested at 8O ⁰ C

melted, with the 80 ⁰ C hot water containing Texapon®NSO and

Dehyton®K, and emulsified with vigorous stirring. The emulsion was then cooled with gentle stirring.

Partial mixture B 2.5 each 1st floor Sodium sulphite aaaaaa ·
a · ·9 · · ·
9 · · · *
9 · aaa
&bull;a aaa · ·· a 1st floor Ammonium sulfate mmol Dye precursors ·· »······· · · ·
···· ·· 9 9 9·
&bull; · · ··· · · · 9 ·
&bull;&bull;a ··· a··
aa· ··· ···
·· ·· ·· 9 ·· ·· · · aaa···· 9·
· · · ·
· 9·· 9
a a · ·
a a · ·
··· a··· ····

H5449 29

Ammonia (25% solution) to pH 10.0
Water 10.0g

The dye precursors were dissolved in the 50 ^° C hot water with the addition of sodium sulfite, ammonium sulfate and ammonia. The dye precursor solution (partial mixture B) was then added to the emulsion (partial mixture A), adjusted to pH 10 with ammonia and made up to 100g with water. Stirring was continued until room temperature was reached.

2. Coloring of the keratin fibers

The resulting coloring cream was mixed in a ratio of 1:1 with water, a 1% H2O2 solution or a 9% H2C>2 solution and applied to strands of standardized, 80% gray but not specially pretreated human hair (Klugmann). After 30 minutes of exposure at 32°C, the hair was rinsed, washed out with a standard shampoo and then dried.

The results of the dyeing tests are shown in the following table, in which the following coupler and developer components were used:

Coupler components:

Kl: 2,4-dichloro-3-aminophenol hydrochloride (according to the invention)

K2: 2,4-diaminophenoxyethanol dihydrochloride

K3: l,3-bis-(2',4'-diaminophenoxy)-propane tetrahydrochloride

K4: 3,4-dioxymethylenephenol

K5: 3,5-diamino-2,6-dimethoxypyridine dihydrochloride

K6: 2,6-Bis(2'-hydroxyethylamino)-toluene

Developer components:

El: l-(2'Hydroxyethyl)-4,5-diaminopyrazole sulfate

30

E2: 4-Hydroxy-2,5,6-triaminopyrimidine sulfate E3: 2,4,5,6-tetraaminopyrimidine sulfate E4: 2,5-diaminophenyl ethanol sulfate E5: Bis-(2-hydroxy-5-aminophenyl)-methane dihydrochloride E6: 3-methyl-4-aminophenol

Furthermore, the following recipes were produced:

1. Gel formulation (Figures in %) raw material 6.75 Edenor®PK 1805 3.50 Texapon®NSO 6.75 Propylene glycol 8.0 Coconut fatty alcohol C12-C18 10.1 Dehydol®LS 2 14.5 Isopropanol 0.3 Sodium metabisulfite 1.2 4,5-Diamino-1-(2'-hydroxy- ethyl)pyrazole sulfate 0.54 1-Naphthol 0.16 2,4-dichloro-3-aminophenol 0.06 5-Amino-2-methylphenol 0.5 Perfume to 100 Water

with ammonia solution (25%) to pH9.5-10

H 5449 31 '* ' " "'

2. Cream recipe (Figures in %) raw material 10.3 Fatty alcohol mixture C12-C18 15.0 Texapon®NSO 10.0 Dehyton®K 0.3 Ascorbic acid 0.2 Sodium metabisulfite 0.1 Turpinal®SL 0.5 Ammonium sulfate 1.2 Polymer®JR400 1.54 4,5-Diamino-1-(2'hydroxy- ethyl)pyrazole sulfate 0.49 5-Amino-2-methylphenol 0.51 2,4-dichloro-3-aminophenol 0.25 1-(2'-Hydroxyethyl)-2,5-di- amino-benzene sulfate 0.07 2,6-bis-(2'-hydroxy- ethyl)aminotoluene (K6) 0.03 3-Amino-2-methylamino- 6-methoxypyridine 0.08 2,4-Diamino-phenoxy- ethanol dihydrochloride (K2) 0.02 1,5-Dihydroxynaphthalene 0.3 Perfume to 100 Water

with ammonia solution (25%) to pH 9.5-10

In both cases, the dyeing was carried out after mixing with a commercial 6% H2O2 developer formulation (Poly Diadem) on white natural hair (code: Kerling natural white) in a liquor ratio of 4:1 for 30 minutes at 32°C.
In the case of the gel recipe, a bright, intense purple tone resulted, while in the case of the cream recipe, an intense violet tone resulted.

Dye- Air oxidation Color result 9 _{% H2O2} combination 1 _{% H2O2} 12E8 El+Cl 9C4 12E8 ruby matt red ruby 14 F3 E2 + K1 15F4 16F5 aubergine dark purple dark purple 19F8 E4 + K1 19F6 19 F6 blackblue lapis blue navy blue 12E8 El + E2 + Kl 12E4 12 F8 ruby grey ruby port wine red 12 F8 El + E3 + Kl 9E3 11F5 port wine red grey-brown violet brown 12 F8 El + E4 + Kl 9D4 12 F8 port wine red reddish brown port wine red 12E8 E1+E5 + K1 10D7 11E8 ruby raspberry red garnet red 12D7 E1+E6 + K1 11D6 11E6 grey ruby brown-violet violet brown 14 F3 E2 + E3 + Cl 15F4 16F5 aubergine dark purple dark purple 9C3 E2 + E5 + Cl 14 E3 14E3 matt red greymagenta greymagenta 11E8 El + Kl + K4 10D4 11E8 garnet red grey Red garnet red 10D3 E2 + K1 + K4 8E3 9E4 grey-brown grey-brown reddish brown 19F8 E4 + K1 + K3 20E8 19F6 blackblue lapis blue navy blue 13E4 E5 + K1 + K6 12 D 4 13E5 greymagenta grey ruby greymagenta 20 F8 E6 + K1 + K5 23 F4 20 F8 blackblue dark blue blackblue

Claims (3)

1. Agent for dyeing keratin fibres, characterized in that it contains, in a medium suitable for dyeing, as oxidation dye precursors, a combination of a) 2,4-dichloro-3-aminophenol and b) at least one further dye precursor selected from 1-(2'-hydroxyethyl)-4,5-diaminopyrazole, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4,5,6-tetraaminopyrimidine, 1-(2'-hydroxyethyl)-2,5-diaminobenzene, p-toluenediamine, bis-(2-hydroxy-5-aminophenyl)-methane and 3-methyl-4-aminophenol and the physiologically acceptable salts of these compounds. 2. Agent according to claim 1, characterized in that it contains at least one further developer component which is selected from p-phenylenediamine, 2-(α,β-dihydroxyethyl)-p-phenylenediamine and N,N-bis-(β-hydroxyethyl)-p-phenylenediamine, N,N'-bis-(β-hydroxyethyl)-N,N'-bis-(4'-aminophenyl)-1,3-diamino-propan-2-ol, N,N' - bis-(4'-aminophenyl)-1,4-diazacycloheptane and 1,10-bis-(2',5'-diaminophenyl)-1,4,7,10-tetraoxadecane, p-aminophenol, 4-amino-2-aminomethylphenol, 4-amino-2-(α,β-dihydroxyethyl)-phenol and 4-Amino-2-(diethyl-aminomethyl)-phenol, 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy -5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine, 4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4'-chlorobenzyl)-pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 5-diamino-1-methyl-3-phenylpyrazole, 4-Amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methylpyrazole, 1-isopropylpyrazole, 4-Amino-5-(β-aminoethyl)-amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4-(β-hydroxyethyl)-amino-1-methylpytazole, 1,5-a]-pyrimidine-3,7-diamine, 2,5-dimethyl-pyrazole-[1,5-a]-pyrimidine-3,7-diamine, pyrazole-[1,5-a]-pyrimidine-3,5-diamine, 2,7-dimethyl-pyrazole-[1,5-a]-pyrimidine-3,5-diamine, 3-aminopyrazole-[1,5-a]- pyrimidin-7-ol, 3-Aminopyrazol-[1,5-a]- pyrimidin-5-ol, 2-(3-Aminopyrazol-[1,5-a]-pyrimidin-7-ylamino)-ethanol, 2-(7- Aminopyrazol-[1,5-a]-pyrimidin-3-ylamino)-ethanol, 2-[(3-Aminopyrazol-[1,5-a]-pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol, 2-[(7-Aminopyrazol-[1,5-a]-pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol, 5,6-Dimethylpyrazol-[1,5-a]-pyrimidin- 3,7-diamin, 2,6-Dimethylpyrazol-[1,5-a]-pyrimidin-3,7-diamin, 3-Amino-7-dimethylamino-2,5-dimethylpyrazole-[1,5-a]-pyrimidine and the physiologically tolerable salts of these compounds. 3. Agent according to one of claims 1 or 2, characterized in that it contains at least one further coupler component which is selected from 2,4-diaminophenoxyethanol, 1,3-bis-(2',4'-diaminophenoxy)-propane, 2,6-bis-(2'-hydroxyethylamino)-toluene, 3,4-dioxymethylphenol, 1-naphthol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxy-3,4-dimethylpyridine and 3,5-diamino-2,6-dimethoxypyridine and the physiologically acceptable salts of these compounds