EP1423355A1

EP1423355A1 - Bridged p-phenylenediamines

Info

Publication number: EP1423355A1
Application number: EP02798707A
Authority: EP
Inventors: Georg KNÜBEL; David Rose; Bernd Meinigke; Horst Höffkes; Helmut Giesa
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2001-09-07
Filing date: 2002-09-04
Publication date: 2004-06-02
Also published as: JP2005503409A; WO2003024917A1; US20040199018A1; DE10144226A1

Abstract

The present invention relates to novel bridged p-phenylenediamines, the use thereof as developer components in oxidation dyes as well as novel oxidation dyes, which contain the aforementioned bridged p-phenylenediamines. Said invention also relates to a method for producing said bridged p-phenylenediamines. Within the frame of said invention, it was discovered that polyoxyalkyl-bridged p-phenylenediamines of formula (I) are extremely well-suited for use as developer components in oxidation dyes.

Description

BRIDGED P-PHENYLENE DIAMINE

The present invention relates to new bridged p-phenylenediamines, their use as a developer component in oxidation colorants and to new oxidation colorants which contain the aforementioned bridged p-phenylenediamines. The present invention further relates to a process for the preparation of the bridged p-phenylenediamines.

A wide variety of colorants are known in the prior art for dyeing keratin fibers, in particular human hair. The so-called oxidation colorants play a preferred role here, since these enable particularly intensive colorations and have good fastness properties. The oxidation colorants contain so-called developer components and coupler components as oxidation dye precursors. The developer components are also referred to as oxidation bases.

The oxidation dye precursors and especially the developers have to meet a wide range of requirements:

With oxidative coupling, you must develop the desired color shades with sufficient intensity and authenticity.

They must also have a good ability to draw onto the fiber, and in particular - with human hair, no noticeable differences between damaged and freshly regrown hair must be discernible (leveling ability).

They should be resistant to light, heat, sweat and the influence of chemical reducing agents, such as permanent wave fluids. Furthermore, they should not stain the scalp too much when used as a hair dye.

In particular, the oxidation dye products should be absolutely harmless from a toxicological and dermatological point of view.

It is also desirable to have good peelability with undesirable ones

Dyeing results.

Typical so-called coupler components are, for example, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols. Particularly suitable coupler substances include 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, l-phenyl 3-methyl-pyrazolon-5, 2,4-dichloro-3-aminophenol, l, 3-bis (2 ', 4'-diaminophenoxy) propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro 6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

Frequently used developer components are primary aromatic amines with a further free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6- Tetraminopyrimidine and its derivatives. The widely used developer components also include p-phenylenediamine (PPD) and methyl-p-phenylenediamine, which is also referred to as p-toluenediamine (PTD). These have been used in permanent oxidation hair colors for decades. Despite their good application properties, PPD and PTD cannot be used without hesitation. Both PPD and PTD are not considered to be completely harmless from a toxicological point of view.

A simple strategy to avoid such toxicological problems is to synthesize larger molecules, since for understandable reasons they are less able to penetrate through the skin and are therefore less or not absorbed at all. In the synthesis and development of larger molecules, for example based on PPD and PTD units, however, it should be noted at the same time that PPD / PTD derivatives with very voluminous substituents have significantly poorer application properties Have properties and are therefore not or only poorly suited for use in oxidation colorants. In particular, the aforementioned PPD / PTD-based developer substances with very voluminous substituents can often only achieve very poor color intensities.

To avoid the toxicological problems described above and taking into account the application properties, it has been proposed in the prior art to link PPD or PTD units to larger molecules, for example to dimers. This has the advantage that not only are larger molecules obtained, but at the same time the number of reactive centers in the molecule is increased, so that an acceptable color intensity can be achieved. The link can be made in different ways or at different locations of the PPD or PTD units.

For example, DE 2518393 describes tetraaminobiphenyls and tetraaminodiphenyl ethers as developer components. The aforementioned dimers are linked to one another via the benzene rings of the PPD units.

In the PPD dimers described in DE 2852272 and DE 3149330, the linkage also takes place directly via the benzene rings. The amino groups on the p-phenylenediamines thus remain free. According to DE 2852272 and DE 3149330 bis (2,5-diaminophenoxy) alkanes are proposed as developer components.

While most of the PPD or PTD dimers known to date in the prior art, as described above, are linked directly via the benzene ring or the benzene rings of the PPD and PTD units, individual examples of developer substances which are based on are also known link PPD and / or PTD via the amino groups. In this context, DE 19707545 should be mentioned, which describes 1,4-diazacycloheptane derivatives as developer substances. A disadvantage with regard to the aforementioned Ν, Ν'-bis (4-aminophenyl) -1, 4-diazacycloheptanes is that the synthesis of such compounds is often only possible with a relatively high level of technical complexity, for example in an autoclave. It was an object of the present invention to provide new developer components which meet the requirements placed on oxidation dye precursors to a particular degree. In particular, it was an object of the present invention to find developer components based on p-phenylenediamine units which, owing to their molecular size, are to be regarded as toxicologically harmless and at the same time lead to the obtaining of oxidative colorations with very good intensity.

In addition, there is a constant need for new, improved dye components, since a developer component or a special coupler / developer combination alone is often unsuccessful in obtaining a color shade that appears natural on the hair. In practice, therefore, combinations of different developer and / or coupler components are usually used.

Surprisingly, it has now been found that p-phenylenediamines and their derivatives which are linked to polyoxaalkyl bridges to form dimers are very suitable as developer substances in oxidation hair colors.

A first subject of the present invention are therefore bridged p-phenylenediamines of the general formula (I)

in the

(B) is a polyoxaalkyl bridge that has at least two oxygen atoms: - X and Y independently of one another for H, Cl, F, a dC ₄ alkyl, aminoalkyl, alkoxy, C ₂ -C ₄ dihydroxyalkyl, C ₁ -C ₄ monohydroxyalkyl or a C ₂ -C alkenyl group stand; and

R 1, R 2, R 3 and R ₄ independently of one another represent H, a CrC ₄ alkyl, a C ₁ -C ₄ monohydroxyalkyl or a C ₂ -C ₄ dihydroxyalkyl group, and acid addition salts derived therefrom.

According to the present invention, symmetrically substituted (Rl = R3 and R2 = R4) polyoxaalkyl-bridged p-phenylenediamines of the general formula (I) are preferred over corresponding asymmetrically substituted derivatives.

X and Y in formula (I) each represent one or more of the substituents specified above. Accordingly, the present invention also includes bridged p-phenylenediamines which, in addition to the two amino groups, have one, two, three or even four substituents on the benzene ring of the phenylenediamine unit (s).

Examples of the C ₁ -C ₄ alkyl groups mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and / or butyl. Ethyl and / or methyl are preferred alkyl groups. A preferred Ci- alkoxy group according to the invention is, for example, a methoxy and / or an ethoxy group. Furthermore, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl and / or a 4-hydroxybutyl group can be mentioned as preferred examples of a C 1 -C -hydroxyalkyl group. Particularly preferred C ₂ -C ₄ dihydroxyalkyl groups are, for example, 1,2-dihydroxyethyl, 1,2-dihydroxypropyl, 1,3-dihydroxypropyl, 2,3-dihydroxypropyl, 1,2-dihydroxybutyl, 1,3- Dihydroxybutyl, 1,4-dihydroxybutyl, 2,3-dihydroxybutyl, 2,4-dihydroxybutyl and / or 3,4-dihydroxybutyl groups. Particularly suitable C ₂ -C ₄ alkenyl groups are the vinyl, the allyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl and / or the 2-methylpropenyl group. According to a particularly preferred embodiment, the present invention relates to bridged p-phenylenediamines with a structure according to formula (II)

in the

- X and Y independently of one another for H, Cl, F, a Q- alkyl, aminoalkyl, alkoxy, C ₂ -C ₄ dihydroxyalkyl, C ₁ -C ₄ monohydroxyalkyl or a C ₂ -C - Alkenyl group; and

R 1, R 2, R 3 and R ₄ independently of one another represent H, a C ₁ -C 8 -alkyl, a C ₁ -C ₄ -monohydroxyalkyl or a C ₂ -C ₄ -dihydroxyalkyl group.

It is particularly preferred that in formula (II) X and Y and the radicals Rl, R2, R3 and R4 are H. The resulting compound is 1,8-bis [(4-aminophenyl) amino] -3, 6-dioxaoctane.

According to a further particularly preferred embodiment, the present invention relates to bridged p-phenylenediamines with a structure according to formula (III)

in the

- X and Y independently of one another for H, Cl, F, a C ₁ -C ₄ alkyl, aminoalkyl, alkoxy, C ₂ -C dihydroxyalkyl, CrC ₄ monohydroxyalkyl or a C ₂ -C ₄ - Alkenyl group; and - Rl, R2, R3 and R4 are independently H, a Cι-C ₄ alkyl, a C ₄ CJ -Monohydroxyalkyl- or a C ₂ -C ₄ -dihydroxyalkyl stand.

It is particularly preferred that in formula (III) X and Y and the radicals Rl, R2, R3 and R4 are H. The resulting compound is 1, 12-bis [(4-aminophenyl) amino] -4,9-dioxadodecane.

According to yet another particularly preferred embodiment, the present invention relates to bridged p-phenylenediamines with a structure according to formula (IV)

in the

- X and Y independently of one another for H, Cl, F, a C ₁ -C ₄ alkyl, aminoalkyl, alkoxy, C ₂ -C dihydroxyalkyl, - monohydroxyalkyl or a C ₂ -C ₄ alkenyl group stand; and

- Rl, R2, R3 and R4 independently represent H, a C alkyl, a Ci- C ₄ -Monohydroxyalkyl- or a C ₂ -C ₄ -dihydroxyalkyl stand.

It is particularly preferred that in formula (III) X and Y and the radicals Rl, R2, R3 and R4 are H. The resulting compound is 1,13-bis [(4-aminophenyl) amino] -4,7, 10-trioxatridecane.

The above-mentioned amino compounds according to the invention can be easily converted into their corresponding acid addition salts. In addition to the free bases, the present invention also relates to the acid addition salts derived from the respective compounds. Water-soluble, physiologically tolerable salts suitable according to the invention include, for example, the hydrochlorides, the hydrobromides, the sulfates, the phosphates, the acetates, the propionates, the citrates and the lactates. Hydrochlorides are particularly preferred.

According to the present invention, a process for the preparation of the bridged p-phenylenediamines according to formulas (I), (II), (III) or (IV) according to the invention is provided, which comprises the following steps: a) reaction of l-fluoro-4- nitrobenzene with a polyoxaalkyl diamine in the presence of a base, l-fluoro-4-nitrobenzene and the polyoxaalkyl diamine preferably being used in a ratio of 2: 1, and b) hydrogenation of the intermediate product obtained in step a).

Polyoxaalkyldiamines suitable according to the invention include linear or branched polyoxaalkyls which have at least two, preferably primary, amino groups. The polyoxaalkyl provided with at least two terminal amino functions forms the “bridge” provided according to the invention in the resulting dimer. When l-fluoro-4-nitrobenzene is reacted with a polyoxaalkyldiamine in the presence of a base, triethylamine or triethanolamine is preferably used as the base. It is preferred to use the 1-fluoro-4-nitrobenzene, the polyoxaalkyl diamine and the base in a ratio of 2: 1: 2.

The reaction of l-fluoro-4-nitrobenzene with polyoxoalkydiamine in DMSO is preferably carried out at elevated temperatures, preferably at a temperature of more than 50 ° C., particularly preferably at about 80 ° C.

It is particularly preferred according to the invention that the polyoxoalkyldiamine to be reacted is selected from the group comprising 2,2 '- (ethylenedioxy) diethylamine, 1,4-bis (3-aminopropoxy) butane and 4,7,10-trioxa-l, 13- tridecanediamine.

The bridged bis [(4-nitrophenyl) amino] compound obtained in step a) of the process according to the invention is reduced in step b) below to the corresponding bis [(4-ammophenyl) amino] compound. The nitro groups can be hydrogenated by processes known per se. For example, the Catalytic hydrogenation with hydrogen in the presence of palladium on activated carbon (Pd / C) has been demonstrated.

According to a further object of the present invention, there is provided an oxidation colorant for dyeing keratin fibers, which contains as developer component at least one polyoxaalkyl-bridged p-phenylenediamine according to the invention.

In a preferred embodiment of the present invention, in addition to the at least one developer component, the oxidation colorant comprises at least one coupler component.

Keratin fibers or keratin fibers in the sense of the present invention are to be understood according to the invention as furs, wool, feathers, hair and in particular human hair. Although the oxidation colorants according to the invention are primarily suitable for dyeing keratin fibers, there is in principle nothing to prevent their use in other areas, particularly in color photography

Oxidation colorants in an aqueous carrier or in powder form are particularly preferred for the purposes of the present invention.

In principle, all coupler substances known in the prior art can be used as coupler components.

According to a preferred embodiment of the present invention, the oxidation colorant contains at least one coupler component selected from the group comprising m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives.

Further coupler components preferred according to the invention are m-aminophenol and its derivatives, such as 5-amino-2-methylphenol, 5- (β-hydroxyethyl) amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2- chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3 - aminophenol, 3-trifluoroacetylamino-2-chloro-6-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) benzene, 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-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1, 3-bis (2', 4 ' -diaminophenyl) -propane, 2,6-

Bis- (2'-hydroxyethylamino) -l-methylbenzene, 3,5-diamino-2-methoxytoluene 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-dimethoxy,

Naphthalene derivatives such as 1-naphthol, 2-methyl-1-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,

Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,

Quinoxaline derivatives such as 6-methyl-l, 2,3,4-tetrahydroquinoxaline,

Pyrazole derivatives such as, for example, 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-methylenedioxybenzene.

Suitable coupler substances are in particular 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinomino methyl ether, m-phenylenediamine, l-phenyl -3-methyl-5-pyrazolone, 2,4-dichloro-3-aminophenol, l, 3-bis- ^(2,, 4'-diaminophenoxy) propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2 -Chlor-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol, 3,5-diamino-2-methoxytoluene, 5- (ß-hydroxyethyl) amino-2-methylphenol and 2-methyl-4-chloro-5-aminophenol.

According to a further preferred embodiment, the oxidation colorant according to the invention comprises, in addition to at least one polyoxaalkyl-bridged p-phenylenediamine according to the invention, at least one further developer component, preferably selected from the group comprising 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis ( 2'-hydroxyethyl) -p-phenylenediamine, 2- (2 ', 5'-diaminophenyl) ethanol, 2- (2', 5'-diaminophenoxy) ethanol, 4-amino-3-methylphenol, 2-aminomethyl 4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine, 1, 3-N, N'-bis (2'-hydroxyethyl) - N, N '-bis (4' -aminophenyl) -diamino-propan-2-ol, 4-amino-2 - ((diethylamino) -methyl) -phenol, bis (2-hydroxy- 5-aminophenyl) methane and 4,5-diamino-l- (2'-hydroxyethylpyrazole) or their salts.

Additional developer components preferred according to the invention further comprise p-phenylenediamine, p-toluenediamine, p-aminophenol, o-aminophenol, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, N, N-bis (2'-hydroxyethyl) - p-phenylenediamine, 2- (2 ', 5'-diaminophenoxy) ethanol, 4-amino-3-methylphenol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2-

Hydroxymethylamino-4-aminophenol, bis- (4-aminophenyl) amine, 4-amino-3-fluoro-henol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, bis- (2-hydroxy-5 -aminophenyl) methane, 1,4-bis (4'-aminophenyl) diazacycloheptane N, N'-bis (2'-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1, 3-diamino-propan-2-ol, 4-amino-2- (2'-hydroxyethoxy) phenol, 1, 10-bis (2 ', 5'-diaminophenyl) -1, 4,7, 10-tetraoxadecane and 4,5-diaminopyrazole derivatives according to EP 0 740 931 or WO 94/08970 such as 4,5-diamino-1 - (2'-hydroxyethyl) pyrazole.

It is provided according to the present invention that the hair colorant can contain any other developer component in addition to the polyoxaalkyl-bridged p-phenylenediamine according to the invention.

It is preferred that the hair colorants according to the invention contain the developer components in an amount of 0.005 to 20% by weight, preferably 0.01 to 15% by weight, more preferably 0.1 to 10% by weight, particularly preferably 0.3 to 5% by weight, most preferably 0.5 to 3% by weight, e.g. 1 and / or 2% by weight, and coupler components in an amount of 0.005 to 20% by weight, preferably 0.01 to 15% by weight, more preferably 0.1 to 10% by weight, particularly preferably 0 , 3 to 5% by weight, most preferably 0.5 to 3% by weight, e.g. 1 and / or 2 wt .-%, each based on the total oxidation colorant.

Developer components and coupler components are generally used in approximately equimolar amounts (taking into account the number of reactive centers in the respective components). If the equimolar use has also proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2 , can be included. In a further preferred embodiment according to the invention, the colorant additionally contains at least one substantive dye.

Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those with the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9 and Acid Black 52 Compounds and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) - aminophenol, 2- (2 ^, -hydroxyethyl) amino-4,6-dinitrophenol, 1 - (2 ^, -hydroxyethyl) amino-4-methyl-2-mtrobenzene, l-amino-4- (2'-hydroxyethyl) amino -5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, l- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-mtrodiphenylamine-2 '-carboxylic acid, 6-nitro-1, 2,3, 4-tetrahydroquinoxaline, 2-hydroxy-l, 4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobene zoic acid and 2-chloro-6-ethylamino-l-hydroxy-4-nitrobenzene.

The agents according to the invention can also contain a cationic direct dye. Are particularly preferred

(a) cationic triphenylmethane dyes, such as, for example, Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,

(b) aromatic systems which are substituted with a quaternary nitrogen group, such as, for example, Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, and

(c) substantive dyes which contain a heterocycle which has at least one quaternary nitrogen atom, as are mentioned, for example, in EP-A2-998 908, to which reference is expressly made here, in claims 6 to 11. Preferred cationic direct dyes of group (c) are in particular the following compounds:

CH ₃ SO ₄ ^"

Cl ^"

The compounds of the formulas (DZl), (DZ3) and (DZ5) are very particularly preferred cationic direct dyes of group (c). The cationic direct dyes, which are sold under the trademark Arianor ^® are, according to the invention also particularly preferred substantive dyes.

The agents according to the invention in accordance with this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20% by weight, based on the total colorant. Furthermore, the agents according to the invention can also contain naturally occurring dyes such as, for example, henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, rotten tree bark, sage, blue wood, madder root, catechu, sedre and alkanna root.

The agents according to the invention preferably contain the substantive dyes in an amount of 0.005 to 20% by weight, preferably 0.01 to 15% by weight, more preferably 0.1 to 10% by weight, particularly preferably 0.3 to 5 % By weight, most preferably 0.5 to 3% by weight, e.g. 1 and / or 2 wt .-%, based on the total oxidation colorant.

It is not necessary that the oxidation dye precursors or the substantive dyes are in each case uniform compounds. Rather, in the hair colorants according to the invention, due to the production processes for the individual dyes, further components may also be present in minor amounts, provided that these do not adversely affect the coloring result or for other reasons, e.g. toxicological, must be excluded.

With regard to the dyes which can be used in the hair colorants and tints according to the invention, reference is also expressly 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 "Dermatology" series (Ed .: Ch. Culnan and H. Maibach), 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 Industry and Commerce for Medicines, Reformed Products and Personal Care Products, Mannheim.

To produce the colorants according to the invention, the oxidation dye precursors can be incorporated into a cosmetically suitable, for example water-containing carrier. Such carriers are for the purpose of hair coloring, for example creams, emulsions, gels or also surfactant-containing foaming solutions, for example shampoos, Foam aerosols or other preparations that are suitable for use on the hair.

The colorants according to the invention can furthermore contain all active substances, additives and auxiliaries known for such preparations. In many cases, the colorants contain at least one surfactant, both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has proven advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.

The agents according to the invention preferably contain surfactants in an amount of 0.1 to 30% by weight, preferably 1 to 20% by weight and particularly preferably 2 to 10% by weight.

Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. 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 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group, linear and / or branched fatty acids with 8 to 22 ° C. -Atoms (soaps), ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16, acyl sarcosides with 10 to 18 C atoms in the acyl group, acyl taurides 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 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates with 12 to 18 carbon atoms, linear alpha-olefin sulfonates with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 carbon atoms, - alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH, O) _χ -SO ₃ H, in which R is one preferably linear alkyl group with 10 to 18 carbon atoms and x = 0 or 1 to 12,

Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-3723 354,

Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-3926 344,

Esters of tartaric acid and citric acid with alcohols, the addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols with 8 to

Represent 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon 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 C ₈ -C ₂ -carboxylic acids, such as oleic acid, stearic acid , Isostearic acid and palmitic acid.

The agents according to the invention can preferably contain anionic surfactants in an amount of 0.5 to 30% by weight, preferably 1 to 20% by weight.

Zwitterionic surfactants are those surface-active compounds which have at least one quaternary ammonium group and at least one -COO ^(" ^ - or -SO ^ group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N dimethylammonium glycinates, for example cocoalkyl dimemylammoniumglycinat, N-acyl-aminopropyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyl dimethylammom ^'umglycinat, and 2- Aιkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethylcarboxymethylglycineate A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine. The agents according to the invention can preferably contain zwitterionic surfactants in an amount of 0.1 to 20% by weight, preferably 1 to 10% by weight.

Ampholytic surfactants are understood to mean those surface-active compounds which, in addition to a C ₈ . ₁₈ -alkyl or -acyl group in the molecule contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N- alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-

Alkyltaurines, N-alkyl sarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids, each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylamino propionate and C ₁₂ . ₁₈ acylsar cosm.

The agents according to the invention can preferably contain ampholytic surfactants in an amount of 0.1 to 20% by weight, preferably 1 to 10% by weight.

Nonionic surfactants contain z as a hydrophilic group. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such connections are, for example

Addition products of 2 to 30 mol ethylene oxide and / or 0 to 5 mol propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group , C ₁₂ . ₂₂ fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol, C Ö.-22 alkyl mono- and oligoglycosides, their ethoxylated analogs and / or their

Esters, e.g. with tartaric acid and / or citric acid,

Addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened

Castor oil,

Addition products of ethylene oxide with sorbitan fatty acid esters

Addition products of ethylene oxide with fatty acid alkanolamides. The agents according to the invention can preferably contain nonionic surfactants in an amount of 0.1 to 30% by weight, preferably 1 to 20% by weight.

Examples of the usable in the inventive hair treatment compositions cationic surfactants are ^'compounds existed in particular, quaternary Ammom. Preference is given to ammonium halides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and Trialkylmemylammom ^'umchloride, for example cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryldimethylammomumchlorid, Lauryldimemylbenzylammoniumchlorid and Tricetyl- methylammomumchlorid. The quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.

Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM -2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

In addition to a good conditioning effect, alkylamidoamines, especially fatty acid amidoamines such as the ^{stearylamidopropyldimemylamine} available under the name Tego Amid ^® S 18, are characterized in particular by their good biodegradability. Also very good biodegradability are quaternary Esterverbindungen, so-called "esterquats", such as those sold under the trademark Stepantex ^® hyαlroxyalkyldialkoyloxyalkyl methyl-ammom ^{'ummethosulfate} as well as the products marketed under the trade name Dehyquart ^® products such as Dehyquart ^® AU-46th

An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ^® 100, according to INCI nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride". The agents according to the invention can preferably contain cationic surfactants in an amount of 0.1 to 20% by weight, preferably 1 to 10% by weight.

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

In the case of the surfactants, which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrowed homolog distribution can be used. “Normal” homolog distribution is understood to mean mixtures of homologs which are obtained as catalysts from the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates. By contrast, narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be preferred.

According to the invention, the use of anionic surfactants in combination with zwitterionic surfactants can be particularly preferred.

Also preferred according to the invention are those compositions which additionally contain a cationic polymer.

The permanent cationic polymers are preferred among the cationic polymers. According to the invention, polymers which have a cationic group irrespective of the pH of the composition are referred to as “permanently cationic”. These are usually polymers that contain a quaternary nitrogen atom, for example in the form of an ammonium group.

Preferred cationic polymers are, for example, quaternized cellulose derivatives, such as are available under the names of Celquat ^® and Polymer JR ^® commercially. The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives, polysiloxanes with quaternary groups, such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone) , Dow Corning ^® 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® - Quat 3270 and 3272 (Manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80),

Cationic guar derivatives, such as, in particular, the products sold under the trade names Cosmedia ^® Guar and Jaguar ^® ,

Polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. The products commercially available under the names Merquat ^® 100 (poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammomum chloride-acrylamide copolymer) are examples of such cationic polymers,

Copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, such as, for example, vinyl pyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are available under the names Gafquat ^® 734 and Gafquat ^® 755 commercially Vinylpyirolidon-Vmylimidazoliummethochlorid copolymers, such as those offered under the names Luviquat ^® FC 370, FC 550, FC 905 and HM 552, quaternized polyvinyl alcohol, as well as the under the names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 known polymers with quaternary nitrogen atoms in the main polymer chain.

Likewise used as cationic polymers are those under the names Polyquaternium-24 (commercial product e.g. Quatrisoft ^® LM 200), Polyquatemium-32, Polyquaternium-35 and Polyquaternium-37 (commercial products e.g. Salcare ^® SC 92 and Salcare ^® SC 95) known polymers. Likewise usable according to the invention are the copolymers of vinyl pyrrolidone, as are available as commercial products Copolymer 845 (manufacturer: ISP), Gaffix ^® VC 713 (manufacturer: ISP), Gafquat ^® ASCP 1011, Gafquat ^® HS 110, Luviquat ^® 8155 and Luviquat ^® MS 370 are.

Cationic polymers preferred according to the invention are quaternized cellulose derivatives, polymeric dimethyldiallylammonium salts, polyquaternium-27 and their copolymers and also polymers of the polyquaternium-2 type. Katiom cellulose derivatives, in particular the commercial product Polymer ^® JR 400, and polymers of the type Polyquaternium-2, in particular the commercial product Mirapol ^® Al 5, are very particularly preferred cationic polymers.

The agents according to the invention can preferably contain cationic polymers in an amount of 0.1 to 10% by weight, preferably 0.2 to 5% by weight.

In many cases, amphopolymers can also be used as an alternative to the cationic polymers. Ampho-polymers are amphoteric polymers, ie polymers that contain both free amino groups and free - COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers that contain quaternary ammonium groups and - COO ^" - or

-SO ₃ ^"groups, and those polymers summarized, the -COOH or SO ₃ H groups and quaternary ammonium groups. An example of the invention can be used according Amphoporymer is that available under the name Amphomer ^® acrylic resin which is a copolymer of tert Butylaminoethyl methacrylate, N- (l, l, 3,3-tetramethylbutyl) acrylamide and two or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple esters Amphopolymers are composed of unsaturated carboxylic acid (e.g. acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acid (e.g. acrylamidopropyltrimethylammonium chloride) and optionally other ionic or nonionic monomers, such as in German Offenlegungsschrift 39 29 973 and the prior art cited therein. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimom ^' chloride, as are commercially available under the name Merquat ^® 2001 N, as well as the commercial product Merquat ^® 280 can also be used according to the invention. Particularly preferred polymers are, for example, acrylantrdopropytrimemylainmoniumchloriάVAcrylat copolymers and / or octylacrylamide memyl -methacrylaτ / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers.

The agents according to the invention can preferably contain amphopolymers in an amount of 0.1 to 10% by weight.

The agents according to the invention likewise preferably contain at least one non-ionic or anionic polymer with thickening properties. Preferred are optionally crosslinked polyacrylic acids, cellulose derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, and xanthan gum.

The agents according to the invention can preferably contain nonionic and / or anionic polymers in an amount of 0.1 to 25% by weight.

Other active ingredients, auxiliaries and additives are, for example

Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol, stericants such as glucose and maleic acid, hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins, and silicone oils,

Protein hydrolyzates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, their condensation products with fatty acids and quaternized protein hydrolyzates, perfume oils, dimethyl isosorbide and cyclodextrins,

Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol,

Anti-dandruff agents such as piroctone olamine and zinc omadine, other substances for adjusting the pH value,

Active ingredients such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and their salts, plant extracts and vitamins, cholesterol, light stabilizers,

Consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as walrus, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters, fatty acid alkanolamides,

Complexing agents such as EDTA, NTA and phosphonic acids,

Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates, opacifiers such as latex,

Pearlescent agents such as ethylene glycol mono- and distearate,

Blowing agents such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air as well as antioxidants.

The constituents of the water-containing carrier are used to produce the colorants according to the invention in amounts customary for this purpose; For example, emulsifiers are used in concentrations of 0.1 to 30% by weight, preferably 0.2 to 10% by weight, particularly preferably 0.3 to 5% by weight, most preferably 0.5 to 3% by weight. %, and thickeners in concentrations of 0.1 to 25% by weight, preferably 0.2 to 10 % By weight, particularly preferably 0.3 to 5% by weight, most preferably 0.5 to 2% by weight, in each case based on the total amount of the colorant.

In principle, the oxidative development of the coloring can take place with atmospheric oxygen. However, a chemical oxidizing agent can also be used. This is particularly preferred if, in addition to the coloring, a lightening effect on human hair is desired. Persulfates, chlorites and in particular hydrogen peroxide or their adducts with urea, melamine and sodium borate are suitable as oxidizing agents. It is also possible to carry out the oxidation with the aid of enzymes. The enzymes (enzyme class 1: oxidoreductases) can transfer electrons from suitable developer components (reducing agents) to atmospheric oxygen. Oxidases such as tyrosinase and laccase are preferred, but also glucose oxidase, uricase or pyruvate oxidase. Furthermore, the enzymes can serve to enhance the effect of small amounts of oxidizing agents present. An example of such an enzymatic process is the procedure to increase the effect of small amounts (e.g. 1% and less, based on the total agent) of hydrogen peroxide by peroxidases.

The preparation of the oxidizing agent is expediently mixed with the preparation from the oxidation dye precursors immediately before hair coloring. The resulting ready-to-use hair color preparation should have a pH in the range from 6 to 13, preferably in a range from 8 to 12, most preferably in a range from 9 to 11. It is particularly preferred to use the hair dye in a weakly alkaline environment. The application temperatures can range between 15 and 40 ° C. After an exposure time of approx. 30 minutes, the hair dye is removed from the hair to be colored by rinsing. Washing with a shampoo is not necessary if a carrier with a high tenside content, e.g. a coloring shampoo was used.

Another object of this invention is the use of the aforementioned agents for dyeing keratin fibers.

The following examples are intended to illustrate the subject matter of the invention, but are not to be understood as a limitation. EMBODIMENTS

a Establishing the connections:

1.18-bis [(4-aminophenvfiamino1-3,6-dioxaoctane x 4 HC1 (1)

1.1 1,8-bis [(4-nitrophenyl) amino] -3,6-dioxaoctane

100 ml of DMSO were placed in a 500 ml stirring apparatus and 10.3 g of triethylamine, 7.6 g of 2,2 '- (ethylenedioxy) diethylamine and 14.4 g of l-fluoro-4-nitrobenzene were added. The mixture was stirred at 80 ° C. for 16 h and, after cooling, poured onto 1 l of ice water. The resulting precipitate was filtered off and washed with water. The mixture was then dried at 40 ° C in a vacuum. Yield: 18.5 g (94%) m.p .: 130-133 ° C

1.2 1,8-bis [(4-aminophenyl) amino] -3,6-dioxaoctane

17.6 g l, 8-bis [(4-mtrophenyl) amino] -3,5-dioxaoctane in 400 ml ethanol were mixed with 1.5 g Pd / C (5%). While shaking, the mixture was reduced catalytically with hydrogen. After the hydrogen uptake had ended, 100 ml of dilute HCl were added, the mixture was filtered off, evaporated to dryness and dried in vacuo at 50.degree. Yield: 22.2 g (103%) mp: 183-225 ° C (dec.)

2. 1, 12-bis | T4-aminophenyl amino ^" | -4.9-dioxadodecane x 4 HC1 (2)

2.1 1, 12-bis [(4-nitrophenyl) amino] -4,9-dioxadodecane

100 ml of DMSO were placed in a 500 ml stirrer and 10.3 g

Triethylamine, 10.5 gl, 4-bis (3-aminopropoxy) butane and 14.4 g l-fluoro-4-nitrobenzene added. After stirring for 20 h at 80 ° C., the mixture was poured onto 1 l of ice water after cooling. The resulting precipitate was filtered off and washed with water. The mixture was then dried at 50 ° C in a vacuum. Yield: 21.3 g (95%) mp: 112-115 ° C

2.2 1, 12-bis [(4-aminophenyl) amino] -4,9-dioxadodecane x 4 HC1

20.1 g l, 12-bis [(4-nitrophenyl) amino] -4,9-dioxadodecane in 400 ml ethanol were mixed with 1.2 g Pd / C (5%). While shaking, the mixture was reduced catalytically with hydrogen. After the hydrogen uptake had ended, 100 ml of dilute HCl were added, the mixture was filtered off and evaporated to dryness and dried in vacuo at 50.degree. Yield: 20.2 g (84%) m.p .: 180 ° C (dec.)

3.1.13-bisr (4-aminophenyl aminol-4,7,10-trioxatridecan x 4 HC1 (3)

3.1 1, 13-bis [(4-nitrophenyl) amino] -4,7, 10-trioxatridecane

100 ml of DMSO were placed in a 500 ml stirring apparatus and 10.3 g of triethylamine, 11.2 g of 4,7,10-trioxa-l, 13-tridecanediamine and 14.4 g of l-fluoro-4-nitrobenzene were added. After stirring at 80 ° C. for 19 hours, the mixture was poured onto 1 l of ice water after cooling. The water was decanted from the resulting oily precipitate, 1 liter of water was added and the mixture was stirred for 12 h. After decanting again, crystallization began. The crystals obtained were recrystallized from 300 ml of H ₂ O / EtOH (1/2). After vacuuming, it is dried at 40 ° C. in vacuo. Yield: 19.7 g (85%) mp: 84-87 ° C

3.2 l, 13-bis [(4-aminophenyl) amino] -4,7,10-trioxatridecane x 4 HC1 18.5 g, 13-bis [(4-nitrophenyl) amino] -4,7,10-trioxatridecane were added in 400 ml ethanol with 1.5 g Pd / C (5%). While shaking, the mixture was reduced catalytically with hydrogen. After the hydrogen uptake had ended, 150 ml of dilute HCl were added, the mixture was filtered off and evaporated to dryness. The resulting oil was mixed several times with EtOH and evaporated until crystallization started. It was then dried in vacuo at 40 ° C. Yield: 19.9 g (90%) mp .: 180-210 ° C (dec.)

b) Coloring examinations

The previously described developer components (1), (2) and (3) according to the invention were used for the coloration tests described below.

For the preparation of the colorant or the coloring cream, 50 g of a cream base were weighed into a 250 ml beaker and melted at 80 ° C. The cream base used had the following composition (data in% by weight): 17.0% Hydreno ^ D ¹

4.0% Lorol tech.

40.0% Texapon ^® NSO ³

25.0% Dehyton ^® K ⁴

1.5% Eumulgin ^® B2 ⁵

12.5% water

C ₁₆ . ₁₈ -Fatty alcohol (INCI name: Cetearyl alcohol) (Cognis)

C ₁₂ . ₁₈ -Fatty alcohol (INCI name: Coconut alcohol) (Cognis)

Lauryl ether sulfate, sodium salt (approx. 27.5% active substance; INCI name: Sodium Laureth Sulfate) (Cognis)

N, N-dimethyl-N- (. C ₈ ₁₈ -kokosamidopropyl) ammom ^{'umacetobetain} (ca. 30% active substance; INCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis) ⁵ cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20)

(Cognis)

The substances to be investigated were suspended separately from the developer and coupler in distilled water or dissolved with heating. 1/400 mol developer or coupler were used in each case. Then ammonia (<1 ml; 25% ammonia solution) was added until the pH was between 9 and 10. A solution was created by adding Ammomak.

The dissolved developers and couplers were worked into the hot cream in succession. The mixture was then made up to 97 g with distilled water and the pH was adjusted to 9.5 with Ammomak. After filling up to 100 g with distilled water, the mixture was stirred cold (<30 ° C.), a homogeneous cream being formed.

The cream was diluted as follows for the different colors:

A) 25 g cream + 25 g distilled water

B) 25 g cream + 25 g H ₂ O ₂ , 1%

C) 25 g cream + 25 g H ₂ O ₂ , 9% '

A lock of hair (80% gray; 330 mg to 370 mg in weight) was added to each of the mixtures thus obtained. The mixtures and the strands of hair were then each placed on a watch glass and the strands of hair were well embedded in the coloring creams. After 30 minutes (± 1 minute) of exposure at room temperature, the strands of hair were removed and washed with Texapon EVR ^® (Na lauryl ether sulfate) until the excess color was removed. The strands of hair were air-dried and their color was determined and noted under the daylight lamp (color testing device HE240A) (Taschenlexikon der Farben, A. Kornerup and JH Wanscher, 3rd unchanged edition 1981, MUSTER-SCHMIDT Verlag; Zurich, Göttingen).

The results obtained in the coloring studies are shown in Tables I and II below. Table: Coloring of the developer components according to the invention with standard couplers (molar ratio developer / coupler = 1/2)

A air oxidation

B oxidation with 1% H? O?

C oxidation with 9% H? O?

Table II: Colorings of the developer (1) according to the invention and a further developer in a ratio of 1/1 and with standard couplers (molar ratio developer / coupler = 1/1)

The following further developer components were used:

El p-toluenediamine

E2 p-aminophenol

E3 2,4,5,6-tetraaminopyrimidine

E4 4,5-diamino-l- (2'-hydroxyethyl) pyrazole

A air oxidation

B Oxidation with 1% EbO?

C oxidation with 9% H _? O?

The results shown in Tables I and II show that the polyoxaalkyl-bridged p-phenylenediamines (1), (2) and (3) according to the invention and the resulting colorants have excellent performance properties. In particular, a wide spectrum of color shades can be covered with the oxidation dyes according to the invention by combining them with different couplers and / or with additional developers. Excellent color intensities were achieved throughout.

Claims

claims

1. Bridged p-phenylenediamines of the general formula (I)

in the

- (B) is a polyoxaalkyl bridge having at least two oxygen atoms;

- X and Y independently of one another for H, Cl, F, a dG _t alkyl, hydroxyalkyl, aminoalkyl, alkoxy, CC ₄ dihydroxyalkyl, C ₁ -C monohydroxyalkyl or a C ₂ -C ₄ - Alkenyl group; and

- Rl, R2, R3 and R4 independently of one another represent H, a Cj-Q-alkyl, a Ci-C ₄ monohydroxyalkyl or a C ₂ -C ₄ -dihydroxyalkyl group, and acid addition salts derived therefrom.

2. Bridged p-phenylenediamines according to claim 1, characterized in that the polyoxaalkyl-bridged p-phenylenediamines have a structure according to formula (II)

in the - X and Y independently of one another for H, Cl, F, a CrC ₄ alkyl, aminoalkyl, alkoxy, C ₂ -C ₄ dihydroxyalkyl, C ₁ -C ₄ monohydroxyalkyl or a C ₂ -C ₄ - Alkenyl group stand; and

R 1, R 2, R 3 and R ₄ independently of one another represent H, a C 1 -C ₄ -alkyl, a C ₁ -C ₄ -monohydroxyalkyl or a C ₂ -C ₄ -dihydroxyalkyl group.

3. Bridged p-phenylenediamines according to claim 1, characterized in that the polyoxaalkyl-bridged p-phenylenediamines have a structure according to formula (III)

in the

- X and Y independently of one another for H, Cl, F, a QC-alkyl, aminoalkyl, alkoxy, C ₂ -C ₄ -dihydroxyalkyl-, C ₁ -C ₄ -monohydroxyalkyl- or a C ₂ -C ₄ - Alkenyl group; and

- Rl, R2, R3 and R4 independently of one another represent H, a d-Gt-alkyl, a d-C ₄ -monohydroxyalkyl or a C ₂ -C ₄ -dihydroxyalkyl group.

4. Bridged p-phenylenediamines according to claim 1, characterized in that the polyoxaalkyl-bridged p-phenylenediamines have a structure according to formula (IV)

in the - X and Y independently of one another represent H, Cl, F, a dC ₄ alkyl, aminoalkyl, alkoxy, C ₂ -C ₄ dihydroxyalkyl, dC ₄ monohydroxyalkyl or a C ₂ -C ₄ alkenyl group ; and

R 1, R 2, R 3 and R ₄ independently of one another represent H, a dC ₄ alkyl, a d C ₄ monohydroxyalkyl or a C ₂ -C ₄ dihydroxyalkyl group.

5. bridged p-phenylenediamines according to one of the preceding claims, characterized in that X and Y and the radicals Rl, R2, R3 and R4 are H.

6. Use of bridged p-phenylenediamines according to one of claims 1 to 5 and / or their water-soluble salts as developer component in oxidation hair.

7. Oxidation colorant for dyeing keratin fibers, containing in a cosmetically acceptable carrier at least one polyoxaalkyl-bridged p-phenylenediamine according to one of claims 1 to 5 as a developer component.

8. Oxidation colorant according to claim 7, characterized in that it contains at least one coupler component.

9. Oxidation dye according to claim 8, characterized in that it contains at least one coupler component selected from the group comprising m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives, particularly preferably selected from 1-naphthol, 1,5- , 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, l-phenyl-3-methyl-pyrazolone-5, 2,4-dichloro- 3-aminophenol, 1,3-bis (2 ', 4'-diaminophenoxy) propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2-chloro-6-methyl-3-aminophenol, 2- Amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol, 3,5-diamino-2-methoxytoluene, 5- (β-hydroxyethyl) amino-2-methylphenol and 2-methyl-4-chloro-5-aminophenol.

10. Oxidation colorant according to one of claims 7 to 9, characterized in that the colorant contains at least one further developer component in addition to at least one polyoxaalkyl-bridged p-phenylenediamine, preferably selected from the group comprising 2,4,5,6-tetraarninopyrimidine, p- Aminophenol, N, N-bis (2'-hydroxyethyl) -p-phenylenediamine, 2- (2 ', 5'-diaminophenyl) ethanol, 2- (2', 5'-diaminophenoxy) ethanol, 4-amino- 3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine, l, 3-N, N'-bis (2'-hydroxyethyl) - N, N '-bis (4' -aminophenyl) -diamino-propan-2-ol, 4-amino-2 - ((diethylamino) -methyl) - phenol, bis (2-hydroxy-5-aminophenyl) methane and 4,5-diamino-1- (2'-hydroxyethylpyrazole) or their salts.

11. Oxidation colorant according to one of claims 7 to 10, characterized in that the colorant developer components in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-% and optionally coupler components in an amount from 0.005 to 20% by weight, preferably 0.1 to 5% by weight, in each case based on the total colorant.

12. Oxidation colorant according to one of claims 7 to 11, characterized in that the colorant contains at least one substantive dye.

13. A process for the preparation of the bridged p-phenylenediamines according to one of claims 1 to 5, characterized in that a) l-fluoro-4-nitrobenzene is reacted with a polyoxaalkyl diamine, l-fluoro-4-nitro benzene and the polyoxaalkyl diamine are preferably used in a ratio of 2: 1, and b) the intermediate product obtained in step a) is then hydrogenated.

14. The method according to claim 13, characterized in that the reaction of l-fluoro-4-nitrobenzene with polyoxoalkydiamine in DMSO takes place at elevated temperatures, preferably at a temperature of more than 50 ° C, particularly preferably at about 80 ° C.

15. The method according to any one of claims 13 or 14, characterized in that the polyoxoalkyldiamine is selected from the group comprising 2,2 '- (ethylenedioxy) diethylamine, 1,4-bis (3-aminopropoxy) butane and 4,7,10 - Trioxa- 1, 13 -tridecanediamine.