DE20013155U1 - Dyes for keratin fibers containing 2,5-diamino-1- (1'-hydroxyalkyl) benzene derivatives - Google Patents

Description

Description

Dyes for keratin fibres containing 2,5-diamino-1-(1'-hydroxyalkyl)benzene derivatives

The present invention relates to agents for the oxidative coloration of keratin fibers, in particular human hair, based on a developer substance/coupler substance combination which contain 2,5-diamino-1-(1'-hydroxyalkyl)-benzene derivatives as developer substance.

Oxidation dyes have become very important in the field of coloring keratin fibers, especially hair coloring. The coloring is created by the reaction of certain developer substances with certain coupler substances in the presence of a suitable oxidizing agent. The developer substances used are in particular 2,5-diaminotoluene, 2-(2,5-diaminophenyl)ethanol, 3-methyl-4-aminophenol and 1,4-diaminobenzene, while the coupler substances used are, for example, resorcinol, 4-chlororesorcinol, 1-naphthol and derivatives of m-aminophenol and m-phenylenediamine.

Oxidation dyes used to dye human hair must meet numerous additional requirements in addition to the desired intensity. The dyes must be safe from a toxicological and dermatological point of view and the hair dyes produced must have good lightfastness, perm fastness, acid fastness and rubbing fastness. In any case, such dyes must be applied without the influence of light, rubbing and chemical agents.

Agents must remain stable over a period of at least 4 to 6 weeks. It is also necessary that a wide range of different color nuances can be produced by combining suitable developer substances and coupler substances.

However, it is not possible to meet all of the above requirements with the dyes currently in use. There is therefore still a need for new developer substances that meet the above requirements to a particularly high degree.

EP-OS O 400 330 discloses oxidation hair dyes with good toxicological properties and low sensitization potential which contain 2-(2,5-diaminophenyl)ethanol as the developer substance. However, 2-(2,5-diaminophenyl)ethanol is relatively easily oxidized and can therefore only be stored for a longer period in the form of its salt. In addition, this compound is relatively difficult to produce and therefore quite expensive. Furthermore, DE-OS 28 31 847 discloses oxidation hair dyes which contain certain 1-hydroxyalkyl-2,5-d!aminobenzenes, such as 1-hydroxymethyl-2,5-diaminobenzene, as the developer substance. However, these compounds also only partially meet the requirements placed on developer substances.

There was therefore still a need for developing substances with good physiological and toxicological properties, good storage stability and good coloring properties.

It has now been found that 1,4-diaminobenzene derivatives according to the general formula (I) meet the requirements placed on developer components to a particularly high degree.

The present invention therefore relates to agents for the oxidative coloration of keratin fibers, such as wool, fur, feathers or hair, and in particular human hair, based on a developer substance-coupler substance combination, which contain as developer substance 2,5-diamino-1-(1'-hydroxyalkyl)-benzene derivatives of the general formula (I) or their physiologically acceptable salts,

OH

CHR

(I)

wherein R is a straight-chain or branched alkyl radical having one to six carbon atoms.

Preferred compounds of formula (I) are those in which R is a methyl or ethyl group.

The compounds of formula (I) can be used both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, such as hydrochloric acid, sulphuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid or citric acid.

The 2,5-diamino-1-(1'-hydroxyalkyl)-benzene derivative of formula (I) is present in the colorant according to the invention in an amount of about 0.005 to

20 percent by weight, with an amount of about 0.01 to 20 percent by weight being particularly preferred.

The preferred coupler substances are 2,6-diaminopyridine, 2-amino-4-[(2-hydroxyethyl)amino]anisole, 2,4-diamino-1-fluoro-5-methylbenzene, 2,4-diamino-1 -methoxy-5-methyl-benzene, 2,4-diamino-1ethoxy-5-methyl-benzene, 2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene, 2,4-di[(2 -hydroxyethyl)amino]-1,5-dimethoxy-benzene, 2,3-diamino-6-methoxypyridine, 3-amino-6-methoxy-2-(methylamino)-pyridine, 2-(ß-hydroxyethyl-amino)- 6-methoxy-3-aminopyridine, 2,6-diamino-3,5-dimethoxy-pyridine, S.S-Diamino^B-dimethoxy-pyridine, 1,3-diaminobenzene, 2,4-diamino-1-(2-hydroxyethoxy)-benzene, 3-(2,4-diaminophenoxy)-1-propanol, 2,4- Diamino-1-(2-methoxyethoxy)-benzene, 2,4-diamino-1,5-di(2-hydroxyethoxy)-benzene, 1-(2-aminoethoxy)-2,4-diamino-benzene, 2-amino -1-(2-hydroxyethoxy)-4-methylamino-benzene, 2,4-diaminophenoxy-acetic acid, 3-[di(2-hydroxyethyl)amino]-aniline, 4-amino-2-di[(2-hydroxyethyl) amino]-1-ethoxybenzene, 5-methyl-2-(1methylethyl)phenol, 3-[(2-hydroxyethyl)amino]aniline, 3-[(2-Aminoethyl)-amino]-aniline, 1,3-Di(2,4-diaminophenoxy)-propane, Di(2,4-diaminophenoxy)-methane, 1,S-Diamino^^-dimethoxy- benzene, 2,6-bis(2-hydroxyethyl)amino-toluene, 4-hydroxyindole, 3-dimethylamino-phenol, 3-diethylamino-phenol, 5-amino-2-methyl-phenol, 5-amino-4-fluoro- 2-methylphenol, 5-amino-4-methoxy-2methyl-phenol, S-amino^-ethoxy^-methylphenol, 3-amino-2,4-dichlorophenol, 5-amino-2,4-dichlorophenol, 3- Amino-2-methyl-phenol, S-Aminc^-chloro-ö-methyl-phenol, 3-amino-phenol, 2-[(3-hydroxyphenyl)amino]acetamide, 5-[(2-Hydroxyethyl)amino]-2-methylphenol, 3-[(2-Hydroxyethyl)amino]-phenol, 3-[(2-methoxyethyl)amino]-phenol, 5-amino-2-ethyl-phenol , 2-(4-Amino-2-hydroxyphenoxy)-ethanol, 5-[(3-Hydroxypropyl)amino]-2-methyl-phenol, 3-[(2,3-Dihydroxypropyl)-amino]-2-methyl- phenol, 3-[(2-hydroxyethyl)amino]-2-methyl-phenol,

2-amino-3-hydroxy-pyridine, δ-amino^-chloro^-methyl-phenol, 1-naphthol, 1,5-dihydroxy-naphthalene, 1,7-dihydroxy-naphthalene, 2,3-dihydroxynaphthalene, 2, 7-Dihydroxy-naphthalene, 2-methyl-1-naphthol acetate, 1,3-dihydroxybenzene, i-chloro^^-dihydroxy-benzene, 2-ChIoM,3-dihydroxybenzene, 1^-dichloro-S.S-dihydroxy^- methyl-benzene, 1,5-dichloro-2,4-dihydroxy-benzene, 1,S-dihydroxy^-methyl-benzene, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 5-[(2-hydroxyethyl )amino]-1,3-benzodioxole, 6-Bromo-1-hydroxy-3,4-methylenedioxy-benzene, 3,4-diaminobenzoic acid, 3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine, 6-amino-3,4-dihydro -1,4(2H)-benzoxazine, 3-methyl-1-phenyl-5-pyrazolone, 5,6-dihydroxy-indole, 5,6-dihydroxy-indoline, 5-hydroxy-indole, 6-hydroxy-indole, 7-Hydroxy-indole and 2,3-lndolindione are considered.

Although the advantageous properties of the diaminobenzene derivatives of the formula (I) described here suggest that they should be used as the sole developing agent, it is of course also possible to use the diaminobenzene derivatives of the formula (I) together with known developing agents. Examples of suitable known developer substances are: p-phenylenediamines such as 1,4-diaminobenzene, 2,5-diamino-toluene, 2-chloro-1,4-diaminobenzene, 1-phenylamino-4-amino-benzene, 2,3-dimethyl-1,4-diaminobenzene, 1-(2-methoxyethyl)amino-4-amino-benzene, 2-(2,5-diaminophenyl)ethanol, N,N-bis-(ß-hydroxyethyl)-p-phenylenediamine, 4,4'-diamino-diphenylamine, 2,6-dimethyl-1,4-diaminobenzene, 2-isopropyl-1,4-diaminobenzene, 2-propyl-1,4-diaminobenzene, 1,3-bis-[(N-hydroxyethyl)-N-(4-aminophenyl)amino]-2-propanol, 2-methyl-4-dimethylamino-aniline, 2-methoxy-1,4-diaminobenzene and 1-(2,5-diaminophenyl)-ethane-1,2-diol; p-aminophenols such as 4-aminophenol, 4-amino-3-methylphenol, 2-hydroxymethyl-4-aminophenol,

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·

2-Methyl-4-aminophenol, ^Amino^-aminomethyl-phenol, 2-((2-Hydroxyethylamino)methyl)-4-aminophenol, 2-Methoxymethyl-4-aminophenol and 1-(5-Amino-2-hydroxyphenyl) -ethane-1,2-diol; o-aminophenols such as 2,4-diaminophenol, 5-methyl-2-aminophenol, 6-methyl-2-aminophenol, 2-ethylamino-4-methyl-phenol and 2-amino-4-methyl-phenol; or heterocyclic compounds such as 2-dimethylamino-5-aminopyridine, 4-hydroxy-2,5 ₎ 6-triamino-pyrimidine, 4,5-diamino-1-(2'-hydroxyethyl)-1H-pyrazole, 4,5-diamino -1-methyl-1 H-pyrazole, 4,5-diamino-1-benzyl-1 H-pyrazole, 4,5-diamino-1-isopropyl-1 H-pyrazole, 4,5-diamino-1-(( 4'-methylbenzyl)-1 H-pyrazole and tetraaminopyrimidine.

The coupler substances and developer substances can be contained in the colorant according to the invention individually or in a mixture with one another, the total amount of coupler substances and developer substances in the colorant according to the invention (based on the total amount of the colorant) being in each case about 0.005 to 20 percent by weight, preferably about 0.01 to 5.0 percent by weight.

The developing substances and couplers are generally used in approximately equimolar amounts; however, it is not disadvantageous if the developing substances are present in a certain excess or deficiency (for example in a ratio (coupler:developer) of 1:2 to 1:0.5).

Furthermore, the colorant according to the invention can additionally contain other color components, for example 6-amino-2-methylphenol and 2-amino-5-methylphenol, as well as conventional direct dyes, for example triphenylmethane dyes such as 4-[(4'-aminophenyl)-(4 ¹ -imino-2",5"-cyclohexadien-r'-ylidene^methyl^-methylaminobenzene monohydrochloride

(C.!. 42 510) and 4-[(4'-amino-3'-methyl-phenyl)-(4"-imino-3"-methyl-2",5"-cyclohexadien-1"-ylidene) -methyl]-2-methyl-amino-benzene monohydrochloride (Cl. 42 520), aromatic nitro dyes such as 4-(2'-hydroxyethyl)amino-nitrotoluene, 2-amino-4,6-dinitrophenol, 2-amino-5-( 2'-hydroxyethyl)amino-nitrobenzene, 2-chloro-6-(ethylamino)-4-nitrophenol, 4-chloro-N-(2-hydroxyethyl-2-nitroaniline, 5-chloro-2-hydroxy-4-nitroaniline, 2-amino-4-chloro-6-nitrophenol and 1-[(2'-ureidoethyl)amino-4-nitrobenzene, Azo dyes such as 2,6-diamino-3-((pyridin-3-yl)azo)pyridine or 6-[(4'-aminophenyl)azo]-5-hydroxy-naphthalene-1-sulfonic acid sodium salt (Cl. 14 805) and disperse dyes such as 1,4-diaminoanthraquinone and 1,4,5,8-tetraaminoanthraquinone. The colorants can contain these color components in an amount of about 0.1 to 4.0 percent by weight.

Of course, the coupler substances and developer substances as well as the other color components, if they are bases, can also be used in the form of physiologically acceptable salts with organic or inorganic acids, such as hydrochloric acid, hydrobromic acid or sulfuric acid, or - if they have aromatic OH groups - in the form of salts with bases, for example as alkali phenolates.

In addition, if the dyes are to be used to color hair, they may also contain other common cosmetic additives, for example antioxidants such as ascorbic acid, thioglycolic acid or sodium sulfite, as well as perfume oils, complexing agents, wetting agents, emulsifiers, thickeners and care substances.

The preparation form of the colorant according to the invention can be, for example, a solution, in particular an aqueous or aqueous

alcoholic solution. However, the most preferred preparation forms are a cream, a gel or an emulsion. Their composition is a mixture of the dye components with the additives customary for such preparations, such as solvents such as water, lower aliphatic alcohols, for example ethanol, propanol or isopropanol, glycerin or glycols such as 1,2-propylene glycol, furthermore wetting agents or emulsifiers from the classes of anionic, cationic, amphoteric or non-ionic surface-active substances such as fatty alcohol sulfates, ethoxylated fatty alcohol sulfates, alkyl sulfonates, alkylbenzenesulfonates, alkyltrimethylammonium salts, alkylbetaines, ethoxylated fatty alcohols, ethoxylated nonylphenols, fatty acid alkanolamides and ethoxylated fatty acid esters, thickeners such as higher fatty alcohols, starch, cellulose derivatives, petrolatum, paraffin oil and fatty acids, as well as care substances such as cationic resins, lanolin derivatives, cholesterol, pantothenic acid and betaine. The above-mentioned components are used in the amounts customary for such purposes, for example the wetting agents and emulsifiers in concentrations of about 0.5 to 30 percent by weight, the thickeners in an amount of about 0.1 to 25 percent by weight and the care substances in a concentration of about 0.1 to 5.0 percent by weight.

Depending on the composition, the colorant according to the invention can react weakly acidic, neutral or alkaline. In particular, it has a pH value of 6.5 to 11.5, with the basic adjustment preferably taking place with ammonia. However, organic amines, for example monoethanolamine and triethanolamine, or inorganic bases such as sodium hydroxide and potassium hydroxide can also be used. For a pH adjustment in the acidic range,

··

&idgr;&idgr;

. · · I &idigr;&idigr; I

inorganic or organic acids, for example phosphoric acid, acetic acid, citric acid or tartaric acid.

For use in the oxidative coloring of hair, the dye described above is mixed with an oxidizing agent immediately before use and a sufficient amount of this mixture for the hair coloring treatment, generally about 60 to 200 grams depending on the thickness of the hair, is applied to the hair.

Particularly suitable oxidizing agents for developing hair coloring are hydrogen peroxide or its addition compounds with urea, melamine, sodium borate or sodium carbonate in the form of a 3 to 12 percent, preferably 6 percent, aqueous solution, but also atmospheric oxygen. If a 6 percent hydrogen peroxide solution is used as the oxidizing agent, the weight ratio between hair dye and oxidizing agent is 5:1 to 1:2, but preferably 1:1. Larger amounts of oxidizing agent are used above all when the dye concentration in the hair dye is higher or when the hair is to be bleached more intensely.

The mixture is left to act on the hair at 15 to 50 degrees Celsius for about 10 to 45 minutes, preferably 30 minutes, then the hair is rinsed with water and dried. If necessary, the hair is washed with a shampoo after this rinse and possibly rinsed with a weak organic acid, such as citric acid or tartaric acid. The hair is then dried.

The dyeing agent according to the invention containing diaminobenzene derivatives of formula (I) enables dyeings with excellent

Color fastness, particularly with regard to light fastness, wash fastness and rub fastness. In terms of coloring properties, the coloring agent according to the invention offers a wide range of different color nuances, depending on the type and composition of the color components, ranging from blonde to brown, purple, violet to blue and black shades. The shades are characterized by their particular color intensity. The very good coloring properties of the coloring agents according to the present application are also shown in the fact that these agents also enable graying hair that has not been chemically damaged to be colored easily and with good coverage.

The 2,5-diamino-1-(1'-hydroxyalkyl)-benzene derivatives of the formula (I) used in the agent according to the invention are readily soluble in water, have good physiological properties and also have excellent storage stability, in particular as a component of the colorants described above.

The preparation of the 2,5-diamino-1-(1'-hydroxyalkyl)benzene derivatives of the formula (I) according to the invention can be carried out using known synthesis processes, for example in analogy to the process described in the embodiments.

The following examples are intended to illustrate the subject matter of the invention in more detail without limiting it thereto.

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11
Examples

Examples 1: Synthesis of 2,5-diamino-1-(i-hydroxakyl)-benzenes

1-[2-Amino-5-(2-chloro-phenylazo)-phenyl]-ethanol or 1-[2-amino-5-(2-chloro-phenylazo)-phenyl]-propanol is hydrogenated with nickel to give 2 _{l of} 5-diamino-1-(1'-hydroxyethyl)-benzene or 2,5-diamino-1-(1'-hydroxypropyl)-benzene, respectively, in analogy to the experimental procedure of Joseph B. Dickey and James G. McNaIIy in Example 6 of US Pat. No. 2,273,564.

Examples of hair dyes

Table 1: Developer substances E1 2,5-Diamino-1-(1'-hydroxyethyl)-benzene (according to Example 1) E8 2,5-Diamino-1-(1'-hydroxypropyl)-benzene (according to Example 1) E2 1,4-Diaminobenzene E3 2-(2,5-diamino-phenyl)ethanol sulfate E4 3-methyl-4-aminophenol E5 4-Amino-2-aminomethylphenol dihydrochloride E6 4-Aminophenol E7 N,N-Bis(2'-hydroxyethyl)-p-phenylenediamine sulfate E9 2,5-Diaminotoluene sulfate Table 2: Direct dyes 2,6-Diamino-3-((pyridin-3-yl)azo)pyridine D1 6-Chloro-2-ethylamino-4-nitrophenol D2 2-Amino-6-chloro-4-nitrophenol D3

♦ii» fr*

» * t t

Table 3: Couplers

K11 1,3-Diaminobenzene K12 2-Amino-4-(2'-hydroxyethyl)aminoanisole sulfate K13 1,3-Diamino-4-(2'-Hydroxyethoxy)benzene sulfate K14 2,4-diamino-5-fluorotoluene sulfate K15 3-Amino-2-methylamino-6-methoxy-pyridine K16 S.S-Diamino^.e-dimethoxy-pyridine dihydrochloride K17 2,4-diamino-5-ethoxy-toluene-sulfate K18 N-(3-Dimethylamino)phenylurea K19 1,3-Bis(2,4-diaminophenoxy)propane tetrahydrochloride K21 3-Aminophenol K22 5-Amino-2-methylphenol K23 S-Amino^-chloro-e-methyl-phenol K24 S-Amino^-fluoro^-methyl phenol sulfate K25 1-Naphthol K26 1 -Acetoxy^-methyl-naphthalene K31 1,3-Dihydroxybenzene K32 2-methyl-1,3-dihydroxybenzene K33 1-Chloro-2,4-dihydroxybenzene K34 4-(2'-Hydroxyethyl)amino-1,2-methylenedioxybenzene*HCl K35 3,4-Methylenedioxy-phenol K36 2-Amino-5-methyl-phenol

13 Examples 2 to 10: Hair dyes

Hair dye solutions of the following composition are produced:

X g developer substance E1 of formula (I) according to Table 1

U g developer substance E2 to E9 according to Table 1

Y g coupler substance K11 to K36 according to Table 3

Z g direct dye D1 to D3 according to Table 2

10.0 g potassium oleate (8% aqueous solution)

10.0 g ammonia (22% aqueous solution)

10.0 g ethanol

0.3 g ascorbic acid

ad 100.0 g water

Immediately before use, 30 g of the above dye solution are mixed with 30 g of a 6% aqueous hydrogen peroxide solution. The mixture is then applied to bleached hair. After an exposure time of 30 minutes at 40 ⁰ C, the hair is rinsed with water, washed with a commercially available shampoo and dried. The dyeing results are summarized in Table 4.

Table 4: Hair dyes

Example No. 2 3 4 (Amount of dye in grams) 0.35 0.30 0.30 Dyes E1 0.30 0.30 E4 0.30 E5 E6 0.18 0.22 K31 0.20 K32 0.30 0.30 K33 0.35 K25 reddish brown reddish brown reddish brown K26 Color

Table 4: (Continuation) 6 7 8th 9 10 (Amount of dye in grams) 0.50 0.40 0.40 0.16 0.15 0.15 5 0.15 Example
No. 0.15 Color
fabrics 0.15 &Egr;1 &Egr;2 0.10 &Egr;3 0.09 0.09 &Egr;9 0.20 0.15 0.20 0.10 0.20 0.10 0.10 &Kgr;12 0.20 &Kgr;13 0.05 &Kgr;31 0.05 &Kgr;32 0.05 0.10 0.10 0.10 &Kgr;33 &Kgr;21 blond blond blond blond blond blond &Kgr;22 &Kgr;23 Color

* »* · * &phgr; +it t· ti-

16 Examples 11 to 16: Hair dye in cream form

Cream-like color carrier masses of the following composition are produced:

X g developer substance E1 of formula (1) according to

Table 1

Y g coupler substance K11 to K36 according to Table Z g direct dye D2 according to Table 2 15.0 g cetyl alcohol
0.3 g ascorbic acid
3.5 g sodium lauryl alcohol diglycol ether sulfate, 28%

aqueous solution

3.0 g ammonia, 22% aqueous solution 0.3 g sodium sulphite, anhydrous ad 100.0 g water

Immediately before use, 30 g of the above coloring cream are mixed with 30 g of a 6% hydrogen peroxide solution. The mixture is then applied to the hair. After a contact time of 30 minutes at room temperature, the hair is rinsed with water, washed with a commercially available shampoo and dried. The coloring results are summarized in the following table.

Table 5: Hair dye 12 13 14 15 16 (Amount of dye in grams) 2.50 2.50 2.50 0.90 0.90 0.90 11 Example
No. 0.10 0.10 0.10 Color
fabrics 1.10 1.10 1.10 E1 1.10 1.10 1.10 0.40 0.40 0.40 K12 0.10 0.10 0.10 K13 0.05 0.10 0.10 0.10 K31 black black black brown brown brown D2 K23 Color

Examples 17 to 25: Hair dyes

Hair dye solutions of the following composition are produced:

X g developer substance E8 of formula (I) according to Table 1

U g developer substance E2 to E9 according to Table 1

Y g coupler substance K11 to K36 according to Table 3

Z g direct dye D1 to D3 according to Table 2

10.0 g potassium oleate (8% aqueous solution)

10.0 g ammonia (22% aqueous solution)

10.0 g ethanol

·· #· ♦♦♦

•-&psgr; · ·

0.3g
to 100.0g

Ascorbic acid
Water

Immediately before use, 30 g of the above dye solution are mixed with 30 g of a 6% aqueous hydrogen peroxide solution. The mixture is then applied to bleached hair. After an exposure time of 30 minutes at 40 ⁰ C, the hair is rinsed with water, washed with a commercially available shampoo and dried. The dyeing results are summarized in Table 6.

Table 6: Hair dyes

Example No. 17 18 19 (Amount of dye in grams) 0.35 0.30 0.30 Dyes E8 0.30 0.30 E4 0.30 E5 E6 0.18 0.22 K31 0.20 K32 0.30 0.30 K33 0.35 K25 reddish brown reddish brown reddish brown K26 Color

• · ♦ ·

·

·

•♦ · ·

Table 6: (Continuation) 21 22 23 24 25 (Amount of dye in grams) 0.50 0.40 0.40 0.16 0.15 0.15 20 0.15 Example
No. 0.15 Color
fabrics 0.15 E8 E2 0.10 E3 0.09 0.09 E9 0.20 0.15 0.20 0.10 0.20 0.10 0.10 K12 0.20 K13 0.05 K31 0.05 K32 0.05 0.10 0.10 0.10 K33 K21 light blonde light blonde light blonde light blonde light blonde light blonde K22 K23 Color

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Examples 26 to 31: Hair dyes in cream form

Cream-like color carrier masses of the following composition are produced:

X g developer substance E8 of formula (1) according to

Table 1

Y g coupler substance K11 to K36 according to Table Z g direct dye D2 according to Table 2 15.0 g cetyl alcohol
0.3 g ascorbic acid
3.5 g sodium lauryl alcohol diglycol ether sulfate, 28%

aqueous solution

3.0 g ammonia, 22% aqueous solution 0.3 g sodium sulphite, anhydrous ad 100.0 g water

Immediately before use, 30 g of the above coloring cream are mixed with 30 g of a 6% hydrogen peroxide solution. The mixture is then applied to the hair. After a contact time of 30 minutes at room temperature, the hair is rinsed with water, washed with a commercially available shampoo and dried. The coloring results are summarized in the following table.

Table 7: Hair dye 27 28 29 30 31 (Amount of dye in grams) 2.50 2.50 2.50 0.90 0.90 0.90 26 Example
No. 0.10 0.10 0.10 Color
fabrics 1.10 1.10 1.10 E8 1.10 1.10 1.10 0.40 0.40 0.40 K12 0.10 0.10 0.10 K13 0.05 0.10 0.10 0.10 K31 black black black light brown light brown light brown D2 K23 Color

All percentages contained in this application are by weight unless otherwise stated.

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Claims (8)

1. Agent for the oxidative dyeing of keratin fibers based on a developer substance-coupler substance combination, characterized in that it contains as developer substance at least one 2,5-diamino-(1'-hydroxyalkyl)-benzene derivative of the general formula (I),


wherein R is a straight-chain or branched alkyl radical having one to six carbon atoms, or a physiologically acceptable salt thereof. 2. Agent according to claim 1, characterized in that R is a methyl group or an ethyl group. 3. Agent according to claim 1 or 2, characterized in that the 2,5-diamino-1-(1'-hydroxyalkyl)-benzene derivative of the formula (1) is contained in an amount of 0.005 to 20 percent by weight. 4. Agent according to one of claims 1 to 3, characterized in that the coupler substance is selected from the group consisting of 2,6-diaminopyridine, 2-amino-4-[(2-hydroxyethyl)amino]anisole, 2,4-diamino-1-fluoro-5-methylbenzene, 2,4-diamino-1-methoxy-5-methylbenzene, 2,4-diamino-1-ethoxy-5-methylbenzene, 2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene, 2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxybenzene, 2,3-diamino-6-methoxypyridine, 3-amino-6-methoxy-2-(methylamino)pyridine, 2-(β-hydroxyethylamino)-6-methoxy-3-aminopyridine, 2,6-Diamino-3,5-dimethoxy-pyridin, 3,5-Diamino-2,6- dimethoxy-pyridin, 1,3-Diaminobenzol, 2,4-Diamino-1-(2-hydroxyethoxy)- benzof, 3-(2,4-Diaminophenoxy)-1-propanol, 2,4-Diamino-1-(2-methoxyethoxy)-benzol, 2,4-Diamino-1,5-di(2-hydroxyethoxy)-benzol, 1-(2-Aminoethoxy)-2,4-diaminobenzol, 2-Amino-1-(2-hydroxyethoxy)-4-methylaminobenzol, 2,4-Diaminophenoxy-essigsäure, 3-[Di(2-hydroxyethyl)amino]- anilin, 4-Amino-2-di[(2-hydroxyethyl)amino]-1-ethoxy-benzol, 5-Methyl-2- (1-methylethyl)-phenol, 3-[(2-hydroxyethyl)amino]-aniline, 3-[(2-aminoethyl)-amino]-aniline, 1,3-di(2,4-diaminophenoxy)-propane, di(2,4-diaminophenoxy)-methane, 1,3-diamino-2,4-dimethoxy-benzene, 2,6-bis(2-hydroxyethyl)amino- toluene, 4-hydroxyindole, 3-dimethylamino-phenol, 3-diethylamino-phenol, 5-amino-2-methyl-phenol, 5-amino-4-fluoro-2-methylphenol, 5-amino-4-methoxy-2methyl-phenol, 5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichlorophenol, 5-amino-2,4-dichlorophenol 3 -Amino-2-methyl-phenol, 3-amino-2-chloro-6-methyl-phenol, 3-Amino-phenol, 2-[(3-Hydroxyphenyl)amino]acetamid, 5-[(2-Hydroxyethyl)amino]-2-methylphenol, 3-[(2-Hydroxyethyl)amino]-phenol, 3-[(2-Methoxyethyl)amino]- phenol, 5-Amino-2-ethyl-phenol, 2-(4-Amino-2-hydroxyphenoxy)-ethanol, 5-[(3-Hydroxypropyl)amino]-2-methyl-phenol, 3-[(2,3-Dihydroxypropyl)- amino]-2-methyl-phenol, 3-((2-Hydroxyethyl)amino)-2-methyl-phenol, 2-Amino-3-hydroxy-pyridin, 5-Amino-4-chlor-2-methyl-phenol, 1-Naphthol, 1,5-Dihydroxy-naphthalin, 1,7-Dihydroxy-naphthalin, 2,3-Dihydroxynaphthalin, 2,7-Dihydroxy-naphthalin, 2-Methyl-1-naphthol acetate, 1,3-dihydroxybenzene, 1-chloro-2,4-dihydroxy-benzene, 2-chloro-1,3-dihydroxybenzene, 1,2-dichloro-3,5-dihydroxy-4-methyl-benzene, 1,5-dichloro-2,4-dihydroxy-benzene, 1,3-dihydroxy-2-methyl-benzene, 3,4-M ethylenedioxyphenol, 3,4-methylenedioxyaniline, 5-((2-hydroxyethyl)amino]-1,3-benzodioxole, 6-bromo-1-hydroxy-3,4-methylenedioxy-benzene, 3,4-diaminobenzoic acid, 3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine, 6-amino-3,4- 1,4(2H)-benzoxazine, 3-Methyl-1-phenyl-5-pyrazolone, 5,6-dihydroxy-indole, 5,6-dihydroxy-indoline, 5-hydroxy-indole, 6-hydroxyindole, 7-hydroxy-indole and 2,3-indolindione. 5. Agent according to one of claims 1 to 4, characterized in that it additionally contains at least one further developer substance which is selected from the group consisting of 1,4-diaminobenzene, 2,5-diamino-toluene, 2-chloro-1,4-diaminobenzene, 1-phenylamino-4-aminobenzene, 2,3-dimethyl-1,4-diaminobenzene, 1-(2-methoxyethyl)amino-4-aminobenzene, 2-(2,5-diaminophenyl)ethanol, N,N-bis-(β-hydroxyethyl)-p-phenylenediamine, 4,4'-diamino-diphenylamine, 2,6-dimethyl-1,4-diaminobenzene, 2-isopropyl-1,4-diaminobenzene, 2-propyl-1,4-diaminobenzene, 1,3-Bis-[(N-hydroxyethyl)-N-(4-aminophenyl)amino]-2-propanol, 2-Methyl- 4-dimethylamino-anilin, 2-Methoxy-1,4-diaminobenzol, 1-(2,5-Diaminophenyi)-ethan-1,2-diol, 4-Amino-phenol, 4-Amino-3-methylphenol, 2-Hydroxymethyl-4-aminophenol, 2-Methyl-4-aminophenol, 4-Amino-2- aminomethyl-phenol, 2-((2-Hydroxy-ethylamino)methyl)-4-aminophenol, 2-Methoxymethyl-4-aminophenol, 1-(5-Amino-2-hydroxyphenyl)-ethan-1,2- diol, 2,4-Diaminophenol, 5-Methyl-2-aminophenol, 6-Methyl-2-aminophenol, 2-Ethylamino-4-methyl-phenol, 2-Amino-4-methyl-phenol, 2-dimethylamino-5-aminopyridine, 4-hydroxy-2,5,6-triamino-pyrimidine, 4,5-diamino-1-(2'-hydroxyethyl)-1H-pyrazole, 4,5-diamino-1-methyl-1H-pyrazole, 4,5-diamino-1-benzyl-1H-pyrazole, 4 ,5-Diamino-1-isopropyl-1H-pyrazole, 4,5-diamino-1-((4'-methyl-benzyl)-1H-pyrazole and tetraaminopyrimidine. 6. Agent according to one of claims 1 to 5, characterized in that the developer substances and coupler substances, based on the total amount of the colorant, are each contained in a total amount of 0.005 to 20 percent by weight. 7. Agent according to one of claims 1 to 6, characterized in that it additionally contains at least one direct dye. 8. Agent according to one of claims 1 to 7, characterized in that it is in the form of a hair dye.