DE10120307A1 - Method of coloring keratin fibers, especially human hair, uses vitamin B6 or derivative in pretreatment agent or colorant containing oxidation dye precursor or indole or indoline derivative - Google Patents

Abstract

Method of coloring keratin fibers, especially human hair, using optional pre-treatment agent M1 and colorant M2 is new Method of coloring keratin fibers, especially human hair, involves (1) applying optional pre-treatment agent M1 and (2) colorant M2, obtained by mixing a component (M2a) containing oxidation dye precursor(s) of the developer type and/or an indole and/or indoline derivative and a component (M2b) containing an oxidant and/or enzyme, immediately before application, optionally with addition of another agent M3 to M2a, M2b or M2; and (3) rinsing the fibers after 5-30 minutes. The novelty is that M1, M2a, M2b and/or M3 contains 3-(hydroxy-, (hydroxy)alkoxy, acyloxy, amino- or phosphato)-methyl-4,5-di-substituted pyridine compound(s) of formula (I) or a salt: A, B' = hydrogen (H), halogen, 1-4 carbon (C) alkyl or monohydroxy- or amino-alkyl, 3-6 C cycloalkyl, 2-4 C oligohydroxyalkyl, -OR or -NR<1>R<2>; R<1>, R<2> = H or 1-4 C alkyl or monohydroxyalkyl; or NR<1>R<2> = a saturated ring; C' = -OR, -NR<1>R<2>, -OP(O)(OR<3>)2, 1-4 C monohydroxyalkyl, 2-4 C oligohydroxyalkyl or 1-4 C alkyl; D = -OR, carboxy, 1-22 C alkoxycarbonyl, formyl (CHO), -CH2OR or -CH2-NR2; E = -OR, -OP(O)(OR<3>)2, 1-4 C monohydroxyalkyl or 2-4 C oligohydroxyalkyl; R = H, 1-4 C alkyl, 1-22 C acyl, hydroxy-(2-22 C)-acyl, 2-10 C carboxyacyl, 3-10 C oligocarboxyacyl, oligocarboxy-mono- or -oligo-hydroxy-(3-10 C)-acyl, 3-8 C cycloalkyl, 1-4 C monohydroxyalkyl, 2-4 C oligohydroxyalkyl, aryl (optionally substituted by hydroxy, nitro or amino), hetaryl or -CH2CH2NR<1>R<2>; and R<3> = H or 1-5C alkyl. Independent claims are also included for: (a) pretreatment agents M1 containing (I) and colorants M2 containing (I); and (b) kits comprising M1 containing (I) and M2a, or M1, M2a and M3 containing (I), packed separately.

Description

The invention relates to methods for dyeing keratin fibers in which at least one Pyridoxine, pyridoxal or pyridoxamine derivative is used and colorants with such compounds, as well as kits for use in the method according to the invention.

Under keratin fibers according to the invention are furs, wool, feathers and in particular the understood human hair. Human hair is involved in many ways today treated hair cosmetic preparations. These include cleaning the hair with Shampoos, the care and regeneration with rinses and cures and bleaching, Dyeing and shaping of hair with coloring, tinting, waving and Styling preparations. Thereby means for changing or nuancing the color of the Head hair a prominent role.

For temporary dyeings usually dyeing or tinting agents are used, which as coloring component so-called Direktzieher included. This is Dye molecules that grow directly on the hair and no oxidative process for Need training of the paint. For example, one of these dyes already belongs Henna known in antiquity for coloring body and hair. These dyes are Shampooing usually sensitive, so that often undesirable Shade shift or even a visible "discoloration" may occur.

For the dyeing of keratin fibers, especially hair, play the so-called Oxidation colorants because of their intense colors and good fastness properties, the be achieved at relatively low dyeing temperature and in short dyeing times, a special role. Such colorants contained in a suitable, usually aqueous carrier  a developer component which is under the influence of atmospheric oxygen or of Oxidants by oxidative coupling forms the dye. This dye can by coupling with another developer component or with so-called Coupler components, which themselves can not form dyes, intensified and in the Nuance be modified.

Good oxidation dye precursors are primarily the following prerequisites You must: In the oxidative coupling you have the desired color shades in form sufficient intensity and authenticity. You also need a good one Have Aufziehvermögen on the fiber, in particular, in human hair no noticeable differences between strained and freshly regrowed hair may (leveling). They should be resistant to light, heat, friction and the Influence of chemical reducing agents, eg. B. permanent wave fluids. After all, they should - if used as a hair dye - do not stain the scalp too much, and Above all, they should be harmless from a toxicological and dermatological point of view. Furthermore, the coloring achieved by bleaching should be easily removed from the hair again if they do not meet the individual wishes of the individual corresponds and should be reversed.

The user of hair dyes intends, among other things, a natural-looking Hair color as a coloring result. This is especially the case when gray hair inconspicuous by a natural-looking coloring is to be laminated. To produce natural-looking shades comes the hair dyeing and tinting agents that in the Color shades in the red and brown range color, a significant importance. Oxidation colorant in the red and brown areas, as z. B. with the combination of 2,4,5,6-tetraaminopyrimidine with 2-methylresorcinol are still not optimal regarding the uniformity of the paint lift. Golden shades were under Use of conventional coupler and developer combinations not yet in satisfactorily available. To get a big variety of shades, can be used for nuancing u. a. direct dyes are used. Latter are usually less washfast and therefore not so good to combine with Oxidizing dyes suitable.  

A naturally appearing hair color also comes from a dyeing process, when in the applied hair dye indole or indoline derivatives as natural analog precursors Dyes are used. The document WO 9906016 A1 describes that by using a combination of derivatives of indole or indoline with usual coupler components partially or totally gray hair in the original natural nuance, so that there is no significant difference to still existing, naturally pigmented hair is visible. This will be blonde up medium brown colorations achieved. Those published in the publication WO 9906016 A1 Dye combinations achieve dark to black colorations without a red shade, the with the classically designated coupler-developer combinations difficult were accessible.

The coloring of keratin fibers using nature-analogous dyes sets one Trend, naturally occurring colorations also with natural or nature-identical To cause dye precursors. It is therefore desirable to have the tint of the hair through Addition of an equally natural or nature-identical oxidation dye precursor of the coupler type in the color scheme to vary. Access to a wider The color palette should be opened up and the most intensive possible, wash and lightfast Coloring be achieved.

In addition to optimizing the coloring of hair dyes is improving the Compatibility of the funds another task. Oxidative components z. In Hair dyes have a damaging effect on the structure of the hair keratin. The hair experiences a weight loss and a measurable decrease in the denaturation temperature of the Keratin. An increasing brittleness and the difficult combability of the hair as well a deterioration of the seat and fullness of the hairstyle are the result. In addition, one has structurally damaged hair has a dull and dull appearance. These problems should be used with structurally improving additives in the staining process, advantageously as constituents of the colorant itself, counteracted.

For these reasons, there is a need for novel oxidation dye Precursors and care ingredients that improve the mentioned parameters  enable. Surprisingly, it has been found that pyridoxine, pyridoxal or Pyridoxamine derivatives meet the requirements in an excellent manner.

Pyridoxine and other compounds of the vitamin B6 group are considered as components in Hair Tonics mentioned to reduce greasiness and to stimulate hair growth Service. In EP 0678293 A2, topical compositions containing Pyridoxine tripropionate is suggested for the treatment of the hair and the skin. In EP 001079 A1 are described cosmetic compositions with antiseborrheic effect, the Pyridoxine tripalmitate as an active ingredient.

In EP-873744 A2 carbonyl compounds, u. a. Pyridoxal, in combination with Amines, hydroxy compounds, peptides, CH-active compounds and others Components as dye precursors in preferably non-oxidative hair dyes disclosed.

Hair dyes, the derivatives of pyridoxine, pyridoxal or pyridoxamine as effective Oxidation dye precursors and as structurally improving additive are included hitherto unknown to the person skilled in the art.

It was surprisingly found by comparison dyeings that vitamin B6 as well certain derivatives have coupler properties. In particular, it has been found that using such compounds as a coupler component in hair dyes the Color palette is extended to medium gold-blonde colors. Furthermore, it was found that the Use of the compounds according to the invention during the dyeing process Improvement of the structure of the hair keratin causes.

A first subject of the invention is therefore a process for dyeing keratin fibers, in particular human hair, in which

• - If desired, a pretreatment agent M1 is applied to the fiber, then
• - a colorant M2 is used on the fiber, possibly immediately before application to the fiber:
  a component M2a containing at least one oxidation dye precursor of the developer type and / or an indole and / or indoline derivative and
  a component M2b containing an oxidizing agent and / or an enzyme

mixing, optionally adding to the individual agents M2a or M2b before the mixing or the mixing M2 another agent M3 and rinsing away this coloring agent M2 from the fiber after a period of 5-30 minutes, characterized in that at least one of the agents M1, M2a, M2b or M3 at least one compound according to formula (I),

in which

• - A and B are each independently hydrogen, halogen, a C ₁ -C ₄ alkyl group, a C ₃ -C ₆ cycloalkyl group, a C ₁ -C ₄ monohydroxyalkyl group, a C ₂ -C ₄ oligohydroxyalkyl group, a C C ₁ -C ₄ -Aminoalkylgruppe, a group -OR or a group -NR ¹ R ² , in which R ¹ and R ^{2 are} independently hydrogen, a C ₁ - C ₄ alkyl group or a C ₁ -C ₄ -Monohydroxyalkylgruppe or R ¹ and R ² together with the nitrogen atom form a saturated ring,
• - C is a group -OR, -NR ¹ R ² , -OP (O) (OR ³ ) ₂ , a C ₁ -C ₄ monohydroxyalkyl group, a C ₂ -C ₄ oligohydroxyalkyl group or a C ₁ -C _4- alkyl group,
• D is a hydroxy group, a carboxy group, a C ₁ -C ₂₂ -alkoxycarbonyl group, a formyl radical, a group -CH ₂ OR or a group -CH ₂ -NR ₂ ,
• E is a group -OR, -OP (O) (OR ³ ) ₂ , a C ₁ -C ₄ -monohydroxyalkyl group or a C ₂ -C ₄ -oligohydroxyalkyl group,

in which

• Each R is hydrogen, a C ₁ -C ₄ -alkyl group, a C ₁ -C ₂₂ -acyl group, a hydroxy-C ₂ -C ₂₂ -acyl group, a C ₂ -C ₁₀ -carboxy-acyl group, a C ₃ -C ₁₀ - oligocarboxyacyl group, an oligocarboxy-monohydroxy-C ₃ -C ₁₀ -acyl group, an oligocarboxy-oligohydroxy-C ₃ -C ₁₀ -acyl group, a C ₃ -C ₈ -cycloalkyl group, a C ₁ -C ₄ -monohydroxyalkyl group, a C ₂ -C ₄ oligohydroxyalkyl group, an aryl group which may contain a hydroxy, nitro or amino group, a heteroaromatic radical or a group -CH ₂ CH ₂ NR ¹ R ² in which R ¹ and R ^{2 are} as defined above are,
• R ^{3 is in} each case hydrogen or a C ₁ -C ₅ -alkyl group,

or one of the corresponding physiologically acceptable salts.

Examples of C ₁ -C ₄ -alkyl groups in the compounds according to the invention are methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl. Preferred alkyl groups are methyl and ethyl, methyl is a particularly preferred alkyl group. Preferred C ₃ -C ₆ -cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl. Cyclohexyl and cyclopentyl are particularly preferred groups. Preferred C ₁ -C ₄ monohydroxyalkyl groups are the groups hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl; Hydroxymethyl and 2-hydroxyethyl are particularly preferred monohydroxyalkyl groups. A preferred C ₂ -C ₄ oligohydroxyalkyl group is the 1,2-dihydroxyethyl group. Preferred C ₁ -C ₂₂ acyl groups are, for example, acetyl, propionyl, butyryl, valeryl, capryl, lauryl, myristyl, palmityl, stearyl, linolyl, behenyl. Examples of a hydroxy-C ₂ -C ₂₂ acyl group are salicylic acid or lactic acid. Preferred C ₂ -C ₁₀ -carboxyacyl groups are derived, for example, from malonic acid, succinic acid or adipic acid. An example of a preferred C ₃ -C ₁₀ oligocarboxyacyl group is glyceric acid. A preferred oligocarboxy-monohydroxy-C ₃ -C ₁₀ acyl group is derived, for. B. from the citric acid or malic acid. Preferred oligocarboxy-oligohydroxy- C ₃ -C ₁₀ acyl groups are, for. B. derived from tartaric acid. Suitable halogen substituents according to the invention are preferably fluorine, chlorine, bromine and iodine, particularly preferred are chlorine and bromine. Physiologically acceptable salts include salts of inorganic or organic acids, eg. As hydrochlorides, sulfates or hydrobromides understood. The other terms used are derived according to the invention from the definitions given here.

The ester derivatives of the compounds according to formula (I) also have physiological and hair structure improving properties. This applies in particular to the esters of pyridoxine, which can be converted into the pyridoxine by hydrolysis. In addition, the ester derivatives have improved lipid solubility compared to the unesterified derivatives. Further examples of carboxylic ester derivatives of pyridoxine are derived from the carboxylic acids such as formic, acetic, propionic, butyric, isobutyric, valeric, isovaleric, pivalic, oxalic, malonic, succinic, glutaric, glyceric, glyoxylic, adipic, pimelic, suberic, azelaic acids , Sebacic, propiolic, crotonic, isocrotonic, elaidic, maleic, fumaric, muconic, citraconic, mesaconic, camphoric, benzoic, o, m, p-phthalic, naphthoic, toluoic, hydratropic, atropic, cinnamic, isonicotinic, nicotinic, bicarbamic, 4 , 4'-dicyano-6,6'-binicotinic acid, 8-carbamoyloctanoic acid, 1,2,4-pentanetricarboxylic acid, 2-pyrrolecarboxylic acid, 1,2,4,6,7-naphthalene pentaacetic acid, malonaldehyde acid, 4-hydroxy phthalamic acid, 1 Pyrazolecarboxylic acid, gallic acid or propane tricarboxylic acid, and selected from the dicarboxylic acids au s of the group formed by compounds of general formula (II),

in the Z is a linear or branched alkyl or alkenyl group having 4 to 12 Carbon atoms, n is a number from 4 to 12 and one of the two groups X and Y for one COOH group and the other is hydrogen or a methyl or ethyl radical, Dicarboxylic acids of the general formula (II), which additionally contains 1 to 3 methyl or Ethyl substituents on the cyclohexene ring and dicarboxylic acids derived from the Dicarboxylic acids according to formula (II) formally by addition of a molecule of water to the Double bond arise in the cyclohexene ring.

Preference is given to compounds of the formula I in which one of the two groups A or B is Hydrogen stands.  

Preference is given to compounds of the formula I in which one of the two groups A or B is hydrogen and the other group is a C ₁ -C ₄ -alkyl group.

Likewise preferred are compounds of the formula I in which C is a hydroxyl group, a C ₁ -C ₄ -monohydroxyalkyl group or a C ₂ -C ₄ -oligohydroxyalkyl group.

The compounds of formula I are preferred according to the invention, in which D is a Hydroxymethyl group, a hydroxy group, a carboxy group or a formyl radical stands.

Also preferred are compounds of the formula I in which E is a hydroxy group or a group -OP (O) (OH) ₂ .

A particularly preferred compound according to formula I is pyridoxine.

Compounds of formula (I), such as. Pyridoxal, pyridoxal-5-phosphonic acid, pyridoxamine, Pyridoxine and 3-hydroxy-5-hydroxymethyl-2-methylpyridine-4-carboxylic acid are commercially available purchase.

A second object of the invention is a means for use in a method for Coloring of keratin fibers, in particular human hair, characterized that there is at least one compound according to formula (I) or one of the corresponding Physiologically acceptable salts, preferably in an amount of 01.-5 wt .-% based on the agent contains. This agent acts as a pretreatment agent M1 in the inventive method. When using the agent M1 is an exposure time of 1-30 minutes preferred.

A third aspect of the invention is a dyeing agent for keratin fibers, in particular the human hair, containing in a first embodiment at least one developer-type oxidation dye precursor thereby in that it additionally contains at least one compound of the formula (I) or one of the contains corresponding physiologically acceptable salts. These funds can optionally containing at least one oxidation dye precursor of the coupler type.  

It may be preferred according to the invention to use as the developer component a p-phenylenediamine derivative or one of its physiologically acceptable salts. Particular preference is given to p-phenylenediamine derivatives of the formula (E1)

in which

• - G ¹ represents a hydrogen atom, a C ₁ -C ₄ alkyl, C ₁ -C ₄ - monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a (C ₁ -C ₄₎ alkoxy (C ₁ - C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C ₁ -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 -C ₄ alkyl, C ₁ -C ₄ - monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a (C ₁ -C ₄₎ alkoxy (C ₁ - C ₄ ) -alkyl radical or a C ₁ -C ₄ -alkyl radical which is 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 -C ₄ alkyl radical, a C ₁ -C ₄ monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical a C ₁ -C ₄ -Hydroxyalkoxyrest, a C ₁ -C ₄ - Acetylaminoalkoxyrest, a C ₁ -C ₄ -Mesylaminoalkoxyrest or a C ₁ -C ₄ - Carbamoylaminoalkoxyrest,
• G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ -C ₄ -alkyl radical or
• when G ³ and G ⁴ are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.

An example of a preferred C ₂ -C ₄ polyhydroxyalkyl group is the α, β-dihydroxyethyl group. Examples of nitrogen-containing groups of the formula (E1) are especially the amino groups, C ₁ -C ₄ monoalkylamino, C ₁ -C ₄ - dialkylamino, C ₁ -C ₄ -Trialkylammoniumgruppen, C ₁ -C ₄ -Monohydroxyalkylamino groups, imidazolinium and ammonium ,

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p- Phenylenediamine, p-toluenediamine, 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- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (β-hydroxyethyl) amino-2- methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p- phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-) Hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3 methyl-p-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ- Dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p- phenylenediamine, 2- (β-hydroxyethyloxy) -p-phenylenediamine, 2- (β-acetylaminoethyloxy) -p- phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1,4-dioxane and their physiologically acceptable salts.

Very particularly preferred according to the invention are p-phenylenediamine derivatives of the formula (E1) p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine and N, N-bis- (Β-hydroxyethyl) -p-phenylenediamine.

It may further be preferred according to the invention, as the developer component compounds containing at least two aromatic nuclei containing amino and / or Hydroxyl groups are substituted.

Among the binuclear developer components which can be used in the dyeing compositions according to the invention, mention may be made in particular of the compounds corresponding to the following formula (E2) and their physiologically tolerated salts:

in which:

• - Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ radical which is optionally substituted by a C ₁ -C ₄ -alkyl radical, by a C ₁ -C ₄ -monohydroxyalkyl radical and / or by a bridging Y or which is optionally part of a bridging ring system,
• - The bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms may be substituted by one or more hydroxyl or C ₁ -C ₈ alkoxy radicals, or a direct bond,
• G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a C ₁ -C ₄ -alkyl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a C ₁ -C ₄ -aminoalkyl radical or a direct connection to the bridge Y,
• G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a C ₁ -C ₄ -alkyl radical,

with the provisos that

• The compounds of the formula (E2) contain only one bridge Y per molecule and
• - The compounds of formula (E2) contain at least one amino group, which carries at least one hydrogen atom.

The substituents used in formula (E2) are analogous to the above according to the invention Executions defined.

Preferred binuclear developer components of the formula (E2) are in particular: N, N'- Bis- (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-)  hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetra methylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methyl-aminophenyl) -tetramethylenediamine, N, N'-bis (ethyl) -N, N'-bis (4'-amino) 3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 1,4-bis (4'-bis) aminophenyl) -diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) -piperazine, N- (4'- Aminophenyl) -p-phenylenediamine and 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane and their physiologically acceptable salts.

Very particularly preferred binuclear developer components of the formula (E2) are N, N'- Bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, bis (2-hydroxy-5- aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane and 1,10-bis- (2 ', 5'- diaminophenyl) -1,4,7,10-tetraoxadecane or one of its physiologically acceptable salts.

Furthermore, it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts. Particular preference is given to p-aminophenol derivatives of the formula (E3)

in which

• - G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₄ alkyl, C ₁ -C ₄ - monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a (C ₁ -C ₄₎ alkoxy- ( C ₁ -C ₄₎ - alkyl group, a C ₁ -C ₄ aminoalkyl radical, a hydroxy (C ₁ -C ₄₎ alkylamino group, a C ₁ - C ₄ -Hydroxyalkoxyrest, a C ₁ -C ₄ hydroxyalkyl ( C ₁ - to C ₄ ) -aminoalkyl or a (di-C ₁ -C ₄ -alkylamino) - (C ₁ -C ₄ ) -alkyl radical, and
• - G ¹⁴ represents a hydrogen or halogen atom, a C ₁ -C ₄ alkyl, C ₁ -C ₄ - hydroxyalkyl, C ₂ -C ₄ polyhydroxyalkyl radical, a (C ₁ -C ₄₎ alkoxy- (C ₁ -C ₄₎ - alkyl group, a C ₁ -C ₄ aminoalkyl radical or a C ₁ -C ₄ -Cyanoalkylrest,
• - G ¹⁵ is hydrogen, a C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl radical, a C ₂ - C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and
• - G ¹⁶ is hydrogen or a halogen atom.

The substituents used in formula (E3) are analogous to the above according to the invention Executions defined.

Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl- p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxy methylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (2- hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4- Amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (β- hydroxyethylaminomethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 2,6- Dichloro-4-aminophenol, 4-amino-2 - ((diethylamino) methyl) phenol and their physiological compatible salts.

Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3- methylphenol, 4-amino-2-aminomethylphenol and 4-amino-2-ol ((Diethylamino) methyl) phenol.

Further, the developer component may be selected from o-aminophenol and its Derivatives such as 2-amino-4-methylphenol or 2-amino-4-chlorophenol.

Furthermore, the developer component may be selected from heterocyclic Developer components, such as the pyridine, pyrimidine, pyrazole, pyrazole Pyrimidine derivatives and their physiologically acceptable salts. To be favoured According to the invention pyrimidine or pyrazole derivatives.

Preferred pyrimidine derivatives are in particular the compounds described in the German patent DE 23 59 399, Japanese Patent Laid-Open JP 02019576 A2 or in the Laid-open 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-1 (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) -pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1 methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino 3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3- methylpyrazole, 4,5-diamino-1- (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-yl hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5- triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4 (β- hydroxyethyl) amino-1-methylpyrazole.

Preferred pyridine derivatives are in particular the compounds described in the patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino-pyridine, 2- (4- Methoxyphenyl) amino-3-amino-pyridine, 2,3-diamino-6-methoxy-pyridine, 2- (β- Methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

Preferred pyrazole-pyrimidine derivatives are, in particular, the derivatives of pyrazolo [1,5-a] pyrimidine of the following formula (E4) and their tautomeric forms, provided that a tautomeric equilibrium exists:

in which:

• - G ^17, G ^18, G ¹⁹ and G ²⁰ are independently a hydrogen atom, a C ₁ - C ₄ alkyl radical, an aryl radical, a C ₁ -C ₄ hydroxyalkyl radical, a C ₂ -C ₄ - polyhydroxyalkyl a (C ₁ -C ₄ ) -alkoxy (C ₁ -C ₄ ) -alkyl radical, a C ₁ -C ₄ -aminoalkyl radical which may optionally be protected by an acetyl-ureide or sulfonyl radical, a (C ₁ C ₄ ) -Alkylamino- (C ₁ -C ₄ ) -alkyl radical, a di - [(C ₁ -C ₄ ) -alkyl] - (C ₁ -C ₄ ) -aminoalkyl radical, wherein the dialkyl radicals optionally have one carbon cycle or a heterocycle with 5 or 6 chain members, form a C ₁ - C ₄ hydroxyalkyl or a di- (C ₁ -C ₄₎ - [hydroxyalkyl] - (C ₁ -C ₄₎ aminoalkyl radical,
• - the X radicals are each independently a hydrogen atom, a C ₁ -C ₄ - alkyl radical, an aryl radical, a C ₁ -C ₄ hydroxyalkyl radical, a C ₂ -C ₄ - polyhydroxyalkyl radical, a C ₁ -C ₄ -Aminoalkylrest, a (C ₁ -C ₄ ) -Alkylamino- (C ₁ -C ₄ ) alkyl radical, a di - [(C ₁ -C ₄ ) alkyl] - (C ₁ -C ₄ ) aminoalkyl radical, wherein the Dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ -C ₄ -hydroxyalkyl or a di (C ₁ -C ₄ -hydroxyalkyl) - aminoalkyl, an amino radical, a C ₁ -C ₄ Alkyl or di (C ₁ -C ₄ hydroxyalkyl) amino, halogen, carboxylic acid or sulfonic acid group,
• - i has the value 0, 1, 2 or 3,
• - p has the value 0 or 1,
• - q has the value 0 or 1 and
• - n has the value 0 or 1,

with the proviso that

• The sum of p + q is not equal to 0,
• if p + q equals 2, n 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);
• when p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

The substituents used in formula (E4) are according to the invention analogous to the above Executions defined.

When the pyrazolo [1,5-a] pyrimidine of the above formula (E4) contains a hydroxy group at one of the 2, 5 or 7 positions of the ring system, there is a tautomeric equilibrium shown, for example, in the following scheme:

In particular, among the pyrazolo [1,5-a] -pyrimidines of the above formula (E4):

• - pyrazole [1,5-a] pyrimidine-3,7-diamine;
• 2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• - pyrazole (1,5-a] pyrimidine-3,5-diamine;
• 2,7-dimethylpyrazolo [1,5-a] -pyrimidine-3,5-diamine;
• 3-amino-pyrazolo [1,5-a] -pyrimidin-7-ol;
• 3-amino-pyrazolo [1,5-a] -pyrimidin-5-ol;
• - 2- (3-amino-pyrazolo [1,5-a] -pyrimidin-7-ylamino) -ethanol;
• - 2- (7-amino-pyrazolo [1,5-a] -pyrimidin-3-ylamino) -ethanol;
• - 2 - [(3-amino-pyrazolo [1,5-a] -pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol;
• - 2 - [(7-amino-pyrazolo [1,5-a] -pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol;
• 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 2,5, N7, N7-tetramethylpyrazolo [1,5-a] -pyrimidine-3,7-diamine;

and their physiologically acceptable salts and their tautomeric forms, when tautomeric equilibrium is present.

The pyrazolo [1,5-a] -pyrimidines of the above formula (E4) can be used as in the literature described by cyclization starting from an aminopyrazole or hydrazine getting produced.

Developer components preferred according to the invention are derivatives of p-phenylenediamine, Derivatives of pyrimidine, derivatives of pyrazole and p-aminophenol.

Particularly preferred developer components according to the invention are p-phenylenediamine, p- Toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, N, N-bis (β-hydroxyethyl) -p-  phenylenediamine, 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, 2,5,6-triaminopyrimidine, 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chloro benzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1- Benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5- Diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1- (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-methyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1 isopropylpyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triamino pyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4 (β-hydroxyethyl) amino-1-methylpyrazole, p-aminophenol, 4-amino-3-methyl phenol, 4-amino-3-fluorophenol, 4-amino-2-aminomethylphenol and 4-amino-2 - ((diethyl amino) methyl) phenol.

Very particularly preferred developer components are according to the invention p- Phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine and N, N-bis- (β-) hydroxyethyl) -p-phenylenediamine, 2,4,5,6-tetraaminopyrimidine, 4,5-diamino-1- (β- hydroxyethyl) pyrazole, 4-amino-3-methylphenol and 4-amino-2-aminomethylphenol

In particular m-phenylenediamine derivatives according to the invention as coupler components, Naphthols, resorcinol and resorcinol derivatives, pyrazolones, and m-aminophenols.

According to preferred coupler components 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, 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, N-cyclopentyl-3- aminophenol, 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, for example, 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) -1- methylbenzene and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene,
• - o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-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,
• Naphthalene derivatives such as, for example, 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-amino benzomorpholine,
• Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline, Pyrazole derivatives such as 1-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, for example, 1-hydroxy-3,4-methylenedioxybenzene, 1- Amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4- methylenedioxybenzene,

Particularly preferred coupler components are 2-amino-3-hydroxypyridine, 2-amino-3 hydroxy-5-chloropyridine, 3-amino-2-methylamino-6-methoxy-pyridine, 3,5-diamino-2,6-  dimethoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, m-phenylenediamine, 2,6-bis (2- hydroxyethylamino) toluene, 3-amino-2,4-dichlorophenol, 3-amino-2-chloro-6-methylphenol, 5- Amino-4-chloro-2-methylphenol, 5- (β-hydroxyethyl) amino-2-methylphenol, 5-amino-2-ol methylphenol, 2-methylresorcinol, 2- (2 ', 4'-diaminophenoxy) ethanol, 1,3-bis (2', 4'-diamino phenoxy) propane, resorcinol, 4-chlororesorcinol, resorcinol monomethyl ether, m-aminophenol, 1,7- 2,7- and 1,5-dihydroxynaphthalene and 4-hydroxyindole and 6-hydroxyindole.

The hair colorants of the invention contain both the developer components as also the coupler components preferably in an amount of 0.005 to 10 wt .-% preferably from 0.1 to 5 wt .-% in each case based on the total oxidation colorant.

In this case, developer components and coupler components are generally approximately used molar amounts to each other. If the molar use as appropriate has proven, so is a certain excess of individual oxidation dye precursors not disadvantageous, so that developer components and coupler components in a mole Ver ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2, may be included.

In a second embodiment, a means for dyeing keratin fibers, especially human hair, containing at least one indole and / or indoline derivative, characterized in that it comprises a compound according to formula (I) or one of the corresponding physiologically acceptable salts.

As precursors of natural-analogous dyes are in the inventive agent of the second Embodiment preferred indoles and / or indolines used, the at least one Hydroxy or amino group, preferably as a substituent on the six-membered ring. These Groups may carry further substituents, e.g. B. in the form of an etherification or Esterification of the hydroxy group or alkylation of the amino group.

Particularly suitable precursors of naturally-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (IIIa),

in the independently of each other
R ¹ represents hydrogen, a C ₁ -C ₄ alkyl group, a C ₃ -C ₆ cycloalkyl group, a C ₂ - C ₄ alkenyl group or a C ₁ -C ₄ hydroxyalkyl group,
R ² is hydrogen or a -COOH group, wherein the -COOH group may also be present as a salt with a physiologically compatible cation,
R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
R ⁴ is hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ in which
R ⁶ is a C ₁ -C ₄ alkyl group, and
R ⁵ represents one of the groups mentioned under R ⁴ ,
and physiologically acceptable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indoline are the 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 and 6-hydroxyindoline, the 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 the 5,6-dihydroxyindoline.

Also suitable as precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindole of the formula (IIIb),

in the independently of each other
R ¹ represents hydrogen, a C ₁ -C ₄ alkyl group, a C ₃ -C ₆ cycloalkyl group, a C ₂ - C ₄ alkenyl group or a C ₁ -C ₄ hydroxyalkyl group,
R ² is hydrogen or a -COOH group, wherein the -COOH group may also be present as a salt with a physiologically compatible cation,
R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
R ⁴ is hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ in which
R ⁶ is a C ₁ -C ₄ alkyl group, and
R ⁵ represents one of the groups mentioned under R ⁴ ,
and 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-dihy droxyindole, 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 in particular the 5,6-dihydroxyindole.

The indoline and indole derivatives can be used in the colorants according to the invention both as free bases as well as in the form of their physiologically acceptable salts with inorganic or organic acids, eg. As the hydrochlorides, sulfates and hydrobromides used become. The indole or indoline derivatives are usually present therein in amounts of 0.05-10% by weight, preferably contain 0.2-5 wt .-%.  

Especially in the use of dye precursors of the indoline or indole type it has proved to be advantageous as alkalizing an amino acid and / or a Use oligopeptide.

Optionally, at least one developer-type oxidation dye precursor may also be present be included. The preferred developers and the amounts used thereof correspond those of the first embodiment.

In a third embodiment, hair colorants of the invention contain the first and second embodiment for further modifying the color shades in addition to the Oxida tion dye precursors additionally customary substantive dyes.

Direct dyes are usually nitrophenylenediamines, nitroaminophenols, Azo dyes, anthraquinones or indophenols. Preferred substantive dyes are under 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 known compounds as well as 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-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) -amino-5-chloro-2 nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2- nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4- naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4- Ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

Also useful as direct dyes according to the invention are cationic substantive dyes. Particularly preferred are

• a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,  
• b) aromatic systems 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, as well
• c) direct dyes containing a heterocycle containing at least one has quaternary nitrogen atom, as described for example in EP-A2-998 908, to the is explicitly referenced at this point, disclosed in claims 6 to 11 become.

Preferred cationic substantive dyes of group (c) are in particular the following compounds:

The compounds of formulas (DZ1), (DZ3) and (DZ5) are most preferred cationic substantive dyes of group (c). The cationic substantive Dyes sold under the trademark Arianor® are in accordance with the invention particularly preferred substantive dyes.

The agents according to the invention according to this embodiment contain the substantive Dyes preferred in an amount of 0.01 to 20 wt .-%, based on the total Colorant.

All colorants according to the invention contain the compounds according to the invention Formula (I) preferably in an amount of 0.05-5 wt .-%, in particular 0.1-1 wt .-%, based on the entire remedy.

Furthermore, the preparations according to the invention can also occur in nature Dyes contain, for example, in henna red, henna neutral, henna black, Chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and Alkana root are included.

The inventive compositions contain dye precursors preferably 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 which are suitable for use on the hair. But it is also conceivable that  Dye precursors in a powdered or tablet-like formulation too integrate.

For the purposes of the present invention, aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing from 3 to 70% by weight of a C ₁ -C ₄ -alcohol, in particular ethanol or isopropanol. The compositions according to the invention may additionally contain further organic solvents, for example methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. Preference is given to all water-soluble organic solvents.

The actual oxidative coloring of the fibers can be done basically with atmospheric oxygen. Preferably, however, a chemical oxidizing agent is used, especially when in addition to the coloring, a lightening effect on human hair is desired. As oxidation Persulfates, chlorites and in particular hydrogen peroxide or its An Storage products of urea, melamine and sodium borate in question. It continues possible to carry out the oxidation by means of enzymes, wherein the enzymes for both Generation of oxidizing per-compounds are used as well as for reinforcement the effect of a small amount of oxidizing agent present. So can the enzymes (Enzyme class 1: oxidoreductases) Electrons from suitable developer components (Reducing agent) transferred to atmospheric oxygen. Oxidases such as Tyrosinase, ascorbate oxidase and laccase but also glucose oxidase, uricase or Pyruvate. Furthermore, the procedure is called the effect of small amounts (eg. 1% and less, based on total agent) of hydrogen peroxide by peroxidases strengthen.

The agents according to the invention can furthermore all be known for such preparations Active substances, additives and auxiliary substances. In many cases, these remedies contain at least a surfactant, whereby in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proved to be proved to be advantageous, the surfactants from anionic, zwitterionic or nonionic Select surfactants.  

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

• - linear fatty acids with 10 to 22 carbon 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 having 10 to 22 C atoms and x = 0 or 1 to 16,
• Acylsarcosides having 10 to 18 C atoms in the acyl group,
• Acyltaurides having 10 to 18 C atoms in the acyl group,
• Acyl isethionates having 10 to 18 C atoms in the acyl group,
• - Sulfobernsteinsäuremono- and -dialkylester having 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters having 8 to 18 carbon atoms in the Alkyl group and 1 to 6 oxyethyl groups,
• Linear alkanesulfonates having 12 to 18 C atoms,
• - linear alpha-olefin sulfonates having 12 to 18 C atoms,
• Alpha-sulfofatty acid methyl esters of fatty acids containing 12 to 18 carbon atoms,
• 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 = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• - Sulfated Hydroxyalkylpolyethylen- and / or Hydroxyalkylenpropylenglykolether according to DE-A-37 23 354,
• - Sulfonates of unsaturated fatty acids having 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,
• - 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 containing 8 to 22 C Represent atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 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 ₂₂ - carboxylic acids such as oleic acid, stearic acid, isostearic acid and palmitic acid.

Nonionic surfactants contain as hydrophilic group z. As a polyol group, a Po lyalkylenglykolethergruppe or a combination of polyol and Polyglykolethergruppe. Such compounds are, for example

• - Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 C atoms, to fatty acids having 12 to 22 C atoms and to alkylphenols having 8 to 15 C atoms in the alkyl group,
• C ₁₂ -C ₂₂ -fatty acid mono- and diesters of addition products of 1 to 30 mol of ethylene oxide with glycerol,
• C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs, and
• - Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated Ri zinusöl.

Preferred nonionic surfactants are alkyl polyglycosides of the general formula R'O- (Z) _x . These connections are identified by the following parameters.

The alkyl radical R 'contains from 6 to 22 carbon atoms and can be both linear and branched be. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-octyl. Stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. Using so-called "oxo-alcohols" as starting materials predominate compounds with an unge number of carbon atoms in the alkyl chain.

The alkyl polyglycosides which can be used according to the invention can contain, for example, only one particular alkyl radical R ¹ . Usually, however, these compounds are made starting 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 particular work-up of these compounds.

Particularly preferred are those alkyl polyglycosides in which R '

• consisting essentially of C ₈ and C ₁₀ -alkyl groups,
• essentially of C ₁₂ and C ₁₄ alkyl groups,
• - Substituted from C ₈ -C ₁₆ alkyl groups or
• - Consists essentially of C ₁₂ -C ₁₆ alkyl groups.

As sugar building block Z it is possible to use any desired mono- or oligosaccharides. Usually, sugars with 5 or 6 carbon atoms and the corresponding Used oligosaccharides. 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 from 1.1 to 5 Sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. Quite be particularly preferred are alkyl glycosides in which x is 1.1 to 1.4.

The alkyl glycosides can also serve, in addition to their surfactant effect, the fixation of Improve fragrance components on the hair. The expert will therefore in the event that an over the duration of the hair treatment going beyond effect of the perfume oil on the Hair is desired, preferably to this class of substance as a further ingredient of he resort to inventive preparations.

The alkoxylated homologs of said alkylpolyglycosides can also be invented be used according to. These homologs can average up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.

Furthermore, zwitterionic surfactants can be used, in particular as cosurfactants. Zwitterionic surfactants are surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ^(-) or -SO ₃ ^(-) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl- 3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the Kokosacylaminoethylhy droxyethylcarboxymethylglycinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Also particularly suitable as co-surfactants are ampholytic surfactants. Ampholytic surfactants are those surface-active compounds which, apart from a C ₈ -C 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 enable the formation of internal salts are. 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 having about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, coco acylaminoethylaminopropionate and C _12-18 acyl sarcosine.

According to the invention, the cationic surfactants are in particular those of the quaternary type Ammonium compounds, the esterquats and the amidoamines used.

Preferred quaternary ammonium compounds are ammonium halides, in particular Chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and Trialkylmethylammoniumchloride, z. Cetyltrimethylammonium chloride, stea ryltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethyl ammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethyl ammonium chloride, as well as those under the INCI names Quaternium-27 and Quaternium-83 known imidazolium compounds. The long alkyl chains of the above surfactants mentioned preferably have 10 to 18 carbon atoms.

Esterquats are known substances which have at least one ester function and at least one quaternary ammonium group as a structural element.  

Preferred ester quats 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 will be For example, sold under the trademarks Stepantex®, Dehyquart® and Armocare®. The products Armocare® VGH-70, an N, N-bis (2-palmitoyloxyethyl) dimethyl ammonium chloride, as well as Dehyquart® F-75 and Dehyquart® AU-35 are examples of such Esterquats.

The alkylamidoamines are usually made by amidation of natural or synthetic Fatty acids and fatty acid sections prepared with dialkylaminoamines. An invention particularly suitable compound from this group of substances that under the name Tegoamid® S 18 is commercially available stearamidopropyl-dimethylamine.

Further cationic surfactants which can be used according to the invention are the quaternized Protein hydrolysates.

Likewise suitable according to the invention are cationic silicone oils, such as those described in US Pat Commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trim thylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-mo modified silicone, also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil® Quat 3270 and 3272 (Her steller: Th. Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80).

An example of a cationic surfactant usable quaternary sugar derivative is the Commercial product Glucquat®100, according to INCI nomenclature a "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride ".

The compounds used as surfactant with alkyl groups may be in each case act uniform substances. However, it is usually preferred in the production These substances are based on native plant or animal raw materials, so that one Substance mixtures with different alkyl chains depending on the respective raw material length receives.  

For the surfactants, the adducts of ethylene and / or propylene oxide to fat represent alcohols or derivatives of these addition products, both products with a "normal" homolog distribution as well as those with a narrow homologue distribution can be used. Under "normal" homolog distribution Mi understood by homologues, which are used in the reaction of fatty alcohol and Al ketylene oxide using alkali metals, alkali metal hydroxides or Alkalime obtains tallalkoholaten as catalysts. Narrow homolog distributions are opposed obtained, for example, when hydrotalcites, alkaline earth metal salts of ether carboxylic acids, Erd alkali metal oxides, hydroxides or alcoholates are used as catalysts. The Use of products with narrow homolog distribution may be preferred.

Furthermore, the agents according to the invention can preferably also have a conditioning Active ingredient selected from the group consisting of cationic surfactants, cationic Polymers, alkylamidoamines, paraffin oils, vegetable oils and synthetic oils is formed.

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

Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, as they are known under the names Celquat® and Po lymer JR® are commercially available. The compounds Celquat® H 100, Celquat® L 200 and Polymer JR®400 are preferred quaternized cellulose derivatives.
• - Dimethyldiallylammoniumsalze polymeric and their copolymers with acrylic acid and Esters and amides of acrylic acid and methacrylic acid. The under the names Merquat®100 (poly (dimethyldiallylammonium chloride)), Merquat®550 (dimethyldial lylammonium chloride-acrylamide copolymer) and Merquat® 280 (dimethyldiallyl ammonium chloride-acrylic acid copolymer are commercially available products Examples of such cationic polymers.
• - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino and methacrylate, such as vinylpyrrolidone quaternized with diethyl sulfate.  Dimethylaminomethacrylate copolymers. Such compounds are among the Designations Gafquat®734 and Gafquat®755 commercially available.
• - Vinylpyrrolidone-Methoimidazoliniumchlorid copolymers, as described under the name Luviquat®.
• - Quaternized polyvinyl alcohol

as well as those under the designations

• - Polyquaternium 2,
• - Polyquaternium 17,
• - Polyquaternium 18 and
• - Polyquaternium 27 known polymers with quaternary nitrogen atoms in the Po lymerhauptkette.

Particularly preferred are cationic polymers of the first four groups, completely Polyquaternium-2, polyquaternium-10 and polyquaternium-22 are particularly preferred.

As an alternative to the cationic polymers are used as conditioning agents zwitterionic or ampholytic polymers are particularly preferably used. preferred Representatives are octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2 Hydroxypropyl methacrylate copolymers, and in particular the acrylamidopropyl trimethylammonium chloride / acrylate copolymer.

Further suitable conditioning agents are silicone oils, in particular dialkyl and alkylarylsiloxanes such as dimethylpolysiloxane and methylphenylpolysi loxan, as well as their alkoxylated and quaternized analogs. Examples of such silicones are those of Dow Corning under the designations DC 190, DC 200, DC 344, DC 345 and DC 1401 distributed products and the commercial products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning® 929 emulsion (containing hydroxylamino-modified silicone, also referred to as amodimethicones), SM- 2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil® Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80).  

Also usable as conditioning agents are paraffin oils, synthetically prepared oligomeric alkenes and vegetable oils such as jojoba oil, sunflower oil, orange oil, Almond oil, wheat germ oil and peach kernel oil.

Likewise suitable hair conditioning compounds are phospholipids, for example Soy lecithin, E1 lecithin and cephaline.

Other active ingredients, auxiliaries and additives are, for example

• Nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, Polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes,
• Anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, Vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, Vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic acid anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
• - Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum ara bicum, karaya gum, locust bean gum, linseed gums, dextrans, cellulose Derivatives, e.g. Methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, Starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. B. Bentonite or fully synthetic hydrocolloids such. For example, polyvinyl alcohol,
• - structurants such as maleic acid and lactic acid,
• Hair-conditioning compounds such as phospholipids, for example soya lecithin, E1 Lecitin and Kephaline,
• Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids as well quaternized protein hydrolysates,
• Perfume oils, dimethylisosorbide and cyclodextrins,
• Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, Glycerine and diethylene glycol,
• - Fiber structure improving agents, in particular mono-, di- and oligosaccharides such for example, glucose, galactose, fructose, fructose and lactose,
• Quaternized amines such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate
• Defoamers like silicones,  
• Dyes for staining the agent,
• Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,
• - Sunscreens, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
• - Substances for adjusting the pH, such as conventional acids, in particular special edible acids and bases,
• - active substances such as allantoin, pyrrolidonecarboxylic acids and their salts, and bisabolol,
• Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , C, E, F and H,
• - plant extracts such as extracts of green tea, oak bark, stinging nettle, witch hazel, Hops, chamomile, burdock root, horsetail, hawthorn, lime blossom, almond, aloe Vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, Lime, wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, Meadowfoam, Quendel, Yarrow, Thyme, Melissa, Hauhechel, Coltsfoot, Marshmallow, meristem, ginseng and ginger root ,.
• - cholesterol,
• Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
• - fats and waxes such as spermaceti, beeswax, montan wax and paraffins,
• - fatty acid,
• Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,
• - Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, Hydrogencarbonates, guanidines, ureas as well as primary, secondary and tertiary phosphates,
• Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
• Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,
• - pigments,
• Stabilizer for hydrogen peroxide and other oxidizing agents,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - antioxidants.

Regarding further optional components as well as the amounts of this com Components are expressly based on the specialist manuals known to those skilled in the art, eg. B.  K. Schrader, Basics and Formulations of Cosmetics, 2nd Edition, Hüthig Buch Verlag, Heidelberg, 1989, referenced.

A third object of the invention is a kit for use in a process for dyeing keratin fibers, in particular human hair. The first embodiment is characterized in that the kit consists of the following separately packaged components:

• A pretreatment means M1 according to one of claims 8 or 18
• A colorant component M2a containing at least one oxidation dye Developer-type precursor and / or an indole and / or indoline derivative, as well as optionally at least one coupler type oxidation dye precursor.

In a preferred embodiment of this kit is additionally packaged separately Means comprising M2b, containing an oxidizing agent and / or enzyme.

In a second embodiment, a kit is claimed consisting of the following separately packaged components:

• A colorant component M2a containing at least one oxidation dye Developer-type precursor and / or an indole or indoline derivative as well optionally at least one coupler type oxidation dye precursor and / or a direct dye,
• An agent M3 containing at least one compound according to formula (I) or one of the corresponding physiologically acceptable salts.

In a preferred embodiment of this kit is additionally packaged separately Means comprising M2b, containing an oxidizing agent and / or enzyme.

In the agent M2b, an enzyme optionally together with an oxidizing agent used, it is preferred according to the invention, M2b in the solid state as a powder assemble.  

A fourth subject of the invention is the use of the kits according to the invention in a method for dyeing keratin fibers, in particular human hair.

The following examples are intended to illustrate the subject matter of the present application.

Examples 1. dyeing examples A) comparison dyeings A1) Preparation of the coloring creams

For the preparation of the reference staining cream or the comparative staining cream was always a Emulsion (mixture A) and a mixture B prepared. The reference dye cream contains only a single developer component. This developer became the Preparation of the comparative staining cream with a compound according to formula (I) in Molar ratio 1: 1 combined (Table 1, Ex. 1.A.1-1.A.5). In one Control experiment, only the compound according to formula (I) was used (Table 1, Ex. 1.A.6).

Partial mixture A

Hydrenol®D ¹ 8.50 g Coconut Chlorol® C12-18 ² 2,00 g Eumulgin®B2 ³ 0.75 g Texapon®NSO ⁴ 20.00 g Dehyton®K ⁵ 12.50 g water 30.00 g ¹ C ₁₆ -C ₁₈ fatty alcohol (INCI name: cetearyl alcohol) (COGNIS) @ ² C ₁₂ -C ₁₈ fatty alcohol (INCI name: Coconut alcohol) (COGNIS) @ ³ Cetearylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (COGNIS) @ ⁴ lauryl ether sulfate, sodium salt (about 27.5% active ingredient; (INCI name: Sodium Laureth Sulfate) (COGNIS) @ ⁵ N, N-dimethyl-N- (C ₈ -C ₁₈ -cocosamidopropyl) ammonium acetobetaine (about 30% active ingredient, INCI name: Aqua (Water), Cocamidopropyl Betaine) (COGNIS)

The substances Hydrenol®D, Kokoslorol®C12-18, Eumulgin®B2, Texapon®NSO and Dehyton®K were melted at 80 ° C, mixed with the 80 ° C hot water and emulsified with vigorous stirring. Thereafter, the emulsion was stirred gently cooled.

Partial mixture B

sodium 1.00 g ammonium sulfate 1.00 g dye precursors as indicated in Table 1 Ammonia (25% aqueous solution) ad pH 10 water 10.00 g

The dye precursors were in the 50 ° C hot water with the addition of Dissolved sodium sulfite and ammonium sulfate. The pH was adjusted to pH 10 with ammonia set.

The sub-mixture B was added with stirring to the mixture A and the resulting Dyeing cream filled up with water to 100 g and cooled to room temperature.  

A2) Coloring of the fibers

50 ml of the dyeing cream obtained according to A1) was mixed with in each case 100 ml of a 3% strength H ₂ O ₂ solution and applied to 5 cm strands of "Euronaturhaar blond" (Kerling). After 30 minutes exposure time at 32 ° C, the hair was rinsed, washed with a conventional shampoo and then dried.

The results are shown in Table 1. The listed CIELAB coordinates are a measure of L (brightness), a (color red-green component), b (color yellow-blue component), C (Chroma) and h (hue) and are calculated from the tristimulus values X, Y, Z which are again from the spectral distributions of the reflectance of the sample (H. G. Völz, Industrial Color Testing, VCH, Weinheim, 1990.).

Table 1

B) Dyeing with pyridoxine in combination with several couplers and developers B1) Preparation of the coloring creams

To prepare the dyeing creams 1 and 2, an emulsion (part mixture A) and the Prepared partial mixtures B for the coloring cream 1 and C for the coloring cream 2.

Partial mixture A

Hydrenol®D ¹ 8.50 g Coconut Chlorol® C12-18 ² 2,00 g Eumulgin®B2 ³ 0.75 g Texapon®NSO ⁴ 15.00 g Dehyton®K ⁵ 12.50 g water 30.00 g ¹ C ₁₆ -C ₁₈ fatty alcohol (INCI name: cetearyl alcohol) (COGNIS) @ ² C ₁₂ -C ₁₈ fatty alcohol (INCI name: Coconut alcohol) (COGNIS) @ ³ Cetearylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (COGNIS) @ ⁴ lauryl ether sulfate, sodium salt (about 27.5% active ingredient; (INCI name: Sodium Laureth Sulfate) (COGNIS) @ ⁵ N, N-dimethyl-N- (C ₈ -C ₁₈ -cocosamidopropyl) ammonium acetobetaine (about 30% active ingredient, INCI name: Aqua (Water), Cocamidopropyl Betaine) (COGNIS)

The substances Hydrenol®D, Kokoslorol®C12-18 and Eumulgin®B2 were at 80 ° C melted with the 80 ° C hot water containing Texapon®NSO and Dehyton®K, mixed and emulsified with vigorous stirring. Thereafter, the emulsion became weak Stirring cooled.  

Partial mixture B (for coloring cream 1)

sodium 1.00 g ammonium 1.00 g Turpinal ¹ SL® 0.12 g ascorbic acid 0.40 g L-arginine 1.00 g p-Toluylenediamine .H ₂ SO ₄ 242.3 mg 2-methyl 50.2 mg 4-chlororesorcinol 48.6 mg 2-methylamino-3-amino-6-methoxypyridine 3.5 mg Vitamin B6 (Pyridoxine.HCl) as indicated in Table 2 Ammonia (25% aqueous solution) ad pH = 8.4 water 10.00 g ¹ 1-Hydroxyethane-1,1-diphosphonic acid (INCI name: Etidronic Acid, Aqua (Water)) (COGNIS)

The dye precursors were in the 50 ° C hot water with the addition of Sodium sulfite, ammonium dihydrogen phosphate, Turpinal® SL, ascorbic acid and L-arginine solved. The pH was adjusted to 8.4 with ammonia.  

Partial mixture C (for coloring cream 2)

sodium 0.40 g ammonium 0.80 g Turpinal ¹ SL® 0.12 g ascorbic acid 0.40 g L-arginine 1.00 g Rodol ² 9R Base® 0.10 g p-Toluylenediamine .H ₂ SO ₄ 528.0 mg 2,4,5,6-tetraaminopyrimidine .H ₂ SO ₄ 528.0 mg 4-amino-3-methylphenol 864.0 mg 4-chlororesorcinol 144.0 mg 2,7-dihydroxynaphthalene 242.0 mg 2,6-di (hydroxyethylamino) toluene 66.0 mg Vitamin B6 (Pyridoxine.HCl) as indicated in Table 2 Ammonia (25% aqueous solution) ad pH = 8.6 water 10.00 g 2N HCl (aqueous solution) 3.5 ml ¹ 1-Hydroxyethane-1,1-diphosphonic acid (INCI name: Etidronic Acid, Aqua (Water)) (COGNIS) @ ² 6-Chloro-4-nitro-2-aminophenol (LOWENSTEIN)

The dye precursors were in the 50 ° C hot, with 3.5 ml of an aqueous 2N HCl Solution added water with the addition of sodium sulfite, ammonium dihydrogen phosphate, Turpinal® SL, ascorbic acid and L-arginine dissolved. The pH was increased with ammonia 8.6 set.

The coloring cream 1 was added to 50 g of the emulsion by adding partial mixture B. (Sub-mixture A) and then filled with water to 100 g. The Preparation of the coloring cream 2 was analogous, but instead of sub-mixture B was the Used sub-mixture C.

B2) Coloring of the fibers

50 ml of the dyeing creams obtained according to B1) were mixed with in each case 40 ml of a 5% H ₂ O ₂ solution and applied to 5 cm long human hair strands (natural white from the company Kerling). After 30 minutes exposure time at 32 ° C, the hair was rinsed, washed with a conventional shampoo and then dried.

The results are shown in Table 2.

Table 2

2. Evidence of the structuring effect of vitamin B6 with simultaneous application of vitamin B6 with the coloring agent A) Analysis method used: HP-DSC (High Pressure Differential Scanning Calorimetry)

Thermoanalytical investigations are particularly suitable for the characterization of Two-phase systems, to which the human hairs are used as fiber keratin with their crystalline α- Helix portion and amorphous matrix portion also belong. On the one hand can Glass transitions and aging behavior of the amorphous matrix are studied on the On the other hand, the melting behavior of the crystalline, helical phase provides important Findings. Thermoanalytical investigations are first described in 1899, first Differential Thermoanalysis (DTA) on protein fibers became the end of the fifties F. Schwenker, J.H. Dusenbury, Text Res. J. 1963, 30, page 800 et seq .; Felix, M.A. McDowall, H. Eyring, ibid. (1963), 33, page 465 ff.). In the following years are different thermoanalytical measuring methods, such as DTA, HP-DTA (High Pressure, High-pressure DTA) and DSC (differential scanning calorimetry, dynamic difference Calorimetry), applied to keratin fibers, for. B. the phenomenon of Supercontraction, α-β phase transitions of helices or denaturing events investigate. Recently, especially at the German wool research institute in  Aachen (F.J. Wortmann, H. Deutz, J. Appl. Polym. Sci. 1993, 48, 137ff.), The method The IIP-DSC used for the study of keratin fibers, the problems with pyrolytic Effects, as they occur in conventional DSC, and problems with the Data collection and interpretation as contained in the DTA rules out. In doing so, DSC Measurements on keratins made with water in commercially available, pressure-tight measuring capsules are included. In the keratin-water system develops when heated above 100 ° C in the encapsulated steel crucibles Water vapor high pressure, from which the HP-DSC analysis is derived. The serious one Difference in HP-DSC thermograms of human hair compared to normal DSC Thermograms is that of the endothermic peaks representing the transformation point and Reproduce conversion enthalpy, here by about 90 ° C to lower temperatures are shifted. This is due to the fact that the water penetrates into the hair fiber after diffusion Weakening and cleavage of hydrogen bonds and salt bonds the protein stability decreases and thus reduces the "gluing temperature" of the keratins. Become through the supercontracting agent such as water only hydrogen bonds and salt bridges dissolved, so the thermal effect is reversible (supercontraction). The process, however, becomes irreversible, as soon as covalent bonds, such. B. disulfide bridges are cleaved. This happens when heated human hair fibers in pressure-resistant capsules with water to above 150 ° C. The irreversible transformation, interpreted as transition of the α-helical regions into the Proteins in a disordered state, resulting in endothermic peaks, the Peak the conversion or denaturation point and the peak area Conversion or denaturation enthalpy.

Using differential scanning calorimetry (DSC) can therefore structural as well as chemical states and changes in fiber keratins and especially in human hair. Under well-defined test conditions can be in human hair, the calorimetric detectable processes using Record thermograms and them regarding the peak suits, structures and surfaces as Indicator for influencing order-disorder transitions due to changes internal and / or external parameters, cause z. B. by cosmetic treatment of Hair, use. Ie. from those recorded in the thermogram of human hair Endothermic peaks can be due to peak (transformation point) and peak area  (Conversion enthalpy) Statements about firmness or damage of the human hair fiber to meet.

Extensive studies on the influence of cystine content on the Denaturation of α-helices in keratins have e.g. For example, it has been shown that the denaturing Temperature (transition temperature) of keratin increases linearly with the cystine content. The increased stability of the matrix area due to the increased degree of crosslinking of the increased Proportion of disulfide bridges in the matrix causes the conversion of the into this matrix embedded helices is difficult and thus results in an increase in the Denaturation temperature. Conversely, a denaturation temperature and especially denaturation enthalpy reduction by perming or bleaching or staining treated human hairs are observed (H. Deutz, doctoral thesis, RWTH Aachen 1993).

B) implementation

Human hair (Alkinco 6634) was targeted by a permanent wave treatment (market product poly Lock extra strong perm; 40 minutes perm, 10 minutes fixation) damaged. Subsequently, the pretreated hair by means of a coloring cream with different Content of pyridoxine.HCl stained. The denaturation temperatures of the dyed hair samples were determined by HP-DSC thermoanalytically.  

B1) Preparation of the dyeing gel and dyeing of the fibers

For the preparation of the dyeing gel, a part mixture A and a part mixture B were prepared.

Partial mixture A

Coco Chlorol® C12-18 ¹ 8.00 g Edenor®PK 1805 ² 6.75 g Texapon®NSO-UP ³ 3.50 g Dehydol® LS 2 ^{4 </ 02844 00070 552 001000280000000200012000285910273300040 0002010120307 00004 02725SUP < 10.10 g Propylenglykol®-1,2-US 6.75 g isopropanol 16.50 g 1 C ₁₂ -C ₁₈ fatty alcohol (INCI name: Coconut alcohol) (COGNIS) @ 2 Oleic acid (INCI name: Oleic Acid) (COGNIS) @ 3 lauryl ether sulfate, sodium salt (about 27.5% active ingredient, pH 10-11.5; (INCI name: Sodium Laureth Sulfate) (COGNIS) @ 4 C12-14-fatty alcohol + 2-EO (INCI name: Laureth-2) (COGNIS) @ 5 propylene glycol (99.7%, INCI name: propylene glycol) (REININGHAUS CHEMIE)}

The components of sub-mixture A were mixed together at room temperature.  

Partial mixture B

sodium 0.40 g ascorbic acid 0.40 g Monoethanolamine 4.50 g L-arginine 1.00 g Gluadin® W 40 ¹ 1.00 g Turpinal ² SL® 0.20 g p-Toluylenediamine .H ₂ SO ₄ 0.19 g 2,4,5,6-tetraaminopyrimidine .H ₂ SO ₄ 1.62 g 4-amino-3-methyl phenol 57.0 mg 2-methyl 1.00 g 1- (β-hydroxyethylamino) -4-methyl-2-nitrobenzene 0.10 g Vitamin B6 (Pyridoxine.HCl) 0.80 g water 37.00 g ¹ wheat protein hydrolyzate (INCI name: Aqua (Water), Hydrolyzed Wheat Protein, Sodium Benzoate, Phenoxyethanol, Methylparaben, Propylparaben) (COGNIS) @ ² 1-Hydroxyethane-1,1-diphosphonic acid (INCI name: Etidronic Acid, Aqua (Water)) (COGNIS) @ ³ 6-Chloro-4-nitro-2-aminophenol.HCl (LOWENSTEIN DYES)

The staining gel was prepared by adding the partial mixture B to the partial mixture A.

B2) staining and analysis of hair samples

50 ml of a dyeing gel prepared according to B1) were mixed with 40 ml of a 5% H ₂ O ₂ solution (pH of the mixture: 9.5) and applied to 0.5 g of damaged human hair. After 30 minutes exposure time at 32 ° C, the hair was rinsed and then dried. HP-DSC measurements were then used to examine the restructuring effects of the active ingredients. The resulting denaturation temperatures are listed in Table 3.

Table 3

The denaturation temperature of the unstained, damaged reference hair sample was 147.2 ° C.

Claims (23)

1. A method for dyeing keratin fibers, in particular human hair, in which

• - If desired, a pretreatment agent M1 is applied to the fiber, then
• - a colorant M2 is used on the fiber, possibly immediately before application to the fiber:
  Component M2a, comprising at least one developer-type oxidation dye precursor and / or an indole and / or indoline derivative, and
  Component M2b, containing an oxidizing agent and / or an enzyme
  mixing, optionally adding to the individual agents M2a or M2b before the mixing or the mixing M2 another agent M3 and rinsing away this coloring agent M2 from the fiber after a period of 5-30 minutes, characterized in that at least one of the agents M1, M2a, M2b or M3 at least one compound according to formula (I),
  wherein
  A and B are each independently hydrogen, halogen, a C ₁ -C ₄ alkyl group, a C ₃ -C ₆ cycloalkyl group, a C ₁ -C ₄ monohydroxyalkyl group, a C ₂ -C ₄ oligohydroxyalkyl group, a C ₁ C ₄ aminoalkyl group, a group -OR or a group -NR ¹ R ² , in which R ¹ and R ² independently of one another represent hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -monohydroxyalkyl group, or R ¹ and R ² together with the nitrogen atom form a saturated ring,
  C represents a group -OR, -NR ¹ R ^2, -OP (O) (OR ³⁾ _2, a C ₁ -C ₄ - monohydroxyalkyl, a C ₂ -C ₄ oligohydroxyalkyl group or a C ₁ -C ₄ - alkyl group,
  D is a group -OR, a carboxy group, a C ₁ -C ₂₂ -alkoxycarbonyl group, a formyl radical, a group -CH ₂ OR or a group -CH ₂ - NR ₂ ,
  E is a group -OR, -OP (O) (OR ³ ) ₂ , a C ₁ -C ₄ -monohydroxyalkyl group or a C ₂ -C ₄ -oligohydroxyalkyl group,
  in which
  Each R is hydrogen, a C ₁ -C ₄ alkyl group, a C ₁ -C ₂₂ acyl group, a hydroxy C ₂ -C ₂₂ acyl group, a C ₂ -C ₁₀ carboxy acyl group, a C ₃ -C _10- oligocarboxyacyl group, an oligocarboxy monohydroxy-C ₃ -C ₁₀ acyl group, an oligocarboxy-oligohydroxy-C ₃ -C ₁₀ acyl group, a C ₃ -C ₈ cycloalkyl group, a C ₁ -C ₄ monohydroxyalkyl group, a C C ₂ -C ₄ oligohydroxyalkyl group, an aryl group which may contain a hydroxy, nitro or amino group, a heteroaromatic radical or a group -CH ₂ CH ₂ NR ¹ R ² , in which R ¹ and R ^{2 are} as defined above .
  Each R ³ is hydrogen or a C ₁ -C ₅ alkyl group,
  or one of the corresponding physiologically acceptable salts.

2. The method according to claim 1, characterized in that one of the two groups A or B is hydrogen. 3. The method according to any one of claims 1 or 2, characterized in that one of the two groups A or B is hydrogen and the other group is a C ₁ -C ₄ alkyl group. 4. The method according to any one of claims 1 to 3, characterized in that C is a hydroxy group, a C ₁ -C ₄ -Monohydroxyalkylgruppe or a C ₂ -C ₄ -Oligohydroxy alkyl group. 5. The method according to any one of claims 1 to 4, characterized in that D for a Hydroxymethyl group, a hydroxy group, a carboxy group or a formyl radical stands. 6. The method according to any one of claims 1 to 5, characterized in that E stands for a hydroxy group or a group -OP (O) (OH) ₂ . 7. The method according to any one of claims 1 to 6, characterized in that the Compound according to formula (I) is pyridoxine. 8. Means for use as pretreatment agent M1 in a process for dyeing of keratin fibers, in particular human hair, characterized in that it at least one compound according to claim 1 or one of the corresponding contains physiologically acceptable salts. 9. means for dyeing keratin fibers, in particular human hair, optionally for use as a colorant M2 in a method according to claim 1, containing at least one developer-type oxidation dye precursor thereby characterized in that it additionally comprises at least one compound according to claim 1 or contains one of the corresponding physiologically acceptable salts. 10. Composition according to claim 9, characterized in that the oxidation dye Developer type precursor is selected from the derivatives of p- Phenylenediamines, derivatives of pyrimidine, derivatives of pyrazole and of p- Aminophenol. 11. Composition according to claim 10, characterized in that the oxidation dye Developer-type precursor is selected from p-phenylenediamine, p- Toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, N, N-bis (β-hydroxyethyl) -p-  phenylenediamine, 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, 2,5,6-triaminopyrimidine, 4,5-diamino-1-methyl pyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1 (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1 phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5- hydrazino pyrazole, 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-hydroxy ethyl) -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-methyl-1-isopropylpyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethyl pyrazole, 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-methylpyrazole, p- Aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-2-amino methylphenol and 4-amino-2 - ((diethylamino) methyl) phenol. 12. Composition according to claim 11, characterized in that the oxidation dye Preproduct is selected from p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) - p-phenylenediamine and N, N-bis (β-hydroxyethyl) -p-phenylenediamine, 2,4,5,6- Tetraaminopyrimidine, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 4-amino-3-methylphenol and 4-amino-2-aminomethylphenol. 13. means for dyeing keratin fibers, in particular human hair, optionally for use as a colorant M2 in a method according to claim 1, containing at least one indole and / or indoline derivative, characterized in that it A compound according to claim 1 or one of the corresponding physiological contains compatible salts. 14. Composition according to claim 13, characterized in that the indole derivative is selected from 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N- Propyl 5,6-dihydroxyindole and N-butyl-5,6-dihydroxyindole.   15. Composition according to one of claims 13 or 14, characterized in that the Indoline derivative is selected from 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline and N-butyl-5,6- dihydroxyindoline. 16. Composition according to one of claims 9 to 15, characterized in that it continues contains a direct dye. 17. Composition according to one of claims 9 to 16, characterized in that it is a Contains oxidizing agent and / or an enzyme. 18. Composition according to one of claims 8 to 17, characterized in that it is a Acrylamidopropyltrimethylammonium chloride / acrylate copolymer contains. 19. Kit for use in a process for dyeing keratin fibers, in particular human hair, characterized in that it as separately packaged components
a pretreatment means M1 according to one of claims 8 or 18,
a colorant component M2a comprising at least one developer-type oxidation dye precursor and / or an indole and / or indoline derivative, and optionally at least one coupler type oxidation dye precursor
contains. 20. Kit according to claim 19 for use in a process for dyeing Keratin fibers, in particular human hair, characterized in that it is known as separately packaged component additionally an agent M2b, containing Contains oxidant and / or enzyme. 21. Kit for use in a process for dyeing keratin fibers, in particular human hair, characterized in that it as separately packaged components
a colorant component M2a comprising at least one developer-type oxidation dye precursor and / or an indole or indoline derivative and optionally at least one coupler-type oxidation dye precursor and / or a substantive dye,
an agent M3 containing at least one compound according to formula (I) or one of the corresponding physiologically acceptable salts. A kit according to claim 21 for use in a method of dyeing Keratin fibers, in particular human hair, characterized in that it is known as separately packaged component additionally an agent M2b, containing Contains oxidizing agent and / or an enzyme. 23. Use of the kit according to any one of claims 19 to 22 in a method for Coloring of keratin fibers, especially human hair.