AU2003282008A1 - Hair treatment agent - Google Patents

Description

IN THE MATTER OF Australian patent application based on International patent application (PCT/EP2003/00981 1) In the name of Henkel Kommanditgesellschaft auf Aktien DECLARATION 1, Pierre KIHN, 234 route d'Arlon, L-8010 STRASSEN, Grand-Duchy of Luxembourg, hereby declare: 1. That I am well acquainted with the German and English languages 2. That the attached document is, to the best of my knowledge and belief, a true and exact translation made by me from German into English of a document furnished to me as the authentic text of the International Patent Application identified above. Declared at Strassen, this 04.02.2005 Pie HN 1 H 05200 PCT RR/Tb Patente (VIP) Application number: PCT/EP2003/009811 Publication number: WO 2004/026272 Filing date: 04.09.2003 Publication date: Bulletin Number: Applicant: Henkel Kommanditgesellschaft auf Aktien HAIR TREATMENT AGENT The invention relates to the use of special combinations of active ingredients in hair treatment agents, an oxidizing hair-dyeing agent containing these combinations of active ingredients, a method for the oxidative dyeing of hair with this agent, as well as to the use of the agent for the gentle, oxidative dyeing of hair. These days, human hair is treated in various ways with cosmetic hair preparations. These treatments include, for example, the cleaning of hair with shampoos, the care and regeneration with rinses and cures, as well as the bleaching, dyeing and shaping of hair with dyeing agents, tinting agents, waving agents and styling preparations. In this connection, agents for changing and nuancing the color of hair play a prominent role. However, especially methods of dyeing hair, in addition to harmful environmental effects, may have a negative effect on the surface and damage the hair structurally. Structurally damaged hair frequently has a brittle, dull and unattractive appearance, which causes the consumer to be dissatisfied. Moreover, a series of dye precursors is known, which has an increased allergenic potential on the scalp and may cause allergic reactions in the consumer.

2 Other components, which are commonly used in the above mentioned hair treatment agents, may also produce allergic reactions on the skin and/or the scalp and/or be a strain on the hair. Examples of such components are certain perfumery oils, preservatives such as parabenes, and sulfites, certain surfactants, fatty alcohols such as wool wax and oxidation dye precursors (so called developer and coupling agent components), such as p-phenylenediamine or p-toluylenediamine. However, oxidizing agents, such as hydrogen peroxide, also have an irritating effect on the skin. Numerous attempts have therefore been made in the past to counteract the damage to the structure of the hair as well as the allergenic potential of some hair treatment and dyeing agents, in that restructuring substances or alternative materials were developed and used instead of the allergenic components. For this purpose, a plurality of care components was used, which were employed selectively for the after treatment of already damaged hair. A different variation includes the simultaneous treatment of the hair with a dyeing agent and a care component. For example, formulations are known, which contain one or more care components in a conventional, commercial fixing agent or dyeing agent. By these means, the damage to the hair during the treatment is to be minimized and already damaged hair is to be treated as gently as possible during the renewed treatment. Accordingly, the use of special amino acids as care materials was proposed in the DE-A1 -196 17 569. In a series of applications, such as the DE-A1-199 33 463, the Beiersdorf Company discloses skin care agents, which are based on ectoin and ectoin derivatives, as well as their use, predominantly in sunscreen formulations for the human skin. The optional use of ectoin or ectoin derivatives for the treatment of oxidatively damaged hair is also mentioned.

3 Ectoin and ectoin derivatives in cosmetic preparations for the treatment of aged and irritated skin are disclosed in the EP 671 161 Al. The WO 00/07560 claims the use of ectoin and certain derivatives of ectoin in cosmetic formulations for protecting the human skin against dryness and excessively high salt concentrations. Surprisingly, it has now been discovered that, with a completely novel combination of active ingredients, including at least one heterocyclic carboxylic acid derivative and at least one care component, damaged hair can be treated and restructured in a significant and unexpected manner. Within the scope of the invention, restructuring is understood to be a decrease in the damage to keratinic fibers, which has arisen due to various influences. In this connection, the restoration of the natural strength, for example, plays a significant role. Examples of damaging influences are permanent wave treatments, oxidative dyeings or bleaching the hair, as well as frequently washing, blow drying and combing the hair. Furthermore, damage may occur due to environmental effects, such as UV light. Restructured fibers are distinguished, for example, by an increased gloss, and improved handle and by a greater ease of combing. Furthermore, successful restructuring can be demonstrated physically by a melting point, which is higher than that of the damaged fibers. A method for demonstrating restructuring, which is referred to specifically in this application, was disclosed, for example, in the WO 01/21139. The object of the present invention therefore is the use of a combination of active ingredients, consisting of at least one compound of the general Formulas (I) or (II) 4

R

3 R3 N -(C-R 4 )n HN-(C-R 4 )1 RI N R 2

R

1 N R 2 H (I) (GI) and/or a physiologically acceptable salt and/or an isomeric or stereoisomeric form of these compounds, in which

R

1 represents a hydrogen atom, a branched or unbranched C1 - C4 alkyl group or a C2 - C4 hydroxyalkyl group,

R

2 represents a hydrogen atom, a -COOR 5 group or a -CO(NH)R 5 group, wherein R 5 represents a hydrogen atom, a C1 - C4 alkyl group, an amino acid group, a dipeptide or tripeptide group,

R

3 and R 4 , independently of one another, represent a hydrogen atom or a C1 C4 alkyl group or one of the two groups represents a hydroxy group and n represents an integer number from 1 to 3, and at least one further component, selected from the group formed by vitamins, provitamins, alkyl polyglucosides, allantoin and bisabolol, as well as the physiologically acceptable derivatives of these compounds, for the treatment of hair. Suitable, physiologically acceptable salts of the general compounds of Formulas (I) or (II) are, for example, the alkali, alkaline earth, ammonium, triethylamine or tris-(2-hydroxyethyl)amine salts, as well as those, which arise from the reaction of compounds of Formulas (I) or (1l) with inorganic or organic acids, such as hydrochloric acid, phosphoric acid, sulfuric acid, linear or branched, substituted or unsubstituted (for example by one or more hydroxy groups) C1 to C4 monocarboxylic or dicarboxylic acids, aromatic carboxylic acids and sulfonic acids, 5 such as acetic acid, citric acid, benzoic acid, maleic acid, fumaric acid, tartaric acid and p-toluenesulfonic acid. Examples of particularly preferred, physiologically acceptable salts are the sodium, potassium, magnesium, calcium and ammonium salts of the compounds of Formulas (I) or (II), as well as the salts, which result from the reaction of compounds of Formulas (1) or (1l) with hydrochloric acid, acetic acid, citric acid and benzoic acid. Pursuant to the invention, isomeric and stereoisomeric forms of the compounds of Formulas (1) or ( II) are understood to be all of the isomers, diastereoisomers, racemates, zwitterions, cations or mixtures thereof, which occur. The concept of amino acid is understood to include the stereoisomeric forms, such as the D and L forms of the following compounds: asparagine, arginine, aspartic acid, glutamine, glutamic acid, p-alanine, y-aminobutyrate, N,-acetyllysine, N8-acetylornithine, Ny-acetyldiaminobutyrate, N, acetyldiaminobutyrate, histidine, isoleucine, leucine, methionine, phenylalanine, serine, threonine and tyrosine. L-amino acids are preferred. Amino acid groups are derived from the corresponding amino acids. The following amino acids are preferred: gly, ala, thr, val, P-ala, y-aminobutyrate, asp, glu, asn, N,-acetyllysine, N6-acetylornithine, Ny-acetyldiaminobutyrate and N,-acetyldiaminobutyrate. The names of the amino acids are abbreviated in the generally customary manner. The di- or tripeptide groups chemically are acid amides and are decomposed by hydrolysis into 2 or 3 amino acids. The amino acids in the di or tripeptide group are linked together by amide bonds. Reference is explicitly made to the EP 0 671 161 Al of the Marbert Company with regard to the synthesis of the di- and tripeptide groups. Examples of di- and tripeptide groups are also disclosed in the EP 0 671161 Al.

6 Examples of Ci - C4 alkyl groups in the inventive compounds are methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl and t-butyl. Methyl and ethyl are the preferred alkyl groups, methyl being particularly preferred. Preferred C2 - C4 hydroxyalkyl groups are the 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl groups; 2-hydroxyethyl is a particularly preferred hydroxyalkyl group. The vitamin and provitamin components, preferred pursuant to the invention, are vitamin B3, vitamin B6, vitamin B12, vitamin C, vitamin E, vitamin F, provitamin B5, niacinamide and pantolactone. Especially preferred vitamins and provitamin components within the scope of the invention are vitamin C, vitamin B6, vitamin H, provitamin B5, niacinamide and pantolactone. Furthermore preferred is the use of the inventive combination of active ingredient in a ratio by weight of the compound of Formulas (I) or (11) to the alkyl polyglucosides of 1:1 to 1:3 and/or in a ratio by weight of the compound of Formulas (1) or (11) to the vitamins, provitamins, allantoin and/or bisabolol of 2:1 to 1:2. The use of compounds of Formulas (1) or (11), for which the R 1 group represents a methyl group, is also preferred.. Furthermore, the use of those compounds of the general Formulas (1) or (II) is favored pursuant to the invention, for which the R 2 group represents the -COOH group. The use of compounds of the general Formulas (1) or (II), for which the R 3 and R 4 groups represent hydrogen or, independently of one another, hydrogen or a hydroxy group, is also preferred.

7 Furthermore, the use of such compounds of the general Formulas (1) or (II), in which n is 2, is particularly preferred. The use of (S)-2-methyl-1,4,5,6-tetrahydro-4-pyrimidine carboxylic acid (ectoin) as compound of the general Formulas (1) or (II) as well as the physiologically acceptable salts of this compound, is particularly preferred. Likewise, the use of (S,S)-5-hydroxy-2-methyl-1,4,5,6-tetrahydro-4 pyrimidine carboxylic acid (hydroxyectoin) as compound of the general Formulas (1) or (II), as well as the physiologically acceptable salts of these compounds is also particularly preferred. The inventive combination of active ingredients, especially with ectoin or its physiologically acceptable salts as compound of the general Formulas (1) or (11), can be used pursuant to the invention in all agents employed for cleaning and treating hair. Examples of such hair-treatment agents are hair shampoos, hair rinses, hair cures, hair tonics, permanent waving and oxidative hair dyeing agents, hair dyeing shampoos, hair consolidators, hair setting agents, hairstyling preparations such as blow-drying lotions, foams consolidators, hair gels, hair waxes and other hair cleaning and treating agents. The use of the inventive combination of active ingredients in oxidative hair dyeing agents is especially preferred. Generally, the compounds of the general Formulas (I) or (II), especially ectoin or its physiologically acceptable salts, can be used in the hair cleaning, hair treating and hair dyeing agents in a concentration ranging from 0.01 to 5% by weight, based on the total weight of the agent.

8 Especially preferred is the use in an amount of 0.1 to 1% by weight of the compound of Formulas (1) or (II), especially of ectoin or its physiologically acceptable salts, based on the total weight of the agent. The use of combinations of active ingredients, for which the vitamin component is vitamin C or one of the physiologically acceptable derivatives of vitamin C, maybe preferred pursuant to the invention. Moreover, the use of those combinations of active ingredients is preferred pursuant to the invention, for which the provitamin is panthenol (provitamin 85) or a physiologically acceptable derivative of pro vitamin B5. In general, the vitamin and/or the provitamin component, as well as its physiologically acceptable derivatives, can be used in the hair cleaning, hair treating and hair dyeing agents in a concentration ranging from 0.01 5% by weight, based on the total weight of the agent. Especially preferred is the use of the vitamin and/or the pro vitamin component and its physiologically acceptable derivatives in an amount of 0.1 1% by weight. Preferred pursuant to the invention is the use of a combination of active ingredients, which contains, as alkyl polyglucosides component, a compound of the general formula R'O-(Z)x, in which R' represents an alkyl group with 6 to 22 carbon atoms, Z represents a sugar component and x represents 1.1 to 5 sugar units. Especially preferred are alkyl polyglucosides with a C12-c1 6 alkyl chain, a Ce sugar component and an x value of 1.4.

9 The use of the alkyl polyglucosides component in an amount of 0.1 to 10% by weight, based on the total weight of the agent, is preferred A further object of the invention is an oxidation dyeing agent, which, in a medium suitable for the dyeing, contains, aside from the inventive combination of active ingredients, a dye precursor, selected from the group of developer components. As oxidation dye precursor of the developer type, primary aromatic amines with a further free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrozones, 4 aminopyrazole derivatives as well as 2,4,5,6-tetraaminopyrimidine and its derivatives usually are used. Pursuant to the invention, the use of a p-phenylenediamine derivative or one of its physiologically acceptable salts may be preferred pursuant to the invention. Especially preferred are p-phenylenediamine derivatives of Formula (Ill)

NG'G

2 G G (IHI) NH-I wherein - G 1 represents a hydrogen atom, a C1 to C 4 alkyl group, a C1 to C4 monohydroxyalkyl group, a C 2 to C 4 polyhydroxyalkyl group, a (C 1 to C 4

)

alkoxy-(C1 to C 4 )-alkyl group, a 4'-aminophenyl group or a C1 to C 4 alkyl 10 group, which is substituted by a nitrogen-containing group, a phenyl group or a 4'-aminophenyl group, - G 2 represents a hydrogen atom, a C1 to C4 alkyl group, a C1 to C4 monohydroxyalkyl group, a C2 to C4 polyhydroxyalkyl group, a (C1 - C4) alkoxy-(C1 to C 4 )-alkyl group or a C1 to C4 alkyl group, 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 C1- to C 4 -alkyl group, a Ci- to C4 monohydroxyalkyl group, a C2- to C 4 -polyhydroxyalkyl group, a Ci- to C4 hydroxyalkoxy group, a Ci- to C 4 -acetylaminoalkoxy group, a C1- to C4 mesylaminoalkoxy group or a C1- to C 4 -carbamoylaminoalkoxy group; - G 4 represents a hydrogen atom, a halogen atom or a C1- to C 4 -alkyl group or - when G 3 and G 4 are in an ortho position to one another, they may jointly form a bridging xto-alkylene oxide group, for example, an ethylene oxide group. Examples of the C1 to C4 alkyl groups, named as substitutes in the inventive compounds, are the methyl, ethyl propyl, i-propyl and butyl groups, ethyl and methyl being preferred. C1 to C4 alkoxy groups, preferred pursuant to the invention, are, for example, a methoxy or ethoxy group. Furthermore, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl may be named as preferred examples of a Ci to C4 hydroxyalkyl group, a 2-hydroxyethyl group being particularly referred. The 1,2-dihydroxyethyl group is a particularly preferred C2 to C4 polyhydroxyalkyl group. Pursuant to the invention, fluorine, chlorine or bromine atoms are examples of a halogen atom, chlorine atoms being particularly preferred. The other concepts used can be derived, pursuant to the invention, from the definitions given here. Examples of nitrogen-containing groups of formula (El) are, in particular, the amino groups, C1 to C4 monoalkylamino 11 groups, C1 to C4 dialkylamino groups, C 1 to C4 trialkylammonium groups, C1 to C4 monohydroxyalkylammino groups imidazolinium and ammonium. Especially preferred p-phenylenediamines of Formula (111) are selected from p-phenylenediamine, p-toluylenediamine, 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-phenylene-diamine, N,N-diethyl-p phenylenediamine, N,N-dipropyl-p-phenylenediamine, 4-amino-3-methy-(N,N diethyl)-aniline, N,N-bis-(p-hydroxyethyl)-p-phenylenedi-amine, 4-N,N-bis-(p hydroxyethyl)-amino-2-methylaniline, 4-N,N-bis-(p-hydroxy-ethyl)-amino-2 chloroaniline, 2-(p-hydroxyethyl)-p-phenylenediamine, 2-(X,p-dihydroxyethyl)-p phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N-(p-hydroxypropyl)-p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N,N-dimethyl-3-methyl-p-phenylenediamine, N,N-(ethyl,p-hydroxyethyl)-p phenylenediamine, N-(p,y-dihydroxypropyl)-p-phenylenediamine, N-(4' aminophenyl)-p-phenylenediamine, N-phenyl-p-phenylenediamine, 2-(p hydroxyethyloxy)-p-phenylenediamine, 2-(p-acetylaminoethyloxy)-p-phenylenedi amine, N-(p-methoxyethyl)-p-phenylenediamine and 5,8-diaminobenzo-1,4 dioxane as well as from their physiologically acceptable salts. p-Phenylenediamine derivative of Formula (111), particularly preferred pursuant to the invention, are p-phenylenediamine, p-toluylenediamine, 2-(p hydroxyethyl)-p-phenylenediamine, 2-(a,p-dihydroxyethyl)-p-phenylenediamine and N,N-bis-(P-hydroxyethyl)-p-phenylenediamine. Furthermore, pursuant to the invention, it may be particularly preferred to use compounds, which contain at least two aromatic rings, which are substituted by amino and/or hydroxyl groups, as developer component.

12 The two-ring developer components, which are used pursuant to the invention in the dye compositions, may, in particular, be compounds, which correspond to the following Formula (IV), as well as their physiologically acceptable salts: -Y G (V Nz -4Y NGGG NG1G wherein: - Z and Z2, independently of one another, represent a hydroxyl or amino group, which optionally is substituted by a C1- to C 4 -alkyl group, by a C1- to

C

4 -hydroxyalkyl group and/or by a Y bridge or which optionally is part of a bridging ring system, - the Y bridge represents an alkylene group with 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which may be interrupted or terminated by one or more nitrogen-containing groups and/or one or more hetero atoms such as oxygen, sulfur or nitrogen atoms, and possibly substituted by one or more hydroxyl or C1 to C8 alkoxy groups, or a direct bond, - G 5 and G , independently of one another, represent a hydrogen or halogen atom, a Ci- to C 4 -alkyl group, a C1 to C4 monohydroxyalkyl group, a C2 to C4 polyhydroxyalkyl group, a C 1 to C4 aminoalkyl group or a direct connection to the Y bridge, - G 7 , G 8 , G 9 , G 10 , G" and G , independently of one another, represent a hydrogen atom, a direct bond to the Y bridge or a C1 to C4 alkyl group, with the proviso that 13

-

the compounds of Formula (IV) contain only one Y bridge per molecule and

.

the compounds of Formula (IV) contain at least one amino group, which carries at least one hydrogen atom. The substitutes, used in Formula (IV), are defined, pursuant to the invention, analogously to the above comments. Preferred, two-ring- developer components of Formula (IV) are, in particular, N,N'-bis-(3-hydroxyethyl)-N,N'-bis-(4'-aminophenyl)-1,3-diamino-2 propanol, N,N'-bis-(@-hydroxyethyl)-N,N'-bis-( 4 '-aminophenyl)-ethylenediamine, N,N'-bis-(4 -aminophenyl)-tetramethylenediamine, ,NN'-bis-(p-hydroxyethy)-N,N' bis-( 4 -aminophenyl)-tetramethylenediamine, N, N-bis-(4-methyl-aminophenyl) tetramethylene-diamine, N, N'-diethyl-N,N'-bis-(4'-amino-3'-methylphenyl) t eth h yne a m n e -d i a m n e ,, N ' -b i s -( 4 ' ethylenedi-amine, bis-(2-hydroxy-5-aminophenyl)-methane, N,N -s( am inophenyl)-1,4-diazacycloheptane, N,d1-bis-(2',' piperazine N-(4'-amino-phenyl)-p-phenylenediamine and 1,1O-bis-(2',5' diaminophenyl)-1,4,7,10-tetraoxa-decane and their physiologically acceptable salts. Particularly preferred two-ring developer components of Formula (IV) are N,N'-bis--hydroxyethyl)-N,N'-bis-(4'-aminophenyl)-1,3-diamino-2-propanol, bis-(2-hydroxy-5-aminophenyl)-me thane N,N'-bis-(4'-aminophenyl)-1,4-diazacyclo heptane and 1

,

1 0-bis-(2',5'-diaminophenyl)-1,4,7,10-tetraoxadecane or one of their physiologically acceptable salts. Furthermore, the use of a p-aminophenol derivative or of one of its physiologically acceptable salts as developer component may be preferred pursuant to the invention. Particularly preferred are p-aminophenol derivatives of Formula

(V)

14 OH 16 13 G G G NHG wherein: - G 13 represents a hydrogen atom, a halogen atom, a C1 to C4 alkyl group, a C1 to C4 monohydroxyalkyl group, a C2 to C4 polyhydroxyalkyl group, a (Ci to C 4 )-alkoxy-(C1- to C 4 )-alkyl group, a C1 to C4 aminoalkyl group, a hydroxy (C'1- to C 4 )-alkylamino group, a Ci to C4 hydroxyalkoxy group, a C1 to C4 hydroxyalkyl-(C1- to C 4 )-aminoalkyl group or a (di-Ci- to C 4 -alkylamino)-(C1 to C 4 )-alkyl group and - G4 represents a hydrogen or halogen atom, a C1 to C4 alkyl group, a C1 to C4 monohydroxyalkyl group, a C2 to C4 polyhydroxyalkyl group, a (C1- to

C

4 )-alkoxy-(C1- to C 4 )-alkyl group, a C1 to C4 aminoalkyl group or a Ci to C4 cyanoalkyl group, - G 15 represents hydrogen, a Ci to C4 alkyl group, a C1 to C4 monohydroxyalkyl group, a C2 to C4 polyhydroxyalkyl group, a phenyl group or a benzyl group and - G represents hydrogen or a halogen atom. Pursuant to the invention, the substituents, used in Formula (V), are defined analogously to the above comments. Preferred p-aminophenols of Formula (V) are, in particular, p-amino phenol, N-methyl-p-aminophenol, 4-amino-3-methyl-phenol, 4-amino-3-fluoro phenol, 2-hydroxy-methylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-(p-hydroxyethyoxy)-phenol, 4-amino-2-methylphenol, 4-amino-2 hydroxy-methylphenol, - 4-amino-2-methoxymethyl-phenol, 4-amino-2- 15 am inomethyl phenol, 4-amino-2-(p-hydroxyethyl-aminomethyl)-phenol, 4-amino-2 (cc,p-dihydroxyethyl)-phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 4 amirio-2,6-dichloro-phenol, 4-amino-2-(diethyl-aminomethyl)-phenol, as well as their physiologically acceptable salts. Particularly preferred compounds of Formula (V) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(a,p dihydroxy-ethyl)-phenol and 4-amino-2-(diethyl-aminomethyl)-phenol. Furthermore, the developer component may be selected from aminophenol and its derivatives, such as 2-amino-4-methylphenol, 2-amino-5 methylphenol or 2-amino-chlorophenol. Furthermore, the developer component may be selected from heterocyclic developer components, such as pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiologically acceptable salts. Preferred pyridine derivatives are, in particular, the compounds, which are described in the British patents 1 026 978 and 1 153 196, such as 2,5 diamino-pyridine, 2-(4'-methoxyphenyl)-amino-3-amino-pyridine, 2,3-diamino-6 methoxy-pyridine, 2-(p-methoxyethyl)-amino-3-amino-6-methoxy-pyridine and 3,4 diamino-pyridine. Preferred pyrimidine derivatives are, in particular, the compounds, which are described in the German patent DE 2,359,399, the Japanese document JP 02019576 A2 or in the Offenlegungsschrift WO 96/15765, such as 2,4,5,6 tetraamino-pyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6 triamino-pyrimidine, 2-dimethyl-amino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6 diaminopyrimidine and 2,5,6-triaminopyrimidine.

16 Preferred pyrazole derivatives are, in particular, the compounds, which are described in the patents DE 3,843,892, DE 4,133,957 and patent applications WO 94/08969, WO 94/08970, EP 740 931 and DE 195 43 988, such as 4,5-diamino-l-methylpyrazole, 4,5-diamino-1-(p-hydroxyethyl)-pyrazole, 3,4 diaminopyrazole, 4,5-diamino-1-(4'-chlorobenzyl)-pyrazole, 4,5-diamino-1,3 dimethylpyrazole, 4,5-diamino-3-methyl-1-phenyl-pyrazole, 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-t-butyl-1-methyl-pyrazole, 4,5-diamino-1 t-butyl-3-methylpyrazole, 4,5-diamino- 1 -(f-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-hydroxy methyl-1-methylpyrazole, 4,5-diamino-3-hyd roxymethyl-1 -isopropylpyrazole, 4,5 diamino-3-methyl-1 -isopropylpyrazole, 4-amino-5-(p-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-(p-hydroxyethyl) amino-1 -methylpyrazole. Preferred pyrazole-pyrimidine derivatives are, in particular, the derivatives of pyrazole-(1,5-a)-pyrimidine of the following Formula (VI) and its isomeric forms, if there is a tautomeric equilibrium:

(X

1 N 3 [-NG G 8 3 (VI) 6 N N, (HO)- 7 -[NG1 9

G

2 ], wherein: 17 - G, G, 18

G

1 " and G 20 , independently of one another, represent a hydrogen atom, a C1 to C4 alkyl group, an aryl group, a C1 to C4 hydroxyalkyl group, a C2 to C4 polyhydroxyalkyl group, a (C1- to C 4 )-alkoxy-(C1- to C 4 )-alkyl group, a C1- to C4 aminoalkyl group, which optionally may be protected by an acetyl ureide or a sulfonyl group, a (Ci- to C 4 )-alkylamino-(C1- to C 4 )-alkyl group, a di-((C1- to C 4 )-alkyl))-(Ci- to C 4 )-aminoalkyl group, the dialkyl groups optionally forming a carbon ring or a heterocyclic ring with 5 or 6 members, a Ci to C4 hydroxyalkyl or a di-(C 1 - to C 4 )-(hydroxyalkyl)-(C1- to C4) aminoalkyl group, - the X groups independently of one another represent a hydrogen atom, a C1 to C4 alkyl group, an aryl group, a Ci to C4 hydroxyalkyl group, a C2 to C4 poly-hydroxyalkyl group, a C1- to C4 aminoalkyl group, a (Ci- to C4) alkylamino-(C1- to C 4 )-alkyl group, a di-((C 1 - to C 4 )-alkyl)-(C1- to C4) aminoalkyl group, the dialkyl groups optionally forming a five-membered or six-membered alicyclic or heterocyclic ring, a C1 to C4 hydroxyalkyl or a di (C1- to C 4 -hydroxyalkyl)-aminoalkyl group, an amino group, a Ci to C4 alkyl or di-(C1- to C 4 -hydroxyalkyl)-amino group, a halogen atom, a carboxylic acid group or a sulfonic acid group. - i has a value of 0, 1, 2, or 3, - p has a value of 0 or 1 - q has a value of 0 or 1 and - n has a value of 0 or 1, with the proviso that the sum of p + q is not equal to 0, - when p + q = 2, n has a value of 0 and the NG 17

G

18 and NG 1 9

G

20 groups occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7); - when p + q = 1, the value of n is 1 and the NG 17

G

1 8 (or NG 19

G

20 ) groups and the OH group occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7).

18 The substituents, used in Formula (VI), are defined analogously as above. When the pyrazole-(1,5-a)-pyrimidine of the above Formula (VI) contains a hydroxy group at one of the positions 2, 5 or 7 of the ring system, there is a tautomeric equilibrium, which is shown, for example, in the following outline 17 19H]71 NG G I NGG N N, -N N~ OH O Of the pyrazole-(1,5-a)-pyrimidines of the above Formula (VI), the following are named in particular; - pyrazole-(1,5-a)-pyrimidine-3,7-diamine; - 2,5-dimethyl-pyrazole-(1,5-a)-pyrimidine-3,7-diamine; - pyrazole-(1,5-a)-pyrimidine-3,5-diamine; - 2,7-dimethyl-pyrazole-(1,5-a)-pyrimidine-3,5-diamine; - 3-aminopyrazole-(1,5-a)-pyrimidine-7-ol; - 3-aminopyrazole-(1,5-a)-pyrimidine-5-ol; - 2-(3-aminopyrazole-(1,5-a)-pyrimidine-7-ylamino)-ethanol; - 2-(7-aminopyrazole-(1,5-a)-pyrimidine-3-ylamino)-ethanol; - 2-(3-aminopyrazole-(1,5-a)-pyrimidine-7-yl)-(2-hydroxy-ethyl)-amino) ethanol; - 2-(7-aminopyrazole-(1,5-a)-pyrimidine-3-yl)-(2-hydroxy-ethyl)-amino) ethanol; - 5,6-dimethylpyrazole-(1,5-a)-pyrimidine-3,7-diamine; - 2,6-dimethylpyrazole-(1,5-a)-pyrimidine-3,7-diamine; 19 - 3-amino-7-dimethylamino-2,5-dimethylpyrazole-(1,5-a)-pyrimidine; as are their physiologically acceptable salts and their tautomeric forms, if there is a tautomeric equilibrium. The pyrazole-(1,5-a)-pyrimidines of the above Formula (VI) can be synthesized, as described in the literature, by cyclizing, starting out from an aminopyrazole or from hydrazine. In a further preferred embodiment, the inventive oxidation dyeing agents furthermore contain at least one dye precursor, selected from the group of coupler components. As oxidation dye precursors of the coupler type, usually m phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are used. Examples of such coupler components are: - m-aminophenol and its derivatives, such as 5-amino-2-methylphenol, 5-(3 hydroxypropylamino)-2-methylphenol), 3-amino-2-chloro-6-methylphenol, 2 hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoro acetylamino-2-chloro-6-methylphenol, 5-ami no-4-chloro-2-methylphenol, 5 am ino-4-methoxy-2-methylphenol, 5-(2'-hydroxyethyl)-amino-2-methyl phenol, 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 2,4-diaminophenoxyethanol, 1,3-bis-(2,4-diaminophenoxy)-propane, 1-methoxy-2-amino-4-(2'-hydroxy- 20 ethylamino)-benzene, 1,3-bis-(2,4-diaminophenyl)-propane, 2,6-bis-(2 hydroxyethylam ino)-1 -methylbenzene and 1-amino-3-bis-(2'-hydroxyethyl) amino-benzene, - o-diaminobenzene and its derivatives, such as 3,4-diaminobenzoic acid and 2,3-diamino-1 -methylbenzene, - dihydroxybenzene and 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-hydroxy pyridine, 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 1-naphthol, 2-methyl-1-naphthol, 2 hydroxymethyl-1 -naphthol, 2-hydroxyethyl-1 -naphthol, 1,5-dihydroxy naphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8 dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxy naphthalene, - morpholine derivatives, such as 6-hydroxybenzomorpholine and 6 aminobenzomorpholine, - quinoxaline derivatives, such as 6-methyl-1,2,3,4-tetrahydroquinoxaline, - pyrazole derivatives, such as 1-phenyl-3-methyl-5-pyrazolone, - indole derivatives, such as 4-hydroxyindole, 6-hydroxyindole and 7 hydroxyindole, - methylenedioxybenzene derivatives, such as 1-hydroxy-3,4-methylene dioxy benzene, 1-amino-3,4-methylenedioxybenzene and 1-(2' hydroxyethyl)-amino-3,4-methylenedioxybenzene.

21 In an embodiment, particularly preferred pursuant to the invention, the combination of active ingredients of the inventive oxidation hair-dyeing agent is combined with developer and coupler components, which are known to have no or only a slight allergenic potential. Preferred examples of such developer components are 3-methyl-4-aminophenol, 1-(2'-hydroxyethyl)-2,5-diaminobenzene, bis-(5-amino-2-hydroxyphenyl)-methane and tetraaminopyrimidine. Preferred examples of such coupler components are 4-chlororesorcinol, 2-aminophenol, 1,5 dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 5-amino-2-methylphenol, 1 phenyl-3-methyl-5-pyrazolone, 2,4-diaminophenoxyethanol, 2-methylresorcinol, 2 am ino-5-methylphenol, 3,4-methylenedioxyphenol, 2-amino-4-(2' hydroxyethylamino)-anisole, 3-amino-2-chloro-6-methylphenol, 1-(2' hydroxyethylamino)-3,4-methylenedioxybenzene, 3,4-methylenedioxyani line, 5 amino-4-chloro-2-methylphenol, 3-amino-2-methylamino-6-methoxypyridine, 2 amino-3-hydroxypyridine, 2,6-bis-(2'-hydroxyethyl)-aminotoluene, 4-hydroxy-2,5,6 triamino-pyrimidine, 1,10-bis-(2,5-diaminophenyl)-1,4,7,10-tetraoxadecane, In a further embodiment, preferred pursuant to the invention, the oxidation hair-dyeing agent has a pH ranging from 6 to 12 and especially from 8.5 to 11. An embodiment, which is furthermore preferred pursuant to the invention, comprises oxidation hair-dyeing agents, which contain the salt of benzoic acid and salicylic acid as preservatives. For further nuancing, substantive dyes may furthermore be added to the inventive oxidation hair-dyeing agent. Substantive dyes usually are nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Particularly suitable substantive dyes are those compounds known under the international 22 nomenclature or trade names as HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Orange 1, HC Red 1, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17, as well as 1,4-bis-(p-hydroxyethyl)-amino-2 nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4 tetra-hydroquinoxaline, hydroxyethyl-2-nitro-toluidine, picramic acid, 2-amino-6 chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid, 2-chloro-6-ethylamino-1 hydroxy-4-nitrobenzene, 4-(2'-hydroxyethylamino)-3-nitrophenol and 6-nitro 1,2,3,4-tetrahydroquinoxaline. Naturally occurring substantive dyes are, for example, the dyeing compounds contained in henna red, henna neutral, henna black, chamomile blossoms, sandalwood, black tea, alder bark, sage, campeachy wood, madder root, catechu, sedre and alkanet root. It is not necessary for the oxidation dye precursors or the substantive dyes to represent in each case uniform compounds. Rather, provided they do not disadvantageously affect the dyeing result or must be excluded for other reasons, such as toxicological reasons, the inventive hair dyeing agents may contain further components, resulting from the production methods for the individual dyes, in subordinate amounts. With regard to the dyes, which can be used in the inventive hair dyeing and tinting agents, explicit reference is made to the monograph of Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250; substantive dyes) as well as Chapter 8, pages 264-267; Oxidation Dye Precursors, issued as volume 7 of the series "Dermatology" (published by Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basle, 1986, as well as to the " Europaische Inventar der Kosmetik-Rohstoffe (European Inventory of Cosmetic Raw Materials)" published by 23 the European Community, attainable in diskette form from the Bundesverband Deutscher Industrie- und Handelsunternehmen fOr Arzneimittel, Reformwaren und Karperpflegemittel e.V., Mannheim. As precursors of dyes similar to natural product, indoles and indolines, for example, as well as their physiologically acceptable salts are used. Preferably, those indoles and indolines are used, which have at least one hydroxy or amino group, preferably as substituents on the six-membered ring. These groups may carry further substituents, for example, in the form of an etherification or esterification of the hydroxy group or an alkylation of the amino group. Particularly advantageous properties are exhibited by 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, 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline, such as 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindole-2 carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole. Within this group, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6 dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5,6-dihydroxyindoline, as well as N-methyl-5,6-dihydroxyindole, N ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6 dihydroxyindole, as well as especially 5,6-dihydroxyindole are particularly preferred. The indoline and indole derivatives are used in the dyeing agents used within the scope of the inventive method as free bases as well as in the form of their physiologically acceptable salts with inorganic or organic acids, such as the hydrochlorides, the sulfates and hydrobromides.

24 When dye precursors of the indoline-type or indole-type are used, it may be preferable to use these together with at least one amino acid and/or at least one oligopeptide. Aminocarboxylic acids, especially a-aminocarboxylic acids and o-aminocarboxylic acids are preferred amino acids. Of the a-aminocarboxylic acids, arginine, lysine, ornithine and histidine are particularly preferred. The use of arginine is especially preferred, particularly in free form, but also as the hydrochloride. Especially when the dyeing is oxidative, either with oxygen from the air or with other oxidizing agents such as hydrogen peroxide, the pH of the hair dyeing agent is usually adjusted to be weakly acidic to weakly alkaline, that is, to a range of about 5 to 12. For this purpose, the dyeing agents contain alkalizing agents, usually alkali or alkaline earth hydroxides, ammonia or organic amines. Preferred alkalizing agents are monoethanolamine, monoisopropanolamine, 2 amino-2-methyl-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3 propanediol, 2-amino-2-methylbutanol and triethanolamine as well as alkali and alkaline earth metal hydroxides. Especially monoethanolamine, triethanolamine, as well as 2-amino-2-methyl-propanol and 2-amino-2-methyl-1,3-propylene glycol are preferred within the scope of this group. It is also possible to use o-amino, such as o-aminocaproic acid as alkalizing agent is possible. If the actual hair dyes are formed within the scope of an oxidative process, conventional oxidizing agents, such as, in particular, hydrogen peroxide or its addition product with urea, melamine or sodium borate can be used. Oxidation with oxygen from the air as only oxidizing agent may, however, be preferred. Furthermore, it is possible to carry out the oxidation with the help of enzymes, the enzymes being used to produce oxidizing per-compounds as well as to reinforce the action of a small amount of oxidizing agent, which is present, or also with enzymes, which transfer electrons from suitable developer components (reducing agents) to oxygen from the air. In this connection, oxidases, such as 25 tyrosinase, ascoabate oxidase and laccase, and also glucose oxidase, uricase or pyruvate oxidase are preferred. Furthermore, the procedure of intensifying the action of small amounts (such as 1% and less, based on the total agent) of hydrogen peroxide by means of the peroxidases, is mentioned. Advisably, the preparation of oxidizing agent is then mixed immediately before the hair is dyed with the preparation of the dye precursors. Furthermore, the development of the dyeing can be supported and intensified owing to the fact that certain metal ions are added to the agent. Such metal ions are, for example, Zn2+, Cu 2 +, Fe2+, Fe 3 +, Mn 2 +, Mn 4 *, Li+, Mg 2 +, Ca2+ and Ala+, Zn2*, Cu2+ and Mn2+ being particularly preferred. In principle, the metal ions can be used in the form of any physiologically acceptable salt. Acetates, sulfates, halides, lactates and tartrates are preferred salts. Not only can the development of the dyeing be accelerated through the use of these metal salts, but the color nuance can also be affected selectively. The inventive oxidation hair-dyeing agents contain dye precursors preferably in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose of dyeing hair, such carriers are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions, such as, for example, shampoos, foam aerosols or other preparations, which are suitable for use on hair. It is, however, also conceivable to integrate the dye precursors in a powdery formulation or also in a tablet-shaped formulation. Within the scope of the present invention, aqueous-alcoholic solutions are understood to be aqueous solutions containing 3 to 70% by weight of a Ci to C4 alcohol, especially ethanol or isopropanol. The inventive agents may contain additional, other organic solvents, such as methoxybutanol, benzyl alcohol, ethylene glycol or 1,2-propylene glycol. In this connection, all water-soluble organic solvents are preferred.

26 The inventive agents may furthermore contain all active ingredients, additives and auxiliary materials, which are known for such preparations. In many cases, these agents contain at least one surfactant, anionic as well as zwitterionic, ampholyic, nonionic and catatonic surfactants being suitable in principle. In many cases, it has, however, proven to be advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants. In inventive preparations, all anionic surface active materials, which are suitable for use on the human body, are suitable as surfactants. These are characterized by a water-solubilizing, anionic group, such as a carboxylate, sulfate, sulfonate or phosphate group, and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester groups, ether groups and amide groups, as well as hydroxyl groups, may be contained in the molecule. Examples of suitable anionic surfactants are, always in the form of the sodium, potassium and ammonium salts, as well as in the form of the mono-, di and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group, - linear fatty acids with 10 to 22 carbon atoms (soaps), - ether carboxylic acids of the Formula R-O-(CH 2

-CH

2 0)x -CH 2 -COOH, in which R is a linear alkyl group with 10 to 22 carbon atoms and x = 0 or I to 16, - acyl sarcosides with 10 to 18 carbon atoms in the a acyl group, - acyl taurides with 10 or 18 carbon atoms in the acyl group, - acyl isethionate with 10 to 18 carbon atoms in the acyl group, - monoalkyl and dialkyl esters of sulfosuccinic acid with 8 to 18 carbon atoms in the alkyl group and monoalkyl polyethylene oxide esters of sulfosuccinic acid with 8 to 18 carbon atoms in the alkyl group and 1 to 6 ethylene oxide groups, - linear alkane sulfonates with 12 to 18 carbon atoms, - linear a-olefin sulfonates with 12 to 18 carbon atoms, - a-sulfofatty acid methyl esters, the fatty acids having 12 to 18 carbon atoms.

27 - alkyl sulfates and alkyl polyglycol ether sulfates of the Formula R-O-(CH 2 CH 2 0)r-SO 3 H, in which R is a preferably linear alkyl group with 10 to 18 carbon atoms and x = 0 or 1 to 12, - mixed, surface-active hydroxy sulfonates of DE-A-37 25 030, - -sulfated hydroxyalkyl polyethylene glycol ethers and/or hydroxyalkylene polypropylene glycol ethers of DE-A-37 23 354, - sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds of DE-A-39 26 344, - esters of tartaric acid and citric acid with alcohols, the products of the addition reaction of about 2-15 molecules of ethylene oxide and/or propylene oxide with fatty alcohols with 8 to 22 carbon atoms. Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, as well as, in particular, salts of saturated and, particularly, unsaturated C8-C22 carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid. Nonionic surfactants contain, for example, a polyol group, a polyalkylene glycol ether group or a combination of a polyol ether group and a polyglycol ether group. Such compounds are, for example, - products of the addition reaction between 2 to 30 moles of ethylene oxide and/or 0 to 5 moles of propylene oxide and linear fatty alcohols with 8 to 22 carbon atoms, and fatty acids with 12 to 22 carbon atoms and with alkylphenols with 8 to 15 carbon atoms in the alkyl group, - monoesters and diesters of C12-C22 fatty acids and the products of the addition reaction of 1 to 30 mol of ethylene oxide and glycerin, - C-C12 alkyl monoglycosides and oligoglycosides and their ethoxylated analogues, as well as 28 - products of the addition reaction of 5 to 60 moles of ethylene oxide and castor oil and hydrogenated castor oil. Preferred nonionic surfactants furthermore include alkyl polyglycosides of the general formula R'O-(Z)x. These compounds are characterized by the following parameters. The alkyl group R' contains 6 to 22 carbon atoms and may be linear as well as branched. Primary, linear aliphatic groups and linear aliphatic groups with a methyl group in the 2 position are preferred. Such alkyl groups are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1 decyl, 1-lauryl, 1-myristyl are particularly preferred. When so-called "oxo-alcohols" are used as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate. The alkyl polyglycosides, which can be used pursuant to the invention, may, for example, contain only a specific alkyl group R'. Usually, however, these compounds are synthesized starting from natural fats and oils or mineral oils. In this case, the alkyl groups R are mixtures corresponding to the starting materials or corresponding to the respective working up of these compounds. Particularly preferred are those alkyl poly glycosides, in which R' consists essentially of - C8- and C1o alkyl groups, - C12- and C14 alkyl groups, - C8-C16 alkyl groups or - C12-C16 alkyl groups As sugar building block Z, any monosaccharides or oligosaccharides may be used. Usually, sugars with 5 or 6 carbon atoms, as well as the 29 corresponding oligosaccharides are used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. Glucose, fructose, galactose, arabinose and sucrose are preferred sugar building blocks; glucose is particularly preferred. The alkyl polyglycosides, which can be used pursuant to the invention, contain, on the average, 1.1 to 5 sugar units. Alkyl polyglycosides with x values of 1.1 to 1.6 are preferred. Particularly preferred are alkyl glycosides, in which x has a value of 1.1 to 1.4. Aside from the surfactant effect, the alkyl glycosides may also improve the fixation of fragrance components in the hair. In the event that the effect of the perfume oil on the hair is to extend beyond the duration of the hair treatment, someone, skilled in the art, would resort to this class of substances as a further component of the inventive preparations. The alkoxylated homologs of the alkyl polyglycosides mentioned may also be use pursuant to the invention. On the average, these homologs may contain up to 10 units of ethylene oxide and/or propylene oxide per alkyl glycosides unit. Furthermore, zwitterionic surfactants can be used particularly as co surfactants. Those surface active compounds are described as zwitterionic surfactants, which contain at least one quaternary ammonium group and at least one -COOH(- or -SO3() group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N,N-dimethylammonium glycinate, for example, coconut alkyl-1-dimethylammonium glycinate, N-acyl aminopropyl-N,N-dimethylammonium glycinates, for example, coconut acylaminopropyl-dimethylammonium glycinate and 2-alkyl-3-carboxylmethyl-3 hydroxyethyl-imidazolines with, in each case, 8 to 18 carbon atoms in the alkyl or 30 acyl group, as well as the coconut acylaminoethylhydroxyethylcarboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative, which is known under the INCI name of cocoamidopropyl betaine. Likewise, ampholytic surfactants are suitable particularly as co surfactants. Ampholytic surfactants are understood to be those surface active compounds, which, in addition to a C8-C1 alkyl or acyl group, contain at least one free amino group and at least one carboxylic or sulfonic acid group in the molecule and are capable of forming an internal salt. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkylimino-dipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycine,

N

alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acids and alkylaminoacetic acids with, in each case, 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are the N-coconut alkylamino propionate, the coconut acylamino-ethylaminopropionate and the C12-18 acylsarcosin. Pursuant to the invention, surfactants of the quaternary ammonium compounds type, the esterquat type and the amidoamine type are used as cationic surfactants. Preferred quaternary ammonium compounds are the ammonium halides, especially the chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyl-dimethyl-ammonium chlorides and trialkylmethylammonium chlorides, for example, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds, known under the INCI names of Quaternium-27 and Quaternium-83. The long alkyl chains of the above-named surfactants preferably have 10 to 18 carbon atoms.

31 The esterquats are known materials, which contain at least one ester function as well as at least one quaternary ammonium group as structural elements. Preferred esterquats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-hydroxypropyldialkylamines. Such products are sold, for example, under the trade names of Stepanex*, Dehyquart* and Armocare*. The products Armocare® VGH-70, a N,N-bis(2 palmitoyloxy-ethyl)dimethylammonium chloride, as well as Dehyquart* F-75 and Dehyquart® AU-35 are examples of such esterquats. The alkylamidoamines are usually synthesized by the amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. The stearamidopropyldimethylamine, commercially obtainable under the name Tegoamid® S 18, is a compound of this group of substances, which is particularly suitable pursuant to the invention. The quaternized protein hydrolysates represent further cationic surfactants, which can be use pursuant to the invention Also suitable pursuant to the invention are cationic silicone oils, such as the commercially obtainable products Q2-7224 (manufactured by Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM-2059 (produced by General Electric), SLM-55067 (produced by Wacker) as well as Abil-Quat 3270 and 3272 (produced by Th. Goldschmidt; a diquaternary polydimethylsiloxane, Quaternium 80). An example of a quaternary sugar derivative, which can be used as a cationic surfactant, is the commercial product Glucquat® 100, which, according to 32 the INCL. nomenclature, is a "lauryl methyl Gluceth-10 hydroxypropyl dimonium chloride". The compounds with alkyl groups, used as surfactant, may in each case be uniform substances. However, as a rule, it is preferred to start out using natural vegetable or animal raw materials for producing these materials, so that substance mixtures with alkyl groups of chain length, which differ depending on the raw material, are obtained. For the surfactants, which represent the products of the addition reaction between ethylene oxide and/or propylene oxide and fatty alcohols or derivatives of these addition products, products with a "normal" distribution of homologs as well as those with a restricted distribution of homologs can be used. A "normal" distribution of homologs is understood to be a mixture of homologs, which is obtained by reacting fatty alcohol with alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates has catalysts. On the other hand, a restricted distribution of homologs is obtained if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids or alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a restricted distribution of homologs may be preferred. Furthermore, the inventive agents preferably may contain a conditioning ingredient, selected from the group formed by cationic surfactants, cationic polymers, alkylamidoamines, paraffin oils, vegetable oils and synthetic oils. Cationic polymers may be preferred as conditioning agreements. As a rule, these are polymers, which contain a quaternary nitrogen atom, for example, in the form of an ammonium group. Preferred cationic polymers are, for example - quaternized cellulose derivatives, like those obtainable commercially under the names Celquat* and Polymer JR*. The compounds Celquat* H 100, 33 Celquat* L 200 and Polymer JR*400 our preferred, quaternized cellulose derivatives, - polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid, as well as esters and amides of acrylic acid and methacrylic acid. The products, obtainable commercially under the names of Merquat*100 (poly(dimethyldiallylammonium chloride)), Merquat*550 (dimethyldiallyl ammonium chloride/acrylamide copolymer) and Merquat* 280 (dimethyldiallylammonium chloride/acrylic acid copolymer), are examples of such cationic polymers. -- Copolymers of vinyl pyrrolidone with quaternary derivatives of dialkylamino acrylates and methacrylates, such as vinyl pyrrolidone/dimethylamino methacrylate copolymers, quaternized with diethyl sulfate. Such compounds are commercially obtainable under the names of Gafquat* 734 and Gafquat* 755, - vinyl pyrrolidone/methoimidazolinium chloride copolymers, as offered under the name of Luviquat*, - quaternized polyvinyl alcohol as well as the polymers with quaternary nitrogen atoms in the main polymer chain, obtainable under the names of - polyquaternium 2, - polyquaternium 17, - polyquaternium 18 and - polyquaternium 27. Especially preferred are cationic polymers of the four aforementioned groups, polyquaternium-2, polyquaternium-10 and polyquaternium-22. Furthermore suitable as conditioning ingredients are silicone oils, especially dialkylsiloxanes and alkylarylsiloxanes, such as dimethylypolysiloxane and 34 methylphenylpolysiloxane, as well as there alkoxylated and quaternized analogues. Examples of such silicones are the products sold by Dow Corning under the names of DC 190, DC 200, DC 344, DC 345 and DC 1401, as well as the commercial products Q2-7224 (produced by Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning® 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM-2059 (produced by General Electric), SLM-55067 (produced by Wacker) as well Abil*-Quat 3270 and 2727 (produced by Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80). Likewise, synthetically produced oligomeric alkenes, as well as vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil and peach kernel oil may also be used as conditioning ingredients. Phospholipids, such as soybean lecithin, egg lecithin and cephalins are likewise suitable. Further active ingredients, auxiliary materials and additives are, for example - anionic polymers, such as vinyl pyrrolidone/vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone/vinyl acetate copolymers and polysiloxanes, - zwitterionic and amphoteric polymers, such as acrylamidopropyltrimethyl ammonium chloride/acrylate copolymers and octylacrylamide/methyl methacrylate/t-butylaminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers, - anionic polymers, such as polyacrylic acids, cross-linked polyacrylic acids, vinyl acetate/crotonic acid copolymers, vinyl pyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, 35 methyl vinyl ether/maleic anhydride copolymers and acrylic acid/ethyl acrylate/N-t-butyl acrylamide terpolymers, - thickening agents such as agar-agar, guar gum, alginates, xanthan gum, gum Arabic, Karaya gum, carob kernel flour, linseed gums, dextrans, cellulose derivatives such as methylcellulose, hyd roxyalkylcellulose and carboxy-methylcellulose, starch factions and derivatives, such as amylose, amylopectin and dextrins, clays, such as bentonite or fully synthetic hydrocolloids, such as polyvinyl alcohol, - structurants, such as maleic and lactic acids, - hair-conditioning compounds such as phospholipids, for example, soybean lecithin, egg lecithin and cephalins, - protein hydrolysates, especially elastin, collagen, keratin, casein, soybean protein and gluten hydrolysates, their condensation products with fatty acids, as well as quaternized protein hydrolysates, - perfume oils, dimethyl isosorbid and cyclodextrins, - solvents and solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol, - fiber structure-improving ingredients, especially mono-, di- and oligo saccharides such as glucose, galactose, fructose, levulose and lactose, - quaternized amines, such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate - defoamers, such as silicones, - dyes for coloring the agent, - anti-dandruff ingredients, such as piroctone olamines, zinc omadines and climbazole, - light-protection agents, especially derivativized benzophenones, cinnamic acid derivatives and triazines, - substances for adjusting the pH, such as conventional acids, especially edible acids and bases, 36 - plant extracts, such as the extracts of green tea, oak bark, nettles, witch hazel, hops, chamomile, bur root, horsetail, hawthorn, lime-tree blossoms, almond, aloe vera, fir needles, buckeye, sandalwood, juniper, coconut, mango, apricot, citron, wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, lady's-smock, thyme, common milfoil, thyme, balm, restharrow, hibiscus, meristem, ginseng and ginger root, - cholesterol, - thickeners such as sugar esters, polyol esters or polyol alkyl ethers, - fats and waxes such as spermaceti, beeswax, lignite wax and paraffins, - fatty acid alkanolamides, - complexing agents such as EDTA, NTA, P-alanine diacetic acid and phosphonic acids, - swelling agents and penetrants, such as glycerin, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas, as well as primary, secondary and tertiary phosphates, - opacifiers such as latex, styrene/PPP copolymers and styrene/acrylamide copolymers, - pearl gloss agents such as ethylene glycol monostearate and distearate, as well as PEG-3-distearate, - pigments - stabilizers for hydrogen peroxide and other oxidizing agents, - blowing agents such as propane-butane mixtures, N 2 0, dimethyl ether, carbon dioxide and air, - antioxidants. Reference is explicitly made to the relevant handbooks, known to those skilled in the art, such as Kh. Schrader, Grundlagen und Rezepturen der Kosmetika (Fundamentals and Formulations of Cosmetics), 2 nd edition, Hothig Buch Verlag, Heidelberg, 1989, with regard to further optional components.

37 A further object of the invention is a method for the oxidative dyeing of keratin fibers, especially of hair, using an inventive oxidation dyeing agent. The actual hair-dyeing agent advisably is prepared directly before use by mixing the preparation of the oxidizing agent with the preparation containing the dye precursors as well as the inventive combination of active ingredients. The thereby resulting, ready-for-use hair-dyeing preparation should preferably have a pH within the range of 6 to 12 and preferably of 8.5 to 11. The use of the hair-dyeing agents in an alkaline medium is particularly preferred. The application temperatures can range from 150 to 400C. After a period of action of 5 to 45 minutes, the hair-dyeing agent is removed by rinsing it from the hair, which is to be dyed. A subsequent washing with a shampoo is omitted when a carrier with a high surfactant content, such as a dyeing shampoo, was used. The actual oxidative dyeing of the fibers basically can be accomplished with oxygen from the air. Preferably, however, a chemical oxidizing agent is used, especially when a brightening effect on human hair, as well as a dyeing, is desired. As oxidizing agent, persulfates, chlorites, and especially hydrogen peroxide or its addition products with melamine as well as sodium borate come into consideration. Furthermore, it is possible to carry out the oxidation with the help of enzymes, the enzymes being used to produce oxidizing per compounds as well as to intensify the action of a small amount of oxidizing agents that are present. For example, the enzymes (enzyme class 1: oxidoreductases) can transfer electrons from suitable developer components (reducing agents) to the oxygen from air. In this connection, oxidases, such as tyrosinases, ascorbate oxidases and laccases, as well as glucose oxidases, uricases or pyruvate oxidases are preferred. Furthermore, the procedure is mentioned of intensifying the action of small amounts (such as 1% and less, based on the total agent) of hydrogen peroxide by peroxidases.

38 A further object of the invention is the use of inventive oxidation hair dyeing agents for gently dyeing keratinic fibers, especially hair. The following examples are intended to explain the object of the invention in greater detail. Examples The synergistic effect of ectoin with further care components was demonstrated by restructuring investigations of oxidatively or reductively damaged hair by means of thermal analysis in aqueous solution as well as in concrete application examples, such as shampoos or hair-dyeing agents. For this purpose, the hair was pretreated (damaged) as follows. Strands from the Alkino Company (0.5 g; code 6634; European human hair, middle brown) were subjected to a normal permanent waving treatment using the commercial product Poly Lock-Normale Dauerwelle. Within the course of this permanent waving treatment, the fibers, in a first step, were exposed for 40 minutes at room temperature to the reducing solution (containing 7.9% by weight of thioglycolic acid), rinsed with clean water and subsequently fixed for 10 minutes at room temperature (oxidizing solution, containing 2.6% by weight of hydrogen peroxide). After the oxidative treatment, the fibers were rinsed and dried. 1) Proof of synergistic action of ectoin and other care components from an aqueous solution at a a) pH of 4 Aqueous solutions of 1 % ectoin were mixed with different other active ingredients in 1% concentrations and adjusted to a pH of 4 with hydrochloric acid.

39 One of these solutions (2 mL) was applied, in each case, on one strand of Alkino 6634, left there for 10 minutes at room temperature and subsequently rinsed off for 1.5 minutes. After the strands had dried, the thermoanalytical measurement was carried out. For comparison, the corresponding solutions with the individual active ingredients were also measured. The following denaturing temperatures were detected: Denaturing Temperature (cC) Without Treatment Treatment Treatment Treatment Treatment Treatment with 1% with 1% with 1% with 1% with 1% Ectoin Allantoin Vitamin C Bisabolol Plantacare 1200 148.19 149.34 149.15 148.38 148.38 149.61 A 1.15 0.96 0.19 0.19 1.42 Subsequently, the strands of hair were treated with the solutions of the combined active ingredients ectoin and allantoin, ectoin and vitamin C, ectoin and bisabolol and ectoin and Plantacare (in each case 1% of the active ingredient) and the following denaturing temperatures were determined: Denaturing Aexpected Ameasured Temperature AEctoin + Aactive

(

0 C) ingredient Ectoin + Allantoin 150.60 2.11 2.41 Ectoin + Vitamin C 150.56 1.34 2.37 Ectoin + Bisabolol 149.67 1.34 1.48 Ectoin + Plantacare 150.29 2.57 2.10 1200 40 The measurements show that ectoin, in combination with allantoin, vitamin C and bisabolol, leads to a significantly higher care effect than does ectoin alone or also the three added active ingredients individually and that the care effect of ectoin, in the combination with Plantacare 1200, is below the value to be expected. aL pH of9 The strands of hair were pretreated and examined as already described under item a); the pH was adjusted to a value of 9 of the addition of monoethanolamine. The following results were obtained: Denaturing Temperature ( 0 C) Without Treatment Treatment Treatment Treatment with 1% with I% with 1% Ectoin Allantoin Plantacare 1200 145.27 147.02 145.77 145.99 A 1.75 0.5 0.72 Subsequently, strands of hair were treated with solutions of the combined active ingredients ectoin and allantoin, as well as ectoin and Plantacare (in each case, 1% of the active ingredient) and the following denaturing temperatures were determined: Denaturing Aexpected Ameasured Temperature AEctoin + Aactive ingredient (OC) Ectoin + Allantoin 148.17 2.25 2.90 Ectoin + Plantacare 148.34 2.47 3.07 1200 __ 41 The measurements show that the care performance of the combination of ectoin and allantoin is even higher, at an alkaline pH than in the acidic range and that the combination of ectoin and Plantacare 1200 also has a significant care performance in an alkaline medium, which was not observed in an acidic medium. 2) Detection of the synergistic effect of ectoin and other care components in a a) Shampoo Formulation After the pretreatment that was described under item 1), a standard shampoo (Provitamin B5-Schauma containing 0.2% of Panthenol) was mixed with 1% of ectoin. In addition, a further care material was added in further formulations. The Alkino 6634 strands (0.5 g) were treated for three minutes at room temperature with these formulations (2 g) and subsequently rinsed and dried The following results were achieved: Denaturing Temperature ( 0 C) Without Treatment Treatment Treatment Treatment Treatment with Schauma with Schauma with Schauma with Schauma Provitamin B5 Provitamin B5 Provitamin B5 Provitamin B5 Shampoo Shampoo and Shampoo and Shampoo and 1% Ectoin 1% Allantoin 1% Plantacare 1200 147.14 147.69 148.64 148.22 148.01 A 0.55 0.95 0.53 0.32 Thereupon, the strands of hair were treated with the Provitamin B5 shampoo, additionally containing the combined active ingredients of ectoin and allantoin, as well as of ectoin and Plantacare (in each case, 1% of the active ingredient) and the following denaturing temperatures were determined: 42 Denaturing Aexpected Ameasured Temperature AShampoo + AEctoin +

(

0 C) Aactive ingredient Ectoin + Allantoin 150.19 2.03 2.50 Ectoin + Plantacare 149.77 1.82 2.63 1200 The values show that the shampoo containing provitamin B5 but no ectoin already shows a tendency to restructure and that an increased effect is achieved by the addition of ectoin; however, a significantly higher (synergistic) effect is achieved by the combination of the materials. b) Oxidation Hair Dye After the pretreatment described under item 1), the formulation Poly Diadem Hellblond (without Plantacare) was mixed with 1% ectoin as well as with 1% of a different active ingredient. The commercial formulation Poly Diadem Hellblond, which already contains 1% of Plantacare 1200, was investigated as reference. Alkino 6634 strands of hair (0.5 g) were treated for 30 minutes at room temperature with these formulations and subsequently rinsed and dried. The subsequent DSC measurement provided the following results: Denaturing Temperature (CC) Treatment with Treatment with Treatment with Treatment with Poly Diadem Poly Diadem Poly Diadem Poly Diadem Hellblond Helliblond with Hellblond Heilbiond without Plantacare without without Plantacare (Commercial Plantacare and Plantacare and (oxidative hair Formulation) 1% Ectoin 1% Allantoin damage) 142.51 143.26 143.30 143.43 A 1 0.75 ] 0.79 J 0.92 43 Subsequently, the strands of hair were treated with the Poly Diadem Hellblond formulation containing the combined active ingredients of ectoin and allantoin, as well as ectoin and Plantacare (in each case, 1% of the active ingredient) and the following denaturing temperatures were determined: Denaturing Aexpected Ameasured Temperature AEctoin + Aactive ingredient

(

0 C) Ectoin + Allantoin 144.97 1.71 2.46 Ectoin + Plantacare 144.15 1.54 1.64 1200 In addition, the commercial formulation Poly Diadem Hellblond, which already contains Plantacare, was mixed with the combination of active ingredients ectoin and allantoin. From the first Table, a A of 2.46 would be expected. However, the denaturing temperature was determined to be 145.100C, which corresponds to a A of 2.59. The results as a whole confirm that the inventive combination of active ingredients restructures damaged hair synergistically and brings about a decrease in the oxidative damage during oxidative dyeing of hair.

Claims (30)

1. Use of a combination of active ingredients, consisting of at least one compound of the general Formula (I) or (11) R 3 N-(C-R4)n HN--(C-R4) RVKNR2 R<N 'R2 H and/or a physiologically acceptable salt and/or an isomeric or stereoisomeric form of these compounds, in which - RI represents a hydrogen atom, a branched or unbranched C1 - C4 alkyl group or a C2 - C4 hydroxyalkyl group, - R 2 represents a hydrogen atom, a -COOR 5 group or a -CO(NH)R 5 group, wherein R 5 represents a hydrogen atom, a C1 - C4 alkyl group, an amino acid group, a dipeptide or a tripeptide group, - R 3 and R 4 , independently of one another, represent a hydrogen atom or a C1 - C4 alkyl group or one of the two groups represents a hydroxy group and - n represents an integer number from 1 to 3, and at least one further component, selected from the group formed by vitamins, provitamins, alkyl polyglucosides, allantoin and bisabolol, as well as the physiologically acceptable derivatives of these compounds, for the treatment of hair. 45

2. The use of claim 1, characterized in that the ratio by weight of the compound of Formula (1) to the alkyl polyglucosides is 1:1 to 1:3 and/or the ratio by weight of the compound of Formula ((I) to the vitamins, pro vitamins, allantoin and/or bisabolol is 2:1 to 1:2.

3. The use of one of the claims 1 or 2, characterized in that R 1 represents a methyl group.

4. The use of one of the claims 1 to 3, characterized in that R 2 represents the COOH group.

5. The use of one of the claims 1 to 4, characterized in that R 3 and R 4 represent hydrogen.

6. The use of one of the claims 1 to 5, characterized in that n represents the integer number 2.

7. The use of one of the claims 1 to 6, characterized in that the compound of Formulas (I) or (11) is ectoin or one of its physiologically acceptable salts.

8. The use of one of the claims 1 to 7, characterized in that, quantitatively, the ectoin or its physiologically acceptable salts represent 0.01 to 5 % by weight of the total weight of the hair-treating agent.

9. The use of one of the claims 1 to 8, characterized in that, quantitatively, the ectoin or its physiologically acceptable salts represent 0.1 to 1% by weight of the total weight of the hair-treating agent.

10. The use of one -of the claims 1 to 9, characterized in that the vitamin component is vitamin C or one of its physiologically acceptable derivatives. 46

11. The use of one of the claims 1 to 10, characterized in that the provitamin is panthenol or one of its physiologically acceptable derivatives

12. The use of claims 10 or 11, characterized in that, quantitatively, the vitamin and/or the provitamin component amounts to 0.01 to 5% by weight of the total weight of the hair-treating agent.

13. The use of one of the claims 1 to 12, characterized in that the alkyl polyglucosides component represents a compound of the general formula R'O-(Z)x, in which R' represents an alkyl group with 6 to 22 carbon atoms, Z represents a sugar, component and x represents 1.1 to 5 sugar units.

14. The use of claim 13, characterized in that the alkyl polyglucoside component has a C12-C16 alkyl chain with a C6 sugar component and an x value of 1.4.

15. The use of claim 14, characterized in that, quantitatively, the C 12 -C16 fatty alcohol-1,4-glucoside amounts to 0.1 to 10% by weight, based on the total weight of the hair-treating agent.

16. The use of one of the claims 1 to 15, characterized in that the active ingredient combination is incorporated in hair shampoos, hair rinses, hair treatments, permanent waving and hair-dyeing agents, hair-dyeing shampoos, hair tonics, hair consolidators, hair-setting agents and/or hair styling preparations.

17. The use of claim 16, characterized in that the active ingredient combination is incorporated in an oxidative hair-dyeing agent. 47

18. Oxidizing hair-dyeing agent, characterized in that, in a medium suitable for dyeing, it contains the combination of active ingredients of one of the claims 1 to 14, as well as at least one dye precursor, selected from the group of developer components.

19. The oxidizing hair-dyeing agent of claim 18, characterized in that it contains at least one pyrimidine derivative and/or a physiologically acceptable salt of a pyrimidine derivative as dye precursor.

20. The oxidizing hair-dyeing agent of one of the claims 18 or 19, characterized in that it contains 2,4,5,6-tetraaminopyrimidine or a physiologically acceptable salt of this compound.

21. The oxidizing hair-dyeing agent of claim 18, characterized in that it contains 1 (2'-hydroxyethyl)-2,5-diaminobenzene or a physiologically acceptable salt of this compound.

22. The oxidizing hair-dyeing agent of claim 18, characterized in that it contains 3 methyl-4-aminophenol or a physiologically acceptable salt of this compound.

23. The oxidizing hair-dyeing agent of claim 18, characterized in that it contains bis-(2-hydroxy-5-aminophenyl)-methane or a physiologically acceptable salt of this compound.

24. The oxidizing hair-dyeing agent of one of the claims 18 to 23, characterized in that it furthermore contains a coupling agent component.

25. The oxidizing hair-dyeing agent of claim 24, characterized in that the coupling agent component is selected from 4-chlororesorcinol, 2-aminophenol, 1,5 dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 5-amino-2-methylphenol, 48 I -phenyl-3-methylpyrazole-5-one, 2-4-diaminophenoxyethanol, 2 methylresorcinol, 2-amino-5-methylphenol, 3,4-methylenedioxyphenol, 2 amino-4-(2'-hydroxyethylamjno)anisole, 3-amino-2-chloro-6-methylphenol, 1 (2'-hydroxyethylamino)-3,4-methylenedioxybenzene, 3,4 methylenedioxyaniline, 5-amino-4-chloro-2-methylphenol, 3-amino-2 methylamino-6-methoxypyridine, 2-amino-3-hydroxypyridine, 2,6-bis-(2' hydroxyethyl)aminotoluene, 4-hydroxy-2,5,6-triaminopyrimidiine, 1,10-bis-(2,5 diaminophenyl)-1,4,7,10-tetraoxadecane, as well as the physiologically acceptable salts of these compounds.

26. The oxidizing hair-dyeing agent of one of the claims 18 to 25, characterized in that it furthermore contains at least one substantive dyestuff, which is selected from the group comprising HC Yellow 4, HC Orange 1, HC Red 1, 4 (2'-hydroxyethylamino)-3-nitrophenol, 4-amino-2-nitro-diphenylamino-2' carboxylic acid, 2-amino-6-chloro-4-nitrophenol, 2-ethylamino-6-chloro-4 nitrophenol and 6-nitro-1,2,3,4-tetrahydroquinoxaline.

27. The oxidizing hair-dyeing agent of one of the claims 18 to 26, characterized in that it furthermore contains a dye, similar to a natural dye, form the group comprising indoles and indolines.

28. The oxidizing hair-dyeing agent of claim 27, characterized in that it contains a compound from the group comprising N-methyl-5,6-dihydroxyindoline, N ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 dihydroxyindoline, 5,6-dihydroxyindoline as well as N-methyl-5,6 dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and 5,6-dihydroxyindole 49

29. Method for the oxidative dyeing of hair, characterized in that an agent of one of the claims 18 to 28 is applied on the hair and, after a period of action, is rinsed out or washed out with a shampoo.

30. Use of an agent of one of the claims 18 to 28 for the gentle, oxidative dyeing of hair.