DE102006022274A1 - Agent, useful for e.g. reductive decoloration of dyed substrate e.g. polyester, polyamide and elastase, comprises a sulfinic acid derivative in a carrier in combination with a compound comprising a quaternary nitrogen atom - Google Patents

Abstract

Agent (A), for reductive decoloration, comprises at least a sulfinic acid derivative (I) in a carrier in combination with a compound comprising at least a quaternary nitrogen atom. Agent (A), for reductive decoloration, comprises at least a sulfinic acid derivative (I) of formula (MO-S(O)-R) in a carrier in combination with at least a quaternary nitrogen atom. M, M 1>-M 3>H or an equivalent of mono- or polyvalent cation; R : a peptide derivative, alkyl compound of formula (R 2>-C(Y 1>)(R 1>)-) (where R 1>and R 2>are not simultaneously H), (M 1>-S(O)-C(Y 2>)(R 14>)-X-C(Y 1>)(R 1>)-), R 10>-NH-CO-, R 13>-SO 2-NH-C(R 11>)(R 12>)- or a phenyl compound of formula (IV); Y 1>, Y 2>OH, -NH 2group or -NR 3>R 4>; R 3>, R 4>1-6C alkyl, 2-6C alkenyl, 1-6C (hydroxy)alkyl, 2-6C polyhydroxyalkyl, aryl or aryl-1-6C alkyl; X : a direct bond or an organic residue with two free valency; either R 1>, R 14>H, 1-6C alkyl or carboxyalkyl-(CH 2) m-COOM 2>; and R 2>H, 1-6C alkyl, carboxyalkyl-(CH 2) n-COOM 3>, 1-6C alkyloxycarbonyl, sulfonic acid group, carbamoyl group, N,N-di[(1-6C)-alkyl]carbamoyl, N,N,N-tri(1-6C alkyl)ammonium-1-6C alkyl, carboxy-2-6C alkenyl, cyano-1-6C alkyl, 1-6C alkoxycarbonyl-1-6C alkyl, aliphatic or aromatic heterocyclic, which is substituted, or (IV); or R 2>R 1>aliphatic 5-7-membered ring containing at least a cationic, quaternary nitrogen atom as a heteroatom, where the cationic load is compensated optionally through an equivalent mono- or polyvalent anions; R 7>carboxy group, sulfonic acid group, 1-6C alkoxycarbonyl, sulfonic amide, cyano, nitro, carboxy-1-6C alkyl, carboxy-1-6C alkoxy or an amine group of formula (-N +>RaRbRc); Ra, Rb, Rc : 1-6C alkyl, 2-6C alkenyl, aryl-1-6C alkyl or 1-6C hydroxyalkyl; R 8>, R 9>H, 1-6C alkyl, 2-6C alkenyl, 1-6C hydroxyalkyl, 2-6C polyhydroxyalkyl, 1-6C alkoxy, OH, amino, carboxy, nitro, cyano or halo; R 10>1-6C alkyl, optionally substituted (hetero)aryl, carboxy-1-6C alkyl, carboxy-2-6C alkenyl, 1-6C alkoxycarbonyl or 1-6C alkoxycarbonyl-1-6C alkyl; R 11>-R 13>H, 1-6C alkyl, 2-6C alkenyl, perfluorinated 1-6C alkyl, 3-6C cycloalkyl, optionally substituted (hetero)aryl, 1-6C hydroxyalkyl, 2-6C polyhydroxyalkyl, aryl-1-6C alkyl, carboxy-1-6C alkyl, carboxy-2-6C alkenyl or 1-6C alkoxycarbonyl-1-6C alkyl; n : 0-6; and m : 0-2. An independent claim is included for a procedure to the reductive decoloration of dyed substrates with natural- and/or synthetic dye comprising applying (A) on the dyed substrate and rinsing after an influential time. [Image].

Description

The This invention relates to reductive color proofing compositions which in addition to organic sulfinic acid derivatives at least one compound having at least one quaternary nitrogen atom, contain. These color proofing agents are suitable for the discoloration of colored substrates such as paper, Textiles and in particular keratin-containing fibers, for example human hair. Likewise, a process for decolorizing colored substrates, and the use of said color proofing agent Invention.

Nice always practiced colored or printed materials on humans a special charm. This fascination still exists today. Either a coloring offers one fashionable component, for example in the form of dyed textiles or dyed hair. Or the coloring, for example in the form of a print, serves to transmit information or art. The dyeing promotes cultural and social identity and is about it It is also a craft that has become lucrative over the years and innovative industries.

At the To dye The dye is applied to the substrate by adsorption to the surface, through Diffuse by formation on and / or in the substrate or transferred by chemical bonding. First, natural Dyes, such as. As purple or carmine used. By the rapid Advances in science have been made over the years for every application customized, synthetic dyes accessible. For dyeing, for example of paper, textiles or keratinous fibers, generally come either direct dyes or oxidation dyes in Question. Oxidative dyes are formed by oxidative coupling of a or multiple developer components with each other or with one or more coupler components. Coupler and developer components are also referred to as oxidation dye precursors. The oxidative Coupling is preferred during the dyeing process instead, so that the dye precursors diffuse into the substrate can and the dye forms in the substrate. Due to the size of the resulting dye molecule is difficult to wash out of the substrate.

When Developer components are commonly used primary aromatic amines with another, in para or ortho position free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used.

Specific Representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxamido-4-amino-pyrazol-5-one, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 4,5-diamino-1- (2-hydroxyethyl) pyrazole.

When Coupler components are usually m-phenylenediamine derivatives, Naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives. As coupler substances Particularly suitable are α-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, Resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4- (2-hydroxyethylamino) -anisole (Lehmann's Blue), 1-phenyl-3-methyl-pyrazol-5-one, 2,4-dichloro-3-aminophenol, 1,3-bis- (2,4-diaminophenoxy) -propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 3-amino-6-methoxy-2-methylamino-pyridine and 3,5-diamino-2,6-dimethoxypyridine.

Under substantive dyes are generally understood to be dyes, that already before the beginning of dyeing are preformed and raise to the substrate. Important representatives this class of dyes are, for example, triphenylmethane dyes, Azo dyes, anthraquinone dyes or nitrobenzene dyes, which can each carry cationic or anionic groups.

One In addition to dyeing, the important technical area is the removal of dyes This is generally understood as the removal of dyeings or printing by washing, chemical change or destruction of the dye. The oxidative or reductive decolorization of colored materials especially in decolorization of textiles or hair application.

Oxidative discoloration usually leads to good results. However, the structure of the substrate can be chemically altered by the strong oxidizing action of the decolorizing oxidizing agent. This is accompanied by an undesirable physical change of the substrate. Textiles or hair For example, they can become brittle or, in particular, even break if they are discolored several times. The visual impression, the feel as well as the durability of the substrate are negatively influenced.

Fewer Influence on the substrate structure, in particular on the structure keratinous fibers, take reductive decolorizing agents. The reductive decolorizing agent bleach hardly the natural hair color, but only affect the through coloring applied dyes reductively. It hardly occurs Brightening of the hair. However, the reductive decolorants require an improvement in decolouring performance.

Mostly Reductive sulfur compounds are used for decolorization. As is known, suitable dithionites or derivatives of 1-hydroxymethylsulfinic acid or of 1-aminomethylsulfinic acid as a reducing agent.

Out US-A-3 892 845 are color reductants which are skilled in the art known, with the help of colored keratin fibers bleach to let. As the reducing agent is 1-hydroxymethylsulfinic acid or a salt thereof in the decolorizing agents contain. According to DE-OS-1 617 829 leaves by adding 1-hydroxymethylsulfinic acid to oxidative decolorizing agents, containing hydrogen peroxide and persulfates, their bleaching action strengthen.

According to the disclosure of EP-A-1 079 018, aminoalkanesulfinates of the formula R ¹ _3-z N (CR ² R ³ -SO ₂ -M) _z (R ² , R ³ = hydrogen or (C ₁ to C ₄ ) - Alkyl) for the partial decolorization of dyed or printed with vat dyes or sulfur dyes textiles.

According to WO-A1-99 / 18067 1-hydroxyalkylsulfinic acids or 1-aminoalkylsulfinic acids are suitable which a carboxy group, a sulfonic acid group, an acyl group, an aminocarbonyl group or an alkoxycarbonyl group wear, for decolorization colored Substrates. Said derivatives have a comparable or better decoloring such as 1-hydroxymethylsulfinic acid (vide supra). In WO-A1-02 / 30369 the discovery is described, that deals with the sulfinic acid derivatives WO-A1-99 / 18067 also discolour keratin-containing fibers, such as hair. More for decolorization Keratinhaltiger fibers suitable sulfinic acid derivatives are found in the documents WO-A1-03 / 026597 and WO-A1-03 / 41668.

substrates those with the sulfinic acid derivatives of the prior art were reductively decoloured, some learn Time after color removal an unwanted darkening.

task It is the object of the present invention to provide reductive decolorizing agents provide that discolor the substrate permanently without darkening. The Substrate structure should be spared. Furthermore, the in the decolorizing agents used reducing agent for a cosmetic use physiologically acceptable and toxicologically harmless be.

Surprisingly The task is solved by means of a combination at least one of the organic according to the invention sulfinic acid derivatives with at least one compound containing at least one quaternary nitrogen atom contain. The discoloration colored Substrates, such as paper, textiles or keratin-containing Fibers, especially human hair, work very well without that itself after the Entfärbevorgang a dimming in the high setting as they go through the use of sulfinic acid derivatives is caused alone. The agents according to the invention are particularly suitable for fiber-sparing discoloration keratin-containing fibers.

Under keratin-containing fibers are for example wool, furs, feathers and especially to understand human hair.

worin
M steht für ein Wasserstoffatom oder ein Äquivalent eines ein- oder mehrwertigen Kations,
R sich ableitet von einem Peptid oder für einen Rest gemäß einer der Formeln (II) bis (VI) steht,

worin bedeuten
Y und Y' unabhängig voneinander eine Hydroxygruppe, eine -NH₂ Gruppe oder eine Gruppe -NR³R⁴, wobei R³ und R⁴ unabhängig voneinander für eine (C₁ bis C₆)-Alkylgruppe, eine (C₂ bis C₆)-Alkenylgruppe, eine (C₁ bis C₆)-Hydroxyalkylgruppe, eine (C₂ bis C₆)-Polyhydroxyalkylgruppe, eine Arylgruppe oder eine Aryl-(C₁ bis C₆)-alkylgruppe stehen,
M' unabhängig von M die unter M aufgeführten Merkmale,
X eine direkte Bindung oder einen organischen Rest mit zwei freien Valenzen,
R¹ und R¹⁴ unabhängig voneinander ein Wasserstoffatom, eine (C₁ bis C₆)-Alkylgruppe oder eine Carboxyalkylgruppe -(CH₂)_m-COOM^II, in der M^II für ein Wasserstoffatom oder für ein Äquivalent eines ein- oder mehrwertigen Kations steht und m die Zahl 0, 1 oder 2 bedeutet,
R² ein Wasserstoffatom, eine (C₁ bis C₆)-Alkylgruppe,
einen Carboxyalkylrest -(CH₂)_n-COOM^III mit
M^III = Wasserstoffatom oder ein Äquivalent eines ein- oder mehrwertigen Kations und n eine ganze Zahl 0, 1, 2, 3, 4, 5 oder 6,
einen (C₁ bis C₆)-Alkyloxycarbonylrest, eine Sulfonsäuregruppe, eine Carbamoylgruppe, eine N,N-Di[(C₁ bis C₆)-alkyl]carbamoylgruppe, eine N,N,N-Tri[(C₁ bis C₆)-alkyl]ammonium-(C₁ bis C₆)-alkylgruppe eine Carboxy-(C₂ bis C₆)-alkenylgruppe, eine Cyano-(C₁ bis C₆)-alkylgruppe oder eine (C₁ bis C₆)-Alkoxycarbonyl-(C₁ bis C₆)-alkylgruppe, einen aliphatischen oder aromatischen Heterozyklus, der substituiert sein kann, oder
einen Rest gemäß Formel (IV) oder
R² zusammen mit R¹ und dem Restmolekül einen aliphatischen 5-, 6-, oder 7-gliedrigen Ring bildet, welcher mindestens ein kationisches, quaterniertes Stickstoffatom als Heteroatom enthält, wobei die kationische Ladung gegebenenfalls durch ein Äquivalent eines ein- oder mehrwertigen Anions kompensiert wird,
R⁷ eine Carboxygruppe, eine Sulfonsäuregruppe, eine (C₁ bis C₆)-Alkoxycarbonylgruppe, eine Sulfonamidgruppe, eine Cyanogruppe, eine Nitrogruppe, eine Carboxy-(C₁ bis C₆)-alkylgruppe, eine Carboxy-(C₁ bis C₆)-alkoxygruppe oder eine Gruppe -N⁺R^IR^IIR^III
mit R^I, R^II und R^III stehen unabhängig voneinander für eine (C₁ bis C₆)-Alkylgruppe, eine (C₂ bis C₆)-Alkenylgruppe, eine Aryl(C₁ bis C₆)-alkylgruppe oder eine (C₁ bis C₆)-Hydroxyalkylgruppe,
R⁸ und R⁹ unabhängig voneinander ein Wasserstoffatom, eine (C₁ bis C₆)-Alkylgruppe, eine (C₂ bis C₆)-Alkenylgruppe, eine (C₁ bis C₆)-Hydroxyalkylgruppe, eine (C₂ bis C₆)-Polyhydroxyalkylgruppe, eine (C₁ bis C₆)-Alkoxygruppe, eine Hydroxygruppe, eine Aminogruppe, eine Carboxygruppe, eine Nitrogruppe, eine Cyanogruppe oder ein Halogenatom,
R¹⁰ eine (C₁ bis C₆)-Alkylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine gegebenenfalls substituierte Heteroarylgruppe, eine Carboxy-(C₁ bis C₆)-alkylgruppe, eine Carboxy-(C₂ bis C₆)-alkenylgruppe, eine (C₁ bis C₆)-Alkoxycarbonylgruppe oder eine (C₁ bis C₆)-Alkoxycarbonyl-(C₁ bis C₆)-alkylgruppe,
R¹¹, R¹² und R¹³ unabhängig voneinander ein Wasserstoffatom, eine (C₁ bis C₆)-Alkylgruppe, eine (C₂ bis C₆)-Alkenylgruppe, eine Perfluor-(C₁ bis C₆)-alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine gegebenenfalls substituierte Heteroarylgruppe, eine (C₁ bis C₆)-Hydroxyalkylgruppe, eine (C₂ bis C₆)-Polyhydroxyalkylgruppe, eine Aryl-(C₁ bis C₆)-alkylgruppe, eine Carboxy-(C₁ bis C₆)-alkylgruppe, eine Carboxy-(C₂ bis C₆)-alkenylgruppe oder eine (C₁ bis C₆)-Alkoxycarbonyl-(C₁ bis C₆)-alkylgruppe,
mit der Maßgabe, dass in Formel (II) R¹ und R² nicht gleichzeitig für ein Wasserstoffatom stehen.
in Kombination mit mindestens einer Verbindung, besitzend mindestens ein quartäres Stickstoffatom.A first subject of the invention is therefore compositions comprising in a carrier at least one sulfinic acid derivative of the formula (I)

wherein
M is a hydrogen atom or one equivalent of a mono- or polyvalent cation,
R is derived from a peptide or is a radical according to one of the formulas (II) to (VI),

in which mean
Y and Y 'independently of one another are a hydroxyl group, an -NH ₂ group or a group -NR ³ R ⁴ , where R ³ and R ⁴ independently of one another represent a (C ₁ to C ₆ ) -alkyl group, a (C ₂ to C ₆ ) Alkenyl group, a (C ₁ to C ₆ ) hydroxyalkyl group, a (C ₂ to C ₆ ) polyhydroxyalkyl group, an aryl group or an aryl (C ₁ to C ₆ ) alkyl group,
M 'independently of M the characteristics listed under M,
X is a direct bond or an organic radical having two free valences,
R ¹ and R ¹⁴ independently represent a hydrogen atom, a (C ₁ to C ₆ ) alkyl group or a carboxyalkyl group - (CH ₂ ) _m -COOM ^II , in which M ^{II represents} a hydrogen atom or one equivalent of a monovalent or polyvalent cation and m is the number 0, 1 or 2,
R ^{2 is} a hydrogen atom, a (C ₁ to C ₆ ) -alkyl group,
a carboxyalkyl radical - (CH ₂ ) _n -COOM ^III with
M ^III = hydrogen atom or one equivalent of a mono- or polyvalent cation and n is an integer 0, 1, 2, 3, 4, 5 or 6,
a (C ₁ to C ₆ ) alkyloxycarbonyl group, a sulfonic acid group, a carbamoyl group, an N, N-di [(C ₁ to C ₆ ) alkyl] carbamoyl group, an N, N, N-tri [(C ₁ to C ₆ ) -alkyl] ammonium (C ₁ to C ₆ ) -alkyl group a carboxy (C ₂ to C ₆ ) -alkenyl group, a cyano (C ₁ to C ₆ ) -alkyl group or a (C ₁ to C ₆ ) Alkoxycarbonyl (C ₁ to C ₆ ) alkyl group, an aliphatic or aromatic heterocycle which may be substituted, or
a radical according to formula (IV) or
R ^{2 forms,} together with R ¹ and the remainder of the molecule, an aliphatic 5-, 6- or 7-membered ring which contains at least one cationic, quaternized nitrogen atom as heteroatom, the cationic charge optionally being compensated by one equivalent of a mono- or polyvalent anion becomes,
R ^{7 is} a carboxy group, a sulfonic acid group, a (C ₁ to C ₆ ) alkoxycarbonyl group, a sulfonamide group, a cyano group, a nitro group, a carboxy (C ₁ to C ₆ ) alkyl group, a carboxy (C ₁ to C ₆ ) alkoxy group or a group -N ⁺ R ^I R ^II R ^III
R ¹ , R ^II and R ^III independently represent a (C ₁ to C ₆ ) alkyl group, a (C ₂ to C ₆ ) alkenyl group, an aryl (C ₁ to C ₆ ) alkyl group or a (C ₁ to C ₆ ) -hydroxyalkyl group,
R ⁸ and R ⁹ are each independently hydrogen, (C ₁ to C ₆ ) alkyl, (C ₂ to C ₆ ) alkenyl, (C ₁ to C ₆ ) hydroxyalkyl, (C ₂ to C ₆ ) Polyhydroxyalkyl group, (C ₁ to C ₆ ) alkoxy group, hydroxy group, amino group, carboxy group, nitro group, cyano group or halogen atom,
R ^{10 is} a (C ₁ to C ₆ ) alkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, a carboxy (C ₁ to C ₆ ) alkyl group, a carboxy (C ₂ to C ₆ ) alkenyl group, a (C ₁ to C ₆ ) alkoxycarbonyl group or a (C ₁ to C ₆ ) alkoxycarbonyl (C ₁ to C ₆ ) alkyl group,
R ¹¹ , R ¹² and R ¹³ independently of one another are a hydrogen atom, a (C ₁ to C ₆ ) -alkyl group, a (C ₂ to C ₆ ) -alkenyl group, a perfluoro (C ₁ to C ₆ ) -alkyl group, a ( C ₃ to C ₆ ) cycloalkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, a (C ₁ to C ₆ ) hydroxyalkyl group, a (C ₂ to C ₆ ) polyhydroxyalkyl group, an aryl (C ₁ to C ₆ ) alkyl group, a carboxy (C ₁ to C ₆ ) alkyl group, a carboxy (C ₂ to C ₆ ) alkenyl group or a (C ₁ to C ₆ ) alkoxycarbonyl (C ₁ to C ₆ ) alkyl group .
with the proviso that in formula (II) R ¹ and R ^{2 are} not simultaneously a hydrogen atom.
in combination with at least one compound possessing at least one quaternary nitrogen atom.

If the compounds according to formula (I) at least one chiral center are included, of course all stereoisomers alone and mixtures thereof, in particular their Racemates, according to the invention.

The compounds of formula (I) may be in addition to the form as the free acid or as its salt also be present as an inner salt, in particular if in addition to the sulfinate group of the formula (I) additionally contains a cationic substituent (see definition R ² and R ⁷ ) in the molecule.

aus Formel (I) bzw. mutatis mutandis aus Formel (III), bzw. der Carboxylat-Fragmente der Reste aus R bzw. R der Formel (II). Das dafür zu verwendende Äquivalent des entsprechenden Kations beträgt 1/z. Das Fragment MO- der Formel (I) bzw. das Fragment M'O- der Formel (III) stehen im Fall der Salzbildung für die Gruppe: 1/z (M^z+)^–O- bzw. die Gruppe: 1/z (M'^z+)^–O-. Gleiches gilt mutatis mutandis für M^II und M^III.When the compound of the formula (I) is present as acid, the radicals M, M ^I , M ^II and / or M ^{III represent} a hydrogen atom. The fragments MO of the formula (I), M'O- the formula (III) and M ^II O- or M ^III O- according to R ¹ or R ² of formula (II) form in this case a hydroxy group. When the sulfinic acid of the formula (I) is in the form of a salt, at least one of the radicals M, M ', M ^II or M ^{III represents} one equivalent of a monovalent or polyvalent cation. The monovalent or polyvalent cation M ^{z +} with a charge number z of one or higher serves, for reasons of electroneutrality, to compensate for the singly negative charge of the salt formation sulfinate fragment

from formula (I) or mutatis mutandis from formula (III), or the carboxylate fragments of the radicals from R or R of the formula (II). The equivalent of the corresponding cation to be used is 1 / z. The fragment MO of the formula (I) or the fragment M'O- of the formula (III) in the case of salt formation for the group: 1 / z (M ^{z +} ) ^- O- or the group: 1 / z ( M ' ^{z +} ) ^- O-. The same applies mutatis mutandis for M ^II and M ^III .

In principle, all cations which do not undergo a redox reaction with the remaining sulfinate fragment of the formula (I) are suitable as corresponding mono- or polyvalent cations. In particular, these are metal cations of the physiologically acceptable metals from groups Ia, Ib, IIa, IIb, IIIb, VIa or VIII of the Periodic Table of the Elements, ammonium ions, as well as cationic organic compounds with quaternized nitrogen atom. The latter are, for example, by protonation of primary, secondary or tertiary organic amines with an acid, such as. B. formed with compounds of formula (I) in their acidic form, or by permanent quaternization of said organic amines. Examples of these cationic organic ammonium compounds are 2-ammonioethanol and 2-trimethylammonioethanol. M, M ', M ^II and M ^III are preferably each independently a hydrogen atom, an ammonium ion, an alkali metal ion, half an equivalent of an alkaline earth metal ion or half an equivalent of a zinc ion, more preferably a hydrogen atom, an ammonium ion, a sodium ion Potassium ion, ½ calcium ion, ½ magnesium ion or ½ zinc ion.

The equivalent of the optionally present mono- or polyvalent anions according to formula (I) is described analogously to the definition of the cation equivalents to maintain the electroneutrality by formulating a stoichiometric coefficient of less than 1 before the name of the anion. Said anions are hereinafter defined as having at ^- symbolized. They are preferably selected from halide, ½ sulfate, hydrogen sulfate, ½ carbonate, hydrogen carbonate, 1/3 phosphate, ½ hydrogen phosphate, dihydrogen phosphate or p-toluenesulfonate. The anion is particularly preferably chloride, bromide, p-toluenesulfonate or hydrogen sulfate.

According to the invention, those sulfinic acid derivatives according to formula (I) are furthermore preferred in which the radicals Y of the formula (II) or formula (III) and Y 'of the formula (III) independently of one another represent a hydroxy group or a group -NH ₂ .

Sulfinic acid derivatives in which R ^{1 is} a hydrogen atom or a methyl group are preferred according to the invention.

Of the Rest R according to formula (I) must to solution the technical task for one of the radicals described above, it being preferred that that R for a radical of the above formulas (II) to (VI).

worin M, Y, R¹ und R² die unter den Formeln (I) und (II) definierte Bedeutung haben. Die zuvor erwähnten bevorzugten Definitionen der Reste M, Y und R¹ gelten auch hier, allein oder gemeinsam auf Formel (Ia) angewendet, als bevorzugt.If the radical R of the formula (I) is a radical of the abovementioned formula (II), then the preferred sulfinic acid derivative of the formula (Ia) according to the invention results from the formula (I) as the preferred first embodiment,

wherein M, Y, R ¹ and R ^{2 have} the meaning defined under the formulas (I) and (II). The aforementioned be Preferred definitions of the radicals M, Y and R ^{1 also} apply here, applied alone or together to formula (Ia), as being preferred.

It is according to the invention, when according to a preferred embodiment of the invention, the radical R ² according to formula (II) or formula (Ia) is an aliphatic or aromatic heterocycle, which may be optionally substituted. If the abovementioned selected aliphatic or aromatic heterocycles of this embodiment are substituted, these are preferably with at least one radical of (C ₁ to C ₆ ) -alkyl, (C ₂ to C ₆ ) -alkenyl, (C ₁ to C ₆ ) -Hydroxyalkyl, aryl- (C ₁ to C ₆ ) -alkyl, hydroxy, (C ₁ to C ₆ ) -alkoxy, amino, di (C ₁ to C ₆ ) alkylamino, nitro, halogen, carbamoyl, sulfonamido, cyano or carboxamido , substituted.

In the context of this embodiment, it is again preferable to select the aliphatic or aromatic heterocycles of the radical R ² from thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyrazyl, pyridazyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, indolyl, Quinolinyl, quinoxalinyl or quinazolinyl, which may optionally be substituted, preferably with the abovementioned substituents, particularly preferably with at least one radical of (C ₁ to C ₆ ) -alkyl, (C ₁ to C ₆ ) -hydroxyalkyl, hydroxy, amino, (C ₁ to C ₆ ) alkoxy, carboxy, halogen, nitro or sulfonic acid.

worin
M, Y und R¹ die unter Formel (I) definierten Bedeutungen haben,
Z¹ für ein Sauerstoffatom, ein Schwefelatom oder eine Gruppe N-R^IV steht, worin R^IV ein Wasserstoffatom, eine (C₁ bis C₆)-Alkylgruppe, eine (C₂ bis C₆)-Alkenylgruppe, eine (C₁ bis C₆)-Hydroxyalkylgruppe oder eine Aryl-(C₁ bis C₆)-alkylgruppe bedeutet,
Z² und Z³ unabhängig voneinander für eine Gruppe CH oder für ein Stickstoffatom stehen,
R⁵ und R⁶ unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₆)-Alkylgruppe, eine (C₂ bis C₆)-Alkenylgruppe, eine (C₁ bis C₆)-Hydroxyalkylgruppe, eine Hydroxygruppe, eine (C₁ bis C₆)-Alkoxygruppe, eine Aminogruppe, eine Di(C₁ bis C₆)alkylaminogruppe, eine Nitrogruppe, eine Halogenatom, eine Carbamoylgruppe, eine Sulfonamidogruppe, eine Cyanogruppe oder eine Carboxamidogruppe oder gemeinsam eine Benzanellierung bilden, welche wiederum substituiert sein kann.Particularly preferred sulfinic acid derivatives of this embodiment are compounds of the following formulas (Ia-1) to (Ia-4)

wherein
M, Y and R ^{1 have} the meanings defined under formula (I),
Z ^{1 represents} an oxygen atom, a sulfur atom or a group NR ^IV , wherein R ^{IV is} a hydrogen atom, a (C ₁ to C ₆ ) alkyl group, a (C ₂ to C ₆ ) alkenyl group, a (C ₁ to C ₆ ) -Hydroxyalkyl group or an aryl- (C ₁ to C ₆ ) -alkyl group,
Z ² and Z ³ independently of one another represent a CH group or a nitrogen atom,
R ⁵ and R ⁶ independently of one another represent a hydrogen atom, a (C ₁ to C ₆ ) -alkyl group, a (C ₂ to C ₆ ) -alkenyl group, a (C ₁ to C ₆ ) -hydroxyalkyl group, a hydroxy group, a (C ₁ to C ₆ ) -alkyl group C ₁ to C ₆ ) alkoxy group, an amino group, a di (C ₁ to C ₆ ) alkylamino group, a nitro group, a halogen atom, a carbamoyl group, a sulfonamido group, a cyano group or a carboxamido group, or together form a benzanellation, which in turn may be substituted can.

The group NR ^IV from residue Z ¹ forms an azandiyl group -NR ^IV - in the ring of the heterocycle. The group CH of the radicals Z ² or Z ³ forms in the ring of the heterocycle a methanylylidene group = CH-, which of course may also be substituted by one of the radicals R ⁵ or R ⁶ .

If in the formulas (Ia-1) or (Ia-2) Z ^{1 is} an oxygen atom, Z ^{2 is} a group CH and Y is a hydroxy group, it is preferred according to the invention, if in the formulas (Ia-1) or (Ia-2) R ⁵ and R ^{6 are} not simultaneously a hydrogen atom.

The aforementioned preferred definitions of the radicals M, Y and R ^{1 also} apply here, alone or together, to formulas (Ia-1) to (Ia-4), as being preferred.

The benzanellation from the radicals R ⁵ and R ^{6 of} the formula (Ia-1) to (Ia-4), when substituted, is preferably at least one radical of (C ₁ to C ₆ ) alkyl, (C ₂ to C ₆ ) alkenyl, (C ₁ to C ₆ ) -hydroxyalkyl, aryl- (C ₁ to C ₆ ) -alkyl, hydroxy, (C ₁ to C ₆ ) -alkoxy, amino, di (C ₁ to C ₆ ) alkylamino, nitro, halogen, carbamoyl, sulfonamido, cyano or carboxamido substituted.

R ⁵ and R ⁶ according to formulas (Ia-1) to (Ia-4) particularly preferably represent a hydrogen atom, a hydroxy group, a (C ₁ to C ₆ ) -alkyl group, a (C ₁ to C ₆ ) -alkoxy group, a (C ₁ to C ₆ ) hydroxyalkyl group, halogen atom or nitro group.

worin
Y die unter Formel (I) beschriebenen Definitionen bedeutet,
M die unter Formel (I) beschriebenen Definitionen oder eine negative Ladung bedeutet,
Z⁸, Z⁹ und Z¹⁰ einer dieser Reste eine Azoniumdiyl-Gruppe N⁺R^VR^VI bedeutet
mit R^V und R^VI stehen unabhängig voneinander für eine (C₁ bis C₆)-Alkylgruppe, eine (C₂ bis C₆)-Alkenylgruppe, eine (C₁ bis C₆)-Hydroxyalkylgruppe oder eine Aryl-(C₁ bis C₆)-alkylgruppe,
und die übrigen dieser Reste für eine CH₂-Gruppe stehen,
R¹⁷ und R¹⁸ unabhängig voneinander ein Wasserstoffatom, eine (C₁ bis C₆)-Alkylgruppe, eine Hydroxygruppe, ein Halogenatom oder eine Carboxygruppe bedeuten,
mit der Maßgabe, dass ein Äquivalent eines ein- oder mehrwertigen Anions zugegen ist, wenn M keine negative Ladung bedeutet.When the radicals R ¹ and R ² according to formula (II) in the first embodiment form, together with the remainder of the molecule, an aliphatic 5-, 6-, or 7-membered ring which contains at least one cationic, quaternized nitrogen atom as heteroatom Charge is optionally compensated by the one equivalent of a monovalent or polyvalent anion, the following compounds according to formulas (Ia-5) and (Ia-6) are preferred,

wherein
Y means the definitions described under formula (I),
M means the definitions described under formula (I) or a negative charge,
Z ⁸ , Z ⁹ and Z ¹⁰ one of these radicals represents an azonium diyl group N ⁺ R ^V R ^VI
R ^V and R ^VI independently represent a (C ₁ to C ₆ ) alkyl group, a (C ₂ to C ₆ ) alkenyl group, a (C ₁ to C ₆ ) hydroxyalkyl group or an aryl (C ₁ to C ₆ ) alkyl group,
and the remaining of these radicals represent a CH ₂ group,
R ¹⁷ and R ¹⁸ independently of one another denote a hydrogen atom, a (C ₁ to C ₆ ) -alkyl group, a hydroxy group, a halogen atom or a carboxy group,
with the proviso that one equivalent of a mono- or polyvalent anion is present when M is not a negative charge.

The CH ₂ group forms a methanediyl fragment -CH ₂ - in the ring of the heterocycle, which of course may also be substituted by one of the radicals R ¹⁷ or R ¹⁸ .

The previously mentioned preferred definitions of the radicals M and Y also apply here, alone or in common, applied to formulas (Ia-5) and (Ia-6), as preferred. The under the proviso described condition describes the formation of an internal salt, this is also a preferred embodiment represents.

worin,
M, Y, R¹, R⁷, R⁸ und R⁹ die unter Formel (I) genannten Bedeutungen haben.If the radical R ^{2 of} the formula (II) is a radical of the abovementioned formula (IV), the formula (i) results in the sulfinic acid derivative of the formula (Ia-7) according to the invention,

wherein,
M, Y, R ¹ , R ⁷ , R ⁸ and R ^{9 have} the meanings given under formula (I).

There are those compounds of formula (Ia-7) are preferred according to the invention in which the radical R ^{7 is} a carboxy group, a sulfonic acid group or a group -N ⁺ R ^I R ^II R ^III with R ^I , R ^II and R ^III are independently a (C ₁ to C ₆ ) alkyl group, a (C ₂ to C ₆ ) alkenyl group, an aryl (C ₁ to C ₆ ) alkyl group or a (C ₁ to C ₆ ) hydroxyalkyl group, and the radicals R ⁸ and R ^{9 represent} a hydrogen atom.

worin M, Y, R¹, n und M^III die unter Formel (I) und (II) genannten Bedeutungen haben. Die zuvor erwähnten bevorzugten Definitionen der Reste M, Y, R¹, n, und M^III gelten auch hier, allein oder gemeinsam auf Formel (Ia-8) angewendet, als bevorzugt.Further compounds of the formula (I) which are preferably used according to the invention are compounds of the formula (Ia-8)

wherein M, Y, R ¹ , n and M ^{III have} the meanings mentioned under formula (I) and (II). The aforementioned preferred definitions of the radicals M, Y, R ¹ , n, and M ^{III also} apply here, applied alone or together to formula (Ia-8), as being preferred.

It are over it addition, such compounds of the formula (Ia-8) are preferred according to the invention, in which Y represents a hydroxy or amino group.

Prefers n in formula (Ia-8) stands for a number 0, 1 or 2.

worin M, M', Y, Y', X, R¹ und R¹⁴ die unter den Formeln (I) und (III) definierte Bedeutung haben. Die zuvor erwähnten bevorzugten Definitionen der Reste M, M', Y, Y', X, R¹ und R¹⁴ gelten auch hier, allein oder gemeinsam auf Formel (Ib) angewendet, als bevorzugt.If the radical R of the formula (I) is a radical of the abovementioned formula (III), then the sulfinic acid derivative of the formula (Ib) according to the invention results from the formula (I) as preferred second embodiment of the invention,

wherein M, M ', Y, Y', X, R ¹ and R ^{14 have} the meaning defined under the formulas (I) and (III). The aforementioned preferred definitions of the radicals M, M ', Y, Y', X, R ¹ and R ^{14 also} apply here, applied alone or together to formula (Ib), as being preferred.

The radical X is preferably an organic radical having two free valencies. As radicals according to the invention are in principle all organodiyl radicals, such as. As aliphatic or alicyclic, aromatic or heteroaromatic diyl radicals. The said organic radical having two free valencies X according to formula (III) or formula (Ib) is preferably selected from the group consisting of optionally substituted radicals of arendiyl, heteroarylenediyl, alkanediyl, alkenediyl, cycloalkanediyl, cycloalkendiyl and di (( C ₁ to C ₆ ) alkylene) -substituted carbocyclic or heterocyclic groups which are aliphatic or aromatic. If the abovementioned selected radicals of this embodiment are substituted, these are preferably having at least one radical of (C ₁ to C ₆ ) -alkyl, (C ₂ to C ₆ ) -alkenyl, (C ₁ to C ₆ ) -hydroxyalkyl, Aryl (C ₁ to C ₆ ) alkyl, hydroxy, (C ₁ to C ₆ ) alkoxy, amino, di (C ₁ to C ₆ ) alkylamino, nitro, halogen, carbamoyl, sulfonamido, cyano or carboxamido substituted.

worin bedeuten
R¹⁵ und R¹⁶ unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine (C₁ bis C₆)-Alkylgruppe oder eine Carboxygruppe,
n eine ganze Zahl von 0 bis 6,
Z⁴ eine Gruppe CH₂, ein Sauerstoffatom, ein Schwefelatom oder eine Gruppe NR', mit R' = Wasserstoffatom, eine (C₁ bis C₆)-Alkylgruppe, eine (C₁ bis C₆)-Hydroxyalkylgruppe oder eine (C₂ bis C₆)-Polyhydroxyalkylgruppe,
Z⁵, Z⁶ und Z⁷ unabhängig voneinander eine Gruppe CH oder ein Stickstoffatom.It is particularly preferred according to the invention if the radical X of the formula (III) or of the formula (Ib) is an organic radical having two free valencies which consists of a (C ₁ to C ₆ ) -alkanediyl group or of radicals of the formulas ( VII) to (XI) is selected,

in which mean
R ¹⁵ and R ¹⁶ independently of one another represent a hydrogen atom, a halogen atom, a (C ₁ to C ₆ ) -alkyl group or a carboxy group,
n is an integer from 0 to 6,
Z ^{4 represents} a group CH ₂ , an oxygen atom, a sulfur atom or a group NR ', with R' = hydrogen atom, a (C ₁ to C ₆ ) -alkyl group, a (C ₁ to C ₆ ) -hydroxyalkyl group or a (C ₂ to C ₆ ) -polyhydroxyalkyl group,
Z ⁵ , Z ⁶ and Z ^{7 are} independently a group CH or a nitrogen atom.

The respective groups CH or CH _{2 of} the radicals Z ⁴ , Z ⁵ , Z ⁶ or Z ⁷ may of course also be substituted according to the invention with all substituents according to the invention within the definition of the formula concerned from the formulas (VII) to (XI).

If the organic radical with two free valencies X from the formulas (VII) and (VIII) the radicals are 2-chloro-cyclopentane-1,3-diyl, 2-bromo-cyclopentane-1,3-diyl, 2-chloro-cyclohexane-1,3-diyl and 2-bromo-cyclohexane-1,3-diyl preferred Representatives.

worin M, R⁷, R⁸ und R⁹ die unter den Formeln (I) und (IV) definierte Bedeutung haben. Die zuvor erwähnten bevorzugten Definitionen der Reste M, R⁷, R⁸ und R⁹ gelten auch hier, allein oder gemeinsam auf Formel (Ic) angewendet, als bevorzugt.If the radical R of the formula (I) is a radical of the abovementioned formula (IV), the formula (I) results in the sulfinic acid derivative of the third embodiment of the formula (Ic) according to the invention,

wherein M, R ⁷ , R ⁸ and R ^{9 have} the meaning defined under the formulas (I) and (IV). The aforementioned preferred definitions of the radicals M, R ⁷ , R ⁸ and R ^{9 also} apply here, applied alone or together to formula (Ic), as being preferred.

Especially R radicals of the formula are preferred (IV) that selected from 4-cyanophenyl, 4-carboxyphenyl, 4-carboxymethyloxy and 4-trimethylammoniophenyl.

worin,
M und R¹⁰ die unter Formel (I) genannten Bedeutungen haben. Die zuvor erwähnten bevorzugten Definitionen der Reste M und R¹⁰ gelten auch hier, allein oder gemeinsam auf Formel (Id) angewendet, als bevorzugt.If the radical R of the formula (I) is a radical of the abovementioned formula (V), the formula (I) results in the sulfinic acid derivative of the fourth embodiment according to the formula (Id) according to the invention,

wherein,
M and R ^{10 have} the meanings given under formula (I). The aforementioned preferred definitions of the radicals M and R ^{10 also} apply here, applied alone or together to formula (Id), as being preferred.

worin,
M, R¹¹, R¹² und R¹³ die unter Formel (I) genannten Bedeutungen haben. Die zuvor erwähnten bevorzugten Definitionen der Reste M, R¹¹, R¹² und R¹³ gelten auch hier, allein oder gemeinsam auf Formel (Ie) angewendet, als bevorzugt.If the radical R of the formula (I) is a radical of the abovementioned formula (VI), the formula (I) results in the sulfinic acid derivative of the fifth embodiment of the formula (Ie) according to the invention,

wherein,
M, R ¹¹ , R ¹² and R ^{13 have} the meanings given under formula (I). The aforementioned preferred definitions of the radicals M, R ¹¹ , R ¹² and R ^{13 also} apply here, applied alone or together to formula (Ie), as being preferred.

In the following, examples of the groups or radicals mentioned as substituents in the context of this application are mentioned. Examples of (C ₁ to C ₆ ) -alkyl radicals are linear, branched or cyclic (C ₁ to C ₆ ) -alkyl groups, preference being given to linear or branched (C ₁ to C ₆ ) -alkyl groups. In particular, the groups methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl and n-hexyl are suitable. Examples of correspondingly suitable cyclic alkyl groups are cyclopentyl and cyclohexyl.

Examples of preferred (C ₂ to C ₆ ) alkenyl radicals are vinyl, allyl and butenyl.

Preferred (C ₁ to C ₆ ) -alkoxy radicals according to the invention are, for example, a methoxy or an ethoxy group.

The methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl and tert-butoxycarbonyl groups are examples of (C ₁ to C ₆ ) alkoxycarbonyl groups; the methoxycarbonyl and ethoxycarbonyl groups are particularly preferred.

The 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-propoxycarbonylethyl, 2-isopropoxycarbonylethyl, 2-butoxycarbonylethyl, 2-sec-butoxycarbonylethyl, 2-tert-butoxycarbonylethyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 3-propoxycarbonylpropyl, 3-isopropoxycarbonylpropyl, 3-butoxycarbo nylpropyl, 3-sec-butoxycarbonylpropyl and 3-tert-butoxycarbonylpropyl groups are examples of (C ₁ to C ₆ ) alkoxycarbonyl (C ₁ to C ₆ ) alkyl groups.

Examples of cyano (C ₁ to C ₆ ) alkyl groups according to the invention are cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl and 5-cyanopentyl.

Further, as preferable examples of a (C ₁ to C ₆ ) monohydroxyalkyl group, there may be mentioned hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl and 6 -Hydroxyhexyl group. A 2-hydroxyethyl group is particularly preferred.

Examples of a (C ₂ to C ₆ ) polyhydroxyalkyl group are the 2,3-dihydroxypropyl group, 3,4-dihydroxybutyl group and the 2,4-dihydroxybutyl group.

The methoxyethyl, ethoxyethyl, methoxypropyl, methoxybutyl, ethoxybutyl and methoxyhexyl groups are examples of (C ₁ to C ₆ ) alkoxy (C ₁ to C ₆ ) alkyl groups according to the invention.

A preferred hydroxy (C ₁ to C ₆ ) alkoxy group is the 2-hydroxyethoxy group. Preferred aryl groups are phenyl, naphthyl and biphenyl.

preferred Heteroaryl groups are thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, Oxazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyrazyl, pyridazyl, benzimidazolyl, Benzothiazolyl, benzoxazolyl, indolyl, quinolinyl, quinoxalinyl and quinazolinyl.

The trifluoromethyl and pentafluoroethyl groups are preferred perfluoro (C ₁ to C ₆ ) alkyl groups.

Examples for halogen atoms are F, Cl, Br or I atoms, with Cl and Br atoms being most preferred are.

Preferred aryl (C ₁ to C ₆ ) alkyl groups are benzyl and 2-phenylethyl.

The trimethylammonium and diethylmethylammonium examples of a group -N ⁺ R ^I R ^II R ^III .

The 2-trimethylammoniumethyl is an example of an N, N, N-tri [(C ₁ to C ₆ ) -alkyl] ammonium (C ₁ to C ₆ ) alkyl group.

A preferred (C ₁ to C ₆ ) carboxyalkyl group is the 3-carboxypropyl group.

The other terms used are derived from the invention definitions given here.

Very particularly preferred representatives of the sulfinic acid derivatives of the formula (I) are the sulfinic acids according to the list below or salts thereof with one equivalent of at least one mono- or polyvalent cation:

For the preferred mono- or meridian cations of all salts of the aforementioned compounds the above applies.

The Preparation of the invention used sulfinic of the formula (I) takes place, for example, from the reaction of dithionite with corresponding aldehydes or ketones analogously to the preparation according to WO-A1-99 / 18067.

Prefers contains the agent of the invention at least one sulfinic acid derivative of the formula (I) in an amount of 0.01 to 20% by weight, especially preferably from 1 to 20 wt .-%, each based on the weight of ready to use agent.

Under Compounds possessing at least one quaternary nitrogen atom understand For the purposes of the invention, all chemical compounds which are at least a quaternary, bear cationic nitrogen atom. These are also called quaternary ammonium compounds designated. The quaternary Nitrogen atom is vierbindig. Thus, quaternary ammonium radicals and quaternary iminium radicals includes. The to the quaternary Nitrogen atom-binding groups are all different from hydrogen and form at least three bonds to carbon atoms of organic Leftovers out.

said Compounds possessing at least one quaternary nitrogen atom are of the sulfinic acids of Formula (I) different.

The agents according to the invention preferably contain at least one compound possessing at least a quaternary Nitrogen atom, selected from the group formed from compounds containing a quaternary nitrogen atom, Compounds with two quaternaries Nitrogen atoms, compounds with three quaternary nitrogen atoms, organic N-oxides and polymers derived from a monomer containing at least one quaternary Nitrogen atom.

Either in general as well all representatives of the previous list are preferred if the Compounds with quaternary Nitrogen atom are net cationically charged. The said connections lie in the latter embodiment consequently not as uncharged zwitterion or even anionic.

The Compounds possessing at least one quaternary nitrogen atom are in the agent of the invention preferably in an amount of 0.01% by weight to 20% by weight, especially preferably from 0.1% by weight to 5 wt .-%, each based on the weight of the ready-to-use By means of, included.

worin bedeuten
R¹ und R² unabhängig voneinander eine lineare oder verzweigte (C₁ bis C₃₀)-Alkylgrupppe, eine (C₂ bis C₃₀)-Acylgruppe oder eine Gruppe -A¹-A²-A³-R⁵
worin
R⁵ eine lineare oder verzweigte (C₈ bis C₃₀)-Alkylgruppe, eine lineare oder verzweigte (C₈ bis C₃₀)-Alkenylgruppe, eine Hydroxy-(C₈- bis C₃₀)-alkylgruppe oder eine Oligohydroxy-(C₈- bis C₃₀)-alkylgruppe bedeutet,
A¹ eine direkte Bindung oder eine Carbonylgruppe bedeutet,
A² eine direkte Bindung, eine Gruppe NH oder ein Sauerstoffatom bedeutet,
A³ eine (C₂ bis C₄)-Alkylengruppe oder eine (C₂ bis C₄)-Hydroxyalkylengruppe bedeutet
R³ eine lineare oder verzweigte (C₈ bis C₃₀)-Alkylgruppe, eine (C₈ bis C₃₀)-Hydroxyalkylgruppe, eine (C₂ bis C₃₀)-Acylgruppe, eine (C₂ bis C₄)-Hydroxyalkylgruppe oder eine Aryl-(C₁ bis C₆)-alkylgruppe,
R⁴ eine (C₁ bis C₄)-Alkylgruppe oder eine (C₂ bis C₄)-Hydroxyalkylgruppe,
X^– ein physiologisch verträgliches organisches oder anorganisches Anion.Particularly suitable compound according to the invention, possessing at least one quaternary nitrogen atom, are compounds of the formula (Q1),

in which mean
R ¹ and R ² are each independently a linear or branched (C ₁ to C ₃₀ ) alkyl group, a (C ₂ to C ₃₀ ) acyl group or a group -A ¹ -A ² -A ³ -R ⁵
wherein
R ^{5 is} a linear or branched (C ₈ to C ₃₀ ) alkyl group, a linear or branched (C ₈ to C ₃₀ ) alkenyl group, a hydroxy (C ₈ to C ₃₀ ) alkyl group or an oligohydroxy (C ₈ - to C ₃₀ ) alkyl group,
A ¹ denotes a direct bond or a carbonyl group,
A ^{2 is} a direct bond, a group NH or an oxygen atom,
A ^{3 represents} a (C ₂ to C ₄ ) -alkylene group or a (C ₂ to C ₄ ) -hydroxyalkylene group
R ^{3 is} a linear or branched (C ₈ to C ₃₀ ) -alkyl group, a (C ₈ to C ₃₀ ) -hydroxyalkyl group, a (C ₂ to C ₃₀ ) -acyl group, a (C ₂ to C ₄ ) -hydroxyalkyl group or a Aryl (C ₁ to C ₆ ) alkyl group,
R ^{4 is} a (C ₁ to C ₄ ) -alkyl group or a (C ₂ to C ₄ ) -hydroxyalkyl group,
X ^- a physiologically acceptable organic or inorganic anion.

R ⁴ is preferably a methyl, an ethyl, a benzyl or a 2-hydroxyethyl group according to formula (Q1).

Examples of a (C ₁ - to C ₄ ) -alkyl group are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl.

Examples of a (C ₈ - to C ₃₀ ) -alkyl group are n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, stearyl, behenyl, isostearyl and eicosyl.

Examples of a (C ₁ to C ₃₀ ) alkyl group are the aforementioned examples of the respective alkyl groups and n-pentyl, an isopentyl, n-hexyl and an n-heptyl group.

Examples of a (C ₂ to C ₄ ) alkenyl group are vinyl, allyl and butenyl.

Examples of a (C ₂ to C ₄ ) hydroxyalkyl group are a 2-hydroxyethyl, a 2-hydroxypropyl, a 3-hydroxypropyl and a 4-hydroxybutyl group.

Examples of a (C ₂ - to C ₄ ) -alkylene group are ethylene, propane-1,2-diyl, propane-1,3-diyl, and butane-1,4-diyl.

Examples of a (C ₂ - to C ₄ ) -hydroxyalkylene group are 2-hydroxyethylene, 1-hydroxy-propane-1,2-diyl, 1-hydroxy-propane-1,3-diyl and 2-hydroxy-propane-1, 3-diyl.

Examples of a (C ₁ to C ₄ ) -alkylene group are methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, and butane-1,4-diyl.

Examples of (C ₂ to C ₃₀ ) acyl groups are octanoyl, decanoyl, dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl and eicosanoyl.

Examples of linear or branched (C ₈ -C ₃₀ ) -alkenyl groups are 9-octadecen-1-yl, 9,12-octadecadien-1-yl, 9,12,15-octadecatrien-1-yl and 13-docosen-1 yl.

Hydroxy (C ₈ -C ₃₀ ) -alkyl groups are, for example, 2-hydroxydecyl, 2-hydroxydodecyl, 2-hydroxytetradecyl, 2-hydroxyhexadecyl and 2-hydroxyoctadecyl.

When physiologically compatible For example, organic or inorganic counterions X according to formula (Q1) are used Halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions into consideration. Preference is given to methosulfate and halide ions, in particular Bromide and chloride.

in denen die Gruppen A³ und R⁵ gemäß Formel (Q1) definiert sind.Preferred representatives of the radical -A ¹ -A ² -A ³ -R ⁵ are according to the invention the groups

in which the groups A ³ and R ^{5 are} defined according to formula (Q1).

• – eine ω-[(C₈- bis C₃₀)-Alkanoyloxy]-(C₂- bis C₄)-alkylgruppe (R⁵ = (C₈- bis C₃₀)-Alkyl, A¹ = Carbonyl, A² = Sauerstoffatom, A³ = (C₂- bis C₄)-Alkylengruppe),
• – eine ω-[(C₈- bis C₃₀)-Alkylamido]-(C₂- bis C₄)-alkylgruppe (R⁵ = (C₈- bis C₃₀)-Alkyl, A¹ = Carbonyl, A² = Gruppe NH, A³ = (C₂- bis C₄)-Alkylengruppe),
• – eine (C₁₀- bis C₃₄)-Hydroxyalkylgruppe (entweder: R⁵ = (C₈- bis C₃₀)-Alkyl, A¹ = direkte Bindung, A² = direkte Bindung, A³ = (C₂- bis C₄)-Hydroxyalkylengruppe oder: R⁵ = (C₈- bis C₃₀)-Hydroxyalkyl oder Oligohydroxy-(C₈- bis C₃₀)-alkylgruppe, A¹ = direkte Bindung, A² = direkte Bindung, A³ = (C₂- bis C₄)-Alkylengruppe.

Particularly preferred radicals -A ¹ -A ² -A ³ -R ⁵ are according to the invention

• An ω - [(C ₈ to C ₃₀ ) alkanoyloxy] (C ₂ to C ₄ ) alkyl group (R ⁵ = (C ₈ to C ₃₀ ) alkyl, A ¹ = carbonyl, A ² = Oxygen atom, A ³ = (C ₂ - to C ₄ ) -alkylene group),
• - an ω - [(C ₈ - to C ₃₀ ) -alkylamido] - (C ₂ - to C ₄ ) -alkyl group (R ⁵ = (C ₈ - to C ₃₀ ) -alkyl, A ¹ = carbonyl, A ² = Group NH, A ³ = (C ₂ - to C ₄ ) -alkylene group),
• A (C ₁₀ to C ₃₄ ) hydroxyalkyl group (either: R ⁵ = (C ₈ to C ₃₀ ) alkyl, A ¹ = direct bond, A ² = direct bond, A ³ = (C ₂ to C) ₄ ) -hydroxyalkylene group or: R ⁵ = (C ₈ - to C ₃₀ ) -hydroxyalkyl or oligohydroxy- (C ₈ - to C ₃₀ ) -alkyl group, A ¹ = direct bond, A ² = direct bond, A ³ = (C ₂ - to C ₄ ) -alkylene group.

Examples of ω - [(C ₈ - to C ₃₀ ) -alkanoyloxy] - (C ₂ - to C ₄ ) -alkyl groups are the preferred 2 - [(C ₈ - to C ₃₀ ) -acyloxy] ethyl groups, in particular 2- ( Dodecanoyloxy) ethyl, 2- (tetradecanoyloxy) ethyl, 2- (hexadecanoyloxy) ethyl and 2- (octadecanoyloxy) ethyl.

The Compounds of the formula (Q1) are preferably selected from at least one compound from the group that is formed from Compounds of the following formulas (Q1-a), (Q1-b) and (Q1-c).

worin

• – R und R unabhängig voneinander eine (C₂ bis C₃₀)-Acylgruppe oder eine lineare oder verzweigte (C₁ bis C₃₀)-Alkylgruppe bedeutet,
• – R^5* eine lineare oder verzweigte (C₈ bis C₃₀)-Alkylgruppe oder eine lineare oder verzweigte (C₈ bis C₃₀)-Alkenylgruppe bedeutet,
• – A¹ eine direkte Bindung oder eine Carbonylgruppe bedeutet,
• – A² eine direkte Bindung, eine Gruppe NH oder ein Sauerstoffatom bedeutet,
• – A³ eine (C₂ bis C₄)-Alkylengruppe oder eine (C₂ bis C₄)-Hydroxyalkylengruppe bedeutet und
• – X^– ein physiologisch verträgliches organisches oder anorganisches Anion ist,

mit der Maßgabe, daß A³ eine (C₂- bis C₄)-Hydroxyalkylengruppe bedeutet, wenn A¹ und A² für eine direkte Bindung stehen.One of the above-mentioned preferred groups of quaternary ammonium compounds of the abovementioned formula (Q1) is defined as compounds of the formula (Q1-a)

wherein

• R and R independently of one another are a (C ₂ to C ₃₀ ) -acyl group or a linear or branched (C ₁ to C ₃₀ ) -alkyl group,
• R ^{5 *} denotes a linear or branched (C ₈ to C ₃₀ ) -alkyl group or a linear or branched (C ₈ to C ₃₀ ) -alkenyl group,
• A ¹ denotes a direct bond or a carbonyl group,
• A ² denotes a direct bond, a group NH or an oxygen atom,
• A ^{3 is} a (C ₂ to C ₄ ) -alkylene group or a (C ₂ to C ₄ ) -hydroxyalkylene group and
• - X ^- is a physiologically compatible organic or inorganic anion,

with the proviso that A ^{3 represents} a (C ₂ to C ₄ ) hydroxyalkylene group when A ¹ and A ^{2 are} a direct bond.

worin

• – R⁸ und R⁹ unabhängig voneinander für eine (C₁- bis C₄)-Alkylgruppe oder (C₂- bis C₄)-Hydroxyalkylgruppe stehen,
• – R⁵ eine lineare oder verzweigte (C₈- bis C₃₀)-Alkylgruppe, lineare oder verzweigte (C₈- bis C₃₀)-Alkenylgruppe, eine Hydroxy-(C₈- bis C₃₀)-alkylgruppe oder eine Oligohydroxy-(C₈- bis C₃₀)-alkylgruppe bedeutet,
• – A^1* eine Carbonylgruppe bedeutet
• – A² eine Gruppe NH oder ein Sauerstoffatom bedeutet,
• – A³ eine (C₂- bis C₄)-Alkylengruppe, eine (C₂- bis C₄)-Hydroxyalkylengruppe bedeutet und
• – X^– ein physiologisch verträgliches organisches oder anorganisches Anion ist.

The other group of preferred quaternary ammonium compounds is selected from compounds of the formula (Q1-b)

wherein

• R ⁸ and R ⁹ independently of one another represent a (C ₁ - to C ₄ ) -alkyl group or (C ₂ - to C ₄ ) -hydroxyalkyl group,
• R ^{5 is} a linear or branched (C ₈ to C ₃₀ ) alkyl group, linear or branched (C ₈ to C ₃₀ ) alkenyl group, a hydroxy (C ₈ to C ₃₀ ) alkyl group or an oligohydroxy ( C ₈ - to C ₃₀ ) -alkyl group,
• - A ^{1 * represents} a carbonyl group
• A ² denotes a group NH or an oxygen atom,
• A ^{3 is} a (C ₂ -C ₄ ) -alkylene group, a (C ₂ -C ₄ ) -hydroxyalkylene group and
• - X ^{- is} a physiologically acceptable organic or inorganic anion.

• – R und R stehen bevorzugt unabhängig voneinander für eine Methylgruppe oder eine 2-Hydroxyethylgruppe.
• – wenn R⁸ und R⁹ gleich sind, stehen sie bevorzugt für eine (C₁- bis C₄)-Alkylgruppe, besonders bevorzugt für eine Methylgruppe.
• – Es ist bevorzugt, daß A³ ausgewählt wird aus Ethylen, Propan-1,3-diyl, Propan-1,2-diyl, 2-Hydroxypropan-1,3-diyl.

According to the invention, those compounds according to formula (Q1-b) are preferred for which at least one of the following conditions applies:

• R and R are preferably, independently of one another, a methyl group or a 2-hydroxyethyl group.
• When R ⁸ and R ^{9 are the} same, they are preferably a (C ₁ - to C ₄ ) -alkyl group, more preferably a methyl group.
• It is preferred that A ^{3 is} selected from ethylene, propane-1,3-diyl, propane-1,2-diyl, 2-hydroxypropane-1,3-diyl.

Further inventively preferred quaternized ammonium compounds of the formula (Q1) are selected from compounds of the formula (Q1-c), (R ¹⁰⁾ _y (Me) _(4-y) N ⁺ X ^- (Q1-C) in which
R ¹⁰ independently of one another a (C ₈ - to C ₃₀ ) -alkyl group,
y is 1 or 2 and
X- is a physiologically acceptable organic or inorganic anion,

In the compounds of the formula (Q1-c), the radical R ^{10 is} preferably an alkyl group having 10 to 22 carbon atoms, particularly preferably having 10 to 18 carbon atoms.

The in the inventive compositions as compounds of formula (Q1-c) contained quaternary ammonium compounds are preferably halides, especially chlorides and bromides.

It apply those for the radicals according to formula (Q1), as examples of the respective radicals or Groups of formulas (Q1-a), (Q1-b) and (Q1-c).

• – Salze, insbesondere Halogenide, des Dicetyldimethylammoniums, Distearyldimethylammoniums (z. B. Dioctadecyldimethylammonium Chlorid als Genamin^® DSAc der Firma Clariant), Cetyltrimethylammoniums (z. B. Hexadecyltrimethylammonium Chlorid als Dehyquart^® A der Firma Cognis), oder des Stearyltrimethylammoniums,
• – quaternierten Estersalzen von Fettsäuren mit Triethanolamin, sogenannte Esterquats, insbesondere den Salzen des N,N-Di(2-(dodecanoyloxy)ethyl)dimethylammoniums, N,N-Di(2-(tetradecanoyloxy)ethyl)dimethylammoniums, N,N-Di(2-(hexadecanoyloxy)ethyl)dimethylammoniums, N,N-Di(2-(hexadecanoyloxy) propyl)dimethylammoniums, N,N-Di(2-(octadecanoyloxy)ethyl)dimethylammoniums mit einem physiologisch verträglichen, organisch oder anorganischen Anion. Bevorzugte Anionen sind Alkylsulfate, wie z. B. Methylsulfat, und Halogenide, wie Chlorid und Bromid. Solche Produkte werden beispielsweise unter den Warenzeichen Stepantex^®, Dehyquart^® und Armocare^® vertrieben. Die Produkte Armocare^® VGH-70, ein N,N-Di(2-Hexadecanoyloxy-ethyl)dimethylammoniumchlorid, sowie Dehyquart^® L80 (INCI-Bezeichnung: Dicocoylethyl Hydroxyethylmonium Methosulfate), Dehyquart^® F-75, Dehyquart^® C-4046, und Dehyquart^® AU-35 sind Beispiele für solche Esterquats. Zur Herstellung können auch Fettsäureschnitte, z. B. aus Talg wie beispielsweise Rindertalg gewonnene Talgfettsäuren, verwendet werden (INCI-Bezeichnungen: Ditallowoylethyl Dimonium Methosulfate, Ditallowoyl PG-dimonium Chloride).
• – Salzen des N,N-Dimethyl-N-(2-hydroxyethyl)-N-(2-hydroxyhexadecyl)-ammoniums. Bevorzugte Halogenide sind Chlorid und Bromid. Diese werden beispielsweise unter der Handelsmarke Dehyquart^® E (INCI-Bezeichnung: Aqua (Water), Hydroxycetyl Hydroxyethyl Dimonium Chloride) von der Firma Cognis vertrieben.
• – quaternierte Amidsalze von Fettsäuren mit Diaminen, wie z. B. Salzen des N-(13-Docosen)amidopropyl-N-2-hydroxyethyl-N,N-dimethylammoniums (INCI-Bezeichnung: Hydroxyethyl Erucamidopropyl Dimonium Chloride) oder des N-Docosylamidopropyl-N-2-hydroxyethyl-N,N-dimethylammoniums welches unter dem Handelsnamen Incroquat^® Behenyl HE (INCI-Bezeichnung: Hydroxyethyl Behenamidopropyl Dimonium Chloride) von der Firma Croda Inc. vertrieben wird.

The compounds of formula (Q1) are preferably selected from the group formed

• - salts, in particular halides, the Dicetyldimethylammoniums, Distearyldimethylammoniums (eg Dioctadecyldimethylammonium chloride as Genamin ^® DSAc Clariant.), Cetyl-trimethyl ammonium (for example, hexadecyltrimethylammonium chloride as Dehyquart ^® A from Cognis.), Or the Stearyltrimethylammoniums,
• Quaternized ester salts of fatty acids with triethanolamine, so-called esterquats, in particular the salts of N, N-di (2- (dodecanoyloxy) ethyl) dimethylammonium, N, N-di (2- (tetradecanoyloxy) ethyl) dimethylammonium, N, N-di (2- (hexadecanoyloxy) ethyl) dimethylammonium, N, N-di (2- (hexadecanoyloxy) propyl) dimethylammonium, N, N-di (2- (octadecanoyloxy) ethyl) dimethylammonium having a physiologically acceptable, organic or inorganic anion. Preferred anions are alkyl sulfates, such as. As methyl sulfate, and halides, such as chloride and bromide. Such products are marketed under the trade names Stepantex® ^{®, ®} and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-di (2-hexadecanoyloxy-ethyl) dimethyl ammonium chloride, as well as Dehyquart ^® L80 (INCI name: Dicocoylethyl Hydroxyethylmonium Methosulfate), Dehyquart ^® F-75, Dehyquart ^® C-4046, and Dehyquart® ^® AU-35 are examples of such esterquats. For the preparation and fatty acid cuts, z. B. tallow such as beef tallow derived tallow fatty acids are used (INCI names: Ditallowoylethyl Dimonium Methosulfate, Ditallowoyl PG-dimonium chlorides).
• - Salts of N, N-dimethyl-N- (2-hydroxyethyl) -N- (2-hydroxyhexadecyl) -ammonium. Preferred halides are chloride and bromide. These are, for example, under the trademark Dehyquart® ^® E: sold by the company Cognis (INCI name Aqua (Water), Hydroxycetyl hydroxyethyl dimonium chloride).
• Quaternized amide salts of fatty acids with diamines, such as. B. salts of N- (13-docoses) amidopropyl-N-2-hydroxyethyl-N, N-dimethylammonium (INCI name: Hydroxyethyl Erucamidopropyl Dimonium Chloride) or N-docosylamidopropyl-N-2-hydroxyethyl-N, N- dimethylammoniums under the trade name Incroquat ^® behenyl HE (INCI name: hydroxyethyl behenamidopropyl dimonium chloride) is marketed by Croda Inc..

As quaternary ammonium compounds from the group of polymers derived from at least one monomer having a quaternary ammonium group, cationic and / or amphoteric polymers are preferably used. Cationic or amphoteric polymers are to be understood as meaning polymers which have a group in the main and / or side chain which is "permanently" cationic. According to the invention, "permanently cationic" refers to those polymers which have a cationic group, irrespective of the pH of the agent. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers in which the quaternary ammonium group is bonded via a (C ₁ to C ₄ ) hydrocarbon group to a polymer main chain composed of acrylic acid, methacrylic acid or derivatives thereof have proven to be particularly suitable.

in der R¹ = -H oder -CH₃ ist, R², R³ und R⁴ unabhängig voneinander ausgewählt sind aus (C₁ bis C₄)-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen, m = 1, 2, 3 oder 4, n eine natürliche Zahl und X^– ein physiologisch verträgliches organisches oder anorganisches Anion ist, sowie Copolymere, bestehend im wesentlichen aus den in Formel (Q2) aufgeführten Monomereinheiten sowie nichtionogenen Monomereinheiten, sind besonders bevorzugte kationische Polymere. Im Rahmen dieser Polymere sind diejenigen erfindungsgemäß bevorzugt, für die mindestens eine der folgenden Bedingungen gilt:

• – R¹ steht für eine Methylgruppe
• – R², R³ und R⁴ stehen für Methylgruppen
• – m hat den Wert 2.

Homopolymers of the general formula (Q2),

in which R ¹ = -H or -CH ₃ , R ² , R ³ and R ^{4 are} independently selected from (C ₁ to C ₄ ) -alkyl, -alkenyl or -hydroxyalkyl groups, m = 1, 2, 3 or 4, n is a natural number and X ^{- is} a physiologically acceptable organic or inorganic anion, and copolymers consisting essentially of the monomer units listed in formula (Q2) and nonionic monomer units are particularly preferred cationic polymers. In the context of these polymers, preference is given to those according to the invention for which at least one of the following conditions applies:

• - R ¹ is a methyl group
• - R ² , R ³ and R ⁴ are methyl groups
• - m has the value 2.

Suitable physiologically tolerated counterions X ^- include, for example, halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions. Preference is given to halide ions, in particular chloride.

A particularly suitable homopolymer (Q2) is the, if desired crosslinked, poly (methacryloyloxyethyltrimethylammonium chloride) with the INCI name Polyquaternium-37. Such products are available, for example under the names Rheocare ^® CTH (Cosmetic Rheologies) and Synthalen® ^® CR (Ethnichem) in trade. If desired, the crosslinking can be carried out with the aid of poly olefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, polyallylpolyglyceryl ethers, or allyl ethers of sugars or sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose or glucose. Methylenebisacrylamide is a preferred crosslinking agent.

The homopolymer is preferably used in the form of a nonaqueous polymer dispersion which should not have a polymer content of less than 30% by weight. Such polymer dispersions are available under the names Salcare ^® SC 95 (about 50% polymer content, additional components: mineral oil (INCI name: Mineral Oil) and tridecyl-polyoxypropylene-polyoxyethylene-ether (INCI name: PPG-1 trideceth-6) ) and Salcare ^® SC 96 (about 50% polymer content, additional components: mixture of diesters of propylene glycol with a mixture of caprylic and capric acid (INCI name: propylene glycol Dicaprylate / Dicaprate) and tridecyl-polyoxypropylene-polyoxyethylene-ether (INCI Designation: PPG-1-trideceth-6)) are commercially available.

Copolymers having monomer units of the formula (Q2) contain as nonionic monomer units preferably acrylamide, methacrylamide, acrylic acid C _1-4 alkyl esters and methacrylic acid C _1-4 alkyl esters. Among these nonionic monomers, the acrylamide is particularly preferred. These copolymers can also be crosslinked, as described above in the case of the homopolymers. A copolymer preferred according to the invention is the crosslinked acrylamide-methacryloyloxyethyltrimethylammonium chloride copolymer. Such copolymers in which the monomers are present in a weight ratio of about 20:80, commercially available as about 50% non-aqueous polymer dispersion under the name Salcare ^® SC 92nd

worin
R eine C₁- bis C₃₀-Alkylgruppe, eine C₁- bis C₄-Aralkylgruppe, eine C₂- bis C₆-Alkenylgruppe oder eine C₂ bis C₆-Hydroxyalkylgruppe bedeutet und
X^– für ein physiologisch verträgliches Anion steht.As quaternary ammonium compound according to the invention, the compositions according to the invention may comprise at least one polymer which comprises at least one structural unit of the formula (Q3),

wherein
R is a C ₁ to C ₃₀ alkyl group, a C ₁ to C ₄ aralkyl group, a C ₂ to C ₆ alkenyl group or a C ₂ to C ₆ hydroxyalkyl group, and
X ^{- stands} for a physiologically acceptable anion.

Preferred polymers of the formula (Q3) which are suitable according to the invention are those in which R is a C ₁ - to C ₁₀ -alkyl group, in particular a methyl group.

Examples of C ₁ - to C ₃₀ -alkyl groups which can be used according to the invention in compounds of the formula (Q3) are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-decyl, n- Dodecyl, stearyl or behenyl.

Examples of C ₂ -C ₆ -alkenyl groups which can be used according to the invention in compounds of the formula (Q3) are vinyl, 2-propen-1-yl (allyl) or 3-buten-1-yl.

Examples of a C ₁ to C ₄ aralkyl group are the benzyl group and the 2-phenylethyl group.

Examples of a C ₂ to C ₆ hydroxyalkyl group are the 2-hydroxyethyl group and the 3-hydroxypro pylgruppe.

By definition, the physiologically acceptable anions X ^- according to formula (Q3) may not only carry a negative charge but may also have a charge number greater than one. In the latter case, the anions X ^- the salt form according to formula (Q3) for maintaining the electroneutrality are described by formulating a stoichiometric coefficient less than 1 before the anion. The physiologically acceptable anions are preferably selected from halide, benzenesulfonate, p-toluenesulfonate, C ₁ -C ₄ -alkanesulfonate, trifluoromethanesulfonate, C ₁ -C ₄ -alkyl sulfate, perchlorate, 0.5 sulfate, hydrogen sulfate, 0.5 carbonate, bicarbonate, 1/3 phosphate , 0.5 hydrogen phosphate, dihydrogen phosphate, lactate, citrate, tetrafluoroborate, hexafluorophosphate or Tetrachlorozinkat. Particularly preferably, X ^- is a halide, particularly chloride, bromide or iodide, C ₁ -C ₄ alkyl sulfate, p-toluenesulfonate, tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, 0.5 sulfate, or bisulfate. Particularly preferably, the anions chloride, methyl sulfate or ethyl sulfate are used as X ^- .

The usable according to the invention Polymers of formula (Q3) have a preferred molecular weight of more than 100,000 g / mol, more preferably of more than 400,000 g / mol.

worin n für 1, 2 oder 3 als Anzahl der Methyleneinheiten steht.It is preferred according to the invention to use a copolymer which, in addition to at least one structural unit according to the above formula (Q3), comprises at least one structural unit of the formula (N1),

wherein n is 1, 2 or 3 as the number of methylene units.

Preferred polymers are sold under the trade names Luviquat ^® FC 370, Luviquat ^® FC 550, Luviquat ^® FC 905 and Luviquat ^® HM 552, as well as Luviquat ^® Hold (INCI name: Polyquaternium-46), Luviquat ^® Supreme (Polyquaternium-68) and / or Luviquat ^® Ultra Care to refer respectively by the company BASF.

Farther preferably usable is a copolymer in which in addition to at least a structural unit of the formula (Q3), at least one structural unit of formula (N1) with n = 1 and at least one further structural unit of formula (N1) with n = 3.

in denen R und X^– die für Formel (Q3) angegebenen Bedeutungen, insbesondere aller zuvor genannten Ausführungsformen, haben.Preference is likewise given to using a terpolymer having the structural units of the formulas

in which R and X ^{- have} the meanings given for formula (Q3), in particular all the aforementioned embodiments.

Such polymers are sold, for example, by BASF under the trade name Luviquat ^® Hold (INCI name: Polyquaternium-46). The weight ratios (in weight percent) of the structural units of formula (I) to the structural units of formula (II) with n = 1 to the structural units of formula (II) with n = 3 in the commercial product 10 to 40 to 50 and the charge density is 0.5 meq / g.

In all usable according to the invention Polymers can in the presence of different structural units, these respectively distributed statistically or as a block.

• – quaternisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat^® und Polymer JR^® im Handel erhältlich sind. Die Verbindungen Celquat^® H 100, Celquat^® L 200 und Polymer JR^® 400 sind bevorzugte quaternierte Cellulose-Derivate,
• – kationische Alkylpolyglycoside gemäß der DE-PS 44 13 686,
• – kationisierter Honig, beispielsweise das Handelsprodukt Honeyquat^® 50,
• – kationische Guar-Derivate, wie insbesondere die unter den Handelsnamen Cosmedia^® Guar und Jaguar^® vertriebenen Produkte,
• – polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure. Die unter den Bezeichnungen Merquat^® 100 (Poly(dimethyldiallylammoniumchlorid)) und Merquat^® 550 (Dimethyldiallylammoniumchlorid-Acrylamid-Copolymer) im Handel erhältlichen Produkte sind Beispiele für solche kationischen Polymere,
• – Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoalkylacrylats und -methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinylpyrrolidon-Dimethylaminoethylmethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat^® 734 und Gafquat^® 755 im Handel erhältlich,
• – quaternierter Polyvinylalkohol,
• – sowie die unter den Bezeichnungen Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 und Polyquaternium 27 bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette.

Further cationic polymers which can be used in the compositions according to the invention are, for example

• - Quaternized cellulose derivatives, such as those under the names Celquat ^® and Polymer JR ^® commercially are available. The compounds Celquat ^® H 100, Celquat L 200 and Polymer JR ^{® ®} 400 are preferred quaternized cellulose derivatives
• Cationic alkyl polyglycosides according to DE-PS 44 13 686,
• - cationized honey, for example the commercial product Honeyquat ^® 50,
• - cationic guar derivatives, such as in particular the products sold under the trade names Cosmedia® ^® Guar and Jaguar ^®,
• - Dimethyldiallylammoniumsalze polymeric and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) commercially available products are examples of such cationic polymers,
• - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate, such as diethyl sulfate quaternized vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers. Such compounds are sold under the names Gafquat ^® 734 and Gafquat ^® 755 commercially,
• - quaternized polyvinyl alcohol,
• - as well as the polymers known under the names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 with quaternary nitrogen atoms in the polymer main chain.

Can be used also as the canonical polymers (. B. commercial product, Quatrisoft ^® LM 200) under the designations Polyquaternium-24, known polymers. Also usable in the invention are the copolymers of vinylpyrrolidone, such as the commercial products Copolymer 845 (manufactured by ISP), Gaffix ^® VC 713 (manufactured by ISP), Gafquat ^® ASCP 1011, Gafquat ^® HS 110, Luviquat ^® 8155 and Luviquat ^® MS 370 available are.

• A) Monomeren mit quartären Ammoniumgruppen der allgemeinen Formel (Z1-a), R¹-CH=CR²-CO-Z-(C_nH_2n)-N⁽⁺⁾R³R⁴R⁵ A^(–) (Z1-a) In der R¹ und R² unabhängig voneinander stehen für Wasserstoff oder eine Methylgruppe und R³, R⁴ und R⁵ unabhängig voneinander für Alkylgruppen mit 1 bis 4 Kohlenstoff-Atomen, Z eine NH-Gruppe oder ein Sauerstoffatom, n eine ganze Zahl von 2 bis 5 und A^(–) das Anion einer organischen oder anorganischen Säure ist und
• B) monomeren Carbonsäuren der allgemeinen Formel (Z1-b), R⁶-CH=CR⁷-COOH (Z1-b)in denen R⁶ und R⁷ unabhängig voneinander Wasserstoff oder Methylgruppen sind.

In addition to canonical polymers or in their place, the agents of the invention may also contain amphoteric polymers. These additionally have at least one negatively charged group in the molecule and are also referred to as zwitterionic polymers. In the context of the present invention, preferably usable zwitterionic polymers (Q4) are composed essentially together

• A) monomers having quaternary ammonium groups of the general formula (Z1-a), R ¹ -CH = CR ² -CO-Z- (C _n H _2n ) -N ⁽⁺⁾ R ³ R ⁴ R ⁵ A ^(-) (Z ¹ -a) In the R ¹ and R ² independently of one another are hydrogen or a methyl group and R ³ , R ⁴ and R ^{5 are} independently alkyl groups having 1 to 4 carbon atoms, Z is an NH group or an oxygen atom, n is an integer of 2 to 5 and A ^{(-) is} the anion of an organic or inorganic acid and
• B) monomeric carboxylic acids of the general formula (Z1-b), R ⁶ -CH = CR ⁷ -COOH (Z ¹ -b) in which R ⁶ and R ^{7 are} independently hydrogen or methyl groups.

suitable Starting monomers are z. Dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, Dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide and Diethylaminoethylacrylamide, when Z according to formula (Z1-a) is an NH group or dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate and diethylaminoethyl acrylate when Z is an oxygen atom.

The a tertiary Amino-containing monomers are then in a known manner quaternized, wherein as alkylating reagents methyl chloride, dimethyl sulfate or diethyl sulfate are particularly suitable. The quaternization reaction can in aqueous solution or in the solvent respectively.

Advantageously, such monomers of the formula (Z1-a), the derivatives of acrylamide or methacrylamide represent. Preference is furthermore given to those monomers which contain halide, methoxysulfate or ethoxysulfate ions as counterions. Also preferred are those monomers of the formula (Z1-a) in which R ³ , R ⁴ and R ^{5 are} methyl groups.

The Acrylamidopropyltrimethylammonium chloride is a very special one preferred monomer of the formula (Z1-a).

When monomeric carboxylic acids of the formula (Z1-b) are acrylic acid, methacrylic acid, crotonic acid and 2-methyl-crotonic acid. Preference is given to using acrylic or methacrylic acid, in particular acrylic acid.

The can be used according to the invention zwitterionic polymers are prepared from monomers of the formulas (Z1-a) and (Z1-b) prepared according to known polymerization. The polymerization can be carried out either in aqueous or aqueous-alcoholic solution respectively. Alcohols are alcohols having 1 to 4 carbon atoms, preferably isopropanol, used simultaneously as a polymerization regulator serve. The monomer solution can but other components are added as a regulator, z. B. formic acid or mercaptans, such as thioethanol and thioglycolic acid. The initiation of the polymerization takes place with the help of radical-forming substances. For this purpose, redox systems and / or thermally decomposing radical formers of the azo compound type, such as Azoisobutyronitrile, Azobis (cyanopentanoic acid) or azo-bis (amidinopropane) dihydrochloride. When Redox systems are suitable for. B. combinations of hydrogen peroxide, Potassium or ammonium peroxodisulfate and tertiary butyl hydroperoxide with sodium sulfite, Sodium dithionite or hydroxylamine hydrochloride as a reduction component.

The Polymerization may be isothermal or under adiabatic conditions carried out be, depending on from the concentration ratios by the released heat of polymerization of the temperature range for the process the reaction between 20 and 200 ° C may vary, and the reaction optionally under the autogenous overpressure carried out must become. Preferably, the reaction temperature is between 20 and 100 ° C.

When According to the invention, such polymers have proved to be particularly effective, in which the monomers of the formula (Z1-a) with respect to the monomers of the formula (Z1-b) in excess. It is therefore preferred according to the invention to use those polymers which consist of monomers of the formula (Z1-a) and the monomers of the formula (Z1-b) in a molar ratio of 60:40 to 95: 5, in particular from 75:25 to 95: 5.

worin bedeuten
R¹ und R² unabhängig voneinander eine lineare oder verzweigte (C₁ bis C₃₀)-Alkylgrupppe, eine Aryl-(C₁ bis C₆)-alkylgruppe, eine (C₂ bis C₃₀)-Acylgruppe, oder eine Gruppe -A¹-A²-A³-R⁵
worin
R⁵ eine lineare oder verzweigte (C₈ bis C₃₀)-Alkylgruppe oder eine lineare oder verzweigte (C₈ bis C₃₀)-Alkenylgruppe bedeutet,
A¹ eine direkte Bindung oder eine Carbonylgruppe bedeutet,
A² eine direkte Bindung, eine Gruppe NH oder ein Sauerstoffatom bedeutet,
A³ eine (C₂ bis C₄)-Alkylengruppe oder eine (C₂ bis C₄)-Hydroxyalkylengruppe bedeutet und
R³ eine lineare oder verzweigte (C₈ bis C₃₀)-Alkylgruppe, eine (C₈ bis C₃₀)-Hydroxyalkylgruppe, eine (C₂ bis C₃₀)-Acylgruppe,
wobei R¹ und R² auch gemeinsam mit dem Restmolekül einen fünf- oder sechsgliedrigen Ring bilden können.Particularly suitable compounds according to the invention from the group of organic N-oxides are compounds of the formula (Q5)

in which mean
R ¹ and R ² are each independently a linear or branched (C ₁ to C ₃₀ ) alkyl group, an aryl (C ₁ to C ₆ ) alkyl group, a (C ₂ to C ₃₀ ) acyl group, or a group -A ¹ -A ² -A ³ -R ⁵
wherein
R ⁵ denotes a linear or branched (C ₈ to C ₃₀ ) -alkyl group or a linear or branched (C ₈ to C ₃₀ ) -alkenyl group,
A ¹ denotes a direct bond or a carbonyl group,
A ^{2 is} a direct bond, a group NH or an oxygen atom,
A ^{3 represents} a (C ₂ to C ₄ ) -alkylene group or a (C ₂ to C ₄ ) -hydroxyalkylene group and
R ^{3 is} a linear or branched (C ₈ to C ₃₀ ) -alkyl group, a (C ₈ to C ₃₀ ) -hydroxyalkyl group, a (C ₂ to C ₃₀ ) -acyl group,
wherein R ¹ and R ² together with the rest of the molecule can form a five- or six-membered ring.

Preferably usable amine oxides are dimethyl (C ₈ - to C ₂₂ ) alkylamine oxides. In particular, cocamidopropylamine oxide, N-cocomorpholine oxide, decyldimethylamine oxide, Dimethylcetylaminoxid, dimethyl cocoamine oxide (Aromox ^® MCDW, Fa. Akzo Nobel), dimethyl hydrogenated tallowamine oxide, dimethyl laurylamine, Dimethylmyristylaminoxid, (2-hydroxyethyl) cocoamine oxide or Oleaminoxid preferred in the inventive compositions as nonionic N -Oxid surfactants used.

Farther can according to the invention as quaternary ammonium compounds from the group of organic N-oxides at least one pyridine N-oxide or derivatives thereof, a pyrimidine N-oxide or derivatives thereof, such as in particular 2,4-diaminopyrimidines-3-oxide (from Chimex), in the agent according to the invention be included.

In addition to the active ingredient combination according to the invention can the agents according to the invention as further component at least one compound from the aldehydes and / or the ketones.

• – Oxocarbonsäuren oder deren Salze,
• – Oxocarbonsäureester,
• – cyclische, lineare oder verzweigte aliphatische Aldehyde,
• – cyclische, lineare oder verzweigte aliphatische Ketone,
• – mono- bis polyhydroxyfunktionalisierte Aldehyde,
• – mono- bis polyhydroxyfunktionalisierte Ketone,
• – alicyclische, aromatische oder heterocyclische Aldehyde sowie
• – alicyclische, aromatische oder heterocyclische Ketone.

The choice of compounds from the aldehydes or ketones is initially no limit. At least one representative from the group proves to be particularly suitable:

• - oxocarboxylic acids or their salts,
• - oxocarboxylic acid ester,
• Cyclic, linear or branched aliphatic aldehydes,
• Cyclic, linear or branched aliphatic ketones,
• Mono- to polyhydroxy-functionalized aldehydes,
• Mono- to polyhydroxy-functionalized ketones,
• - alicyclic, aromatic or heterocyclic aldehydes and
• - alicyclic, aromatic or heterocyclic ketones.

As a general rule holds that in the above-mentioned compounds of the cyclic, alicyclic or heterocyclic ketones the keto group (s) endocyclic (and / or) or may be bonded exocyclically.

worin bedeuten
R ein Wasserstoffatom, eine (C₁ bis C₆)-Alkylgruppe, eine (C₁ bis C₆)-Hydroxyalkylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine gegebenenfalls substituierte Heteroarylgruppe, eine (C₂ bis C₆)-Alkenylgruppe oder eine Carboxy-(C₁ bis C₆)-alkylgruppe,
n eine Zahl 0, 1, 2 oder 3.Oxocarboxylic acids are organic compounds which, in addition to at least one carboxyl group, carry a carbonyl group and are thus aldehyde or ketocarboxylic acids. Preferred oxocarboxylic acids are α-oxocarboxylic acids, β-oxocarboxylic acids, γ-oxocarboxylic acids and ω-oxocarboxylic acids of the formula (XII) or salts thereof,

in which mean
R is a hydrogen atom, a (C ₁ to C ₆ ) -alkyl group, a (C ₁ to C ₆ ) -hydroxyalkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, a (C ₂ to C ₆ ) -alkenyl group or a carboxy- (C ₁ to C ₆ ) alkyl group,
n is a number 0, 1, 2 or 3.

Especially the oxocarboxylic acids are preferred selected from at least one member of the group glyoxylic acid, acetoacetic acid, 3-oxoglutaric acid, 4-oxovaleric acid and Pyruvic acid or salts of the aforementioned acids.

The oxocarboxylic acid esters are preferably selected from (C ₁ to C ₆ ) -alkyl esters of the preferred oxocarboxylic acids according to the invention.

Under cyclic, linear or branched aliphatic aldehydes according to the invention aliphatic To understand aldehydes whose formyl group (s) are not in conjugation with an aromatic π-electron system stand. The corresponding aldehydes may carry aromatic radicals, as long as the π electrons the formyl group (s) not over such an aromatic system may be delocalized. Preferred cyclic, linear or branched aliphatic aldehydes are saturated or unsaturated and are particularly preferably selected from at least one representative from the group formaldehyde, acetaldehyde, glyoxal, propionaldehyde, Butanal, pentanal, isopentanal, hexanal, cyclohexanal, heptanal, Octanal, malondialdehyde, glutaraldehyde, 2-methylpentanal, 2-ethylhexanal, 3,5,5-trimethylhexanal, 2-ethylbutyraldehyde, 2-methylbutyraldehyde, isobutyraldehyde, 3-phenylpropanal, 3- (4-methylphenyl) propanal, 3- (4-methoxyphenyl) propanal, 3- (2-methoxyphenyl) propanal, 2-butenal, acrolein, 3-methyl-2-butenal, 3,7-dimethyl-2,6-octadienal, 2,4-pentadienal 3,7-dimethyl-6-octenal, 2,4-dimethyl-3-cyclohexene carboxaldehyde and 2,6-nonadienal.

Under cyclic, linear or branched aliphatic ketones According to the invention aliphatic ketones to understand their keto group (s) not in conjugation with a aromatic π-electron system stand. The corresponding ketones are allowed however, carry aromatic radicals, as long as the π-electrons of the keto group (s) do not have a such aromatic system may be delocalized. Preferred cyclic, linear or branched aliphatic ketones are saturated or unsaturated and selected from at least one member of the group acetone, 2-butanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, butane-2,4-dione, pentane-2,4-dione, hexane-2,5-dione, Cyclohexanone, cyclopentanone, 4-methylpentan-2-one, 5-methyl-3-hexen-2-one, 2- (3-oxopropyl) benzoate and 4- (3-oxopropyl) benzoic acid methyl ester.

Preferred monohydroxy-functionalized aldehydes are selected from at least a member of the group 1-hydroxypropanal, 5-hydroxypentanal, 3,7-dimethyl-7-hydroxyoctanal, hydroxyisohexyl-3-cyclohexene-1-carboxaldehyde and 2,6,6-trimethyl-1,3-cyclohexadiene-1-carboxaldehyde ,

Polyhydroxyfunktionalisierte Aldehydes are preferred according to the invention the so-called aldoses and are particularly preferably selected from at least one member of the group 2,3-dihydroxypropionaldehyde, D-erythrose, D-threose, D-ribose, D-arabinose, D-lyxose, D-xylose, D-allose, D-altrose, D-galactose, D-glucose, D-idose, D-mannose, D-rhamnose and D-talose, as well as the L-configurations L-erythrose, L-threose, L-ribose, L-arabinose, L-lyxose, L-xylose, L-allose, L-altrose, L-galactose, L-glucose, L-idose, L-mannose, L-rhamnose and L-talose.

Monohydroxyfunktionalisierte Ketones, which are inventively particularly are suitable, are preferably selected from at least one member of the group 1-hydroxy-2-propanone, 1-hydroxy-2-butanone, 3-hydroxy-2-butanone and benzoin.

Polyhydroxyfunktionalisierte Ketones are preferred according to the invention the so-called ketoses and are particularly preferably selected from at least one member of the group consisting of 1,3-dihydroxyacetone, D-psicose, D-fructose, D-sorbose, D-tagatose, D-ribulose, D-xylulose, D-erythrulose and the L-configurations L-Psicose, L-Fructose, L-Sorbose, L-Tagatose, L-Ribulose, L-Xylulose, L-Erythrulose.

• – Benzylidenketone, insbesondere den Benzylidenketonen aus der Patentanmeldung DE-A1-19717281 (siehe DE-A1-19717281: Formel (I) des 1. Anspruchs und die Vertreter gemäß 4. Anspruch), auf die ausdrücklich bezuggenommen wird,
• – Imidazolin-2,4-dion und dessen Derivaten, insbesondere Allantoin und/oder 5,5-Dimethylhydantoin.

Preferred alicyclic, aromatic or heterocyclic ketones are preferably selected from at least one member of the group

• Benzylidene ketones, in particular the benzylidene ketones from the patent application DE-A1-19717281 (see DE-A1-19717281: formula (I) of the first claim and the representatives according to claim 4), to which reference is expressly made,
• - imidazoline-2,4-dione and its derivatives, in particular allantoin and / or 5,5-dimethylhydantoin.

• – Benzaldehyd und seinen Derivaten,
• – Zimtaldehyd und seinen Derivaten sowie
• – Naphthaldehyd und seinen Derivaten.

Preferred alicyclic, aromatic or heterocyclic aldehydes are preferably selected from at least one member of the group

• - benzaldehyde and its derivatives,
• - cinnamaldehyde and its derivatives as well
• - Naphthaldehyde and its derivatives.

The derivatives of benzaldehydes, naphthaldehydes or cinnamaldehydes are preferably selected from at least one member selected from benzaldehyde, 1-naphthaldehyde, coniferylaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde , 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxy-benzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4 Hydroxy-2-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 3,5-diethoxy 4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxy-benzaldehyde, 3-hydroxy-2-methoxybenzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2 Ethoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde , 2,5-dimethoxybenzal dehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3,6-trimethoxybenzaldehyde, 2,4,6- Trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,4-dihydroxy-3- methyl-benzaldehyde, 2,4-dihydroxy-5-methyl-benzaldehyde, 2,4-dihydroxy-6-methylbenzaldehyde, 2,4-dihydroxy-3-methoxy-benzaldehyde, 2,4-dihydroxy-5-methoxy benzaldehyde, 2,4-dihydroxy-6-methoxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-2-methylbenzaldehyde, 3,4-dihydroxybenzaldehyde 5-methylbenzaldehyde, 3,4-dihydroxy-6-methylbenzaldehyde, 3,4-dihydroxy-2-methoxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5- Trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,5,6-tri hydroxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 3,5-dichloro-4-hydroxybenzaldehyde, 4-hydroxy-3, 5-diiodobenzaldehyde, 3-chloro-4-hydroxybenzaldehyde, 5-chloro-3,4-dihydroxybenzaldehyde, 5-bromo-3,4-dihydroxybenzaldehyde, 3-chloro-4-hydroxy-5-methoxybenzaldehyde, 4-hydroxybenzaldehyde 3-iodo-5-methoxybenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy 1-naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4- dimethylamino-1-naphthaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3- nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3-nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 4,5-dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2.5- Dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 4-dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino 2-methylbenzaldehyde, 4-diethylamino-cinnamic aldehyde, 4-dibutylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4- (1-imidazolyl) benzaldehyde and piperonal.

All Aldehyde or keto compounds are said to be physiologically tolerated or non-toxic compounds are selected when the agent according to the invention should be used as a cosmetic agent.

The Connections selected from aldehydes and / or ketones are preferred according to the invention in an amount of 0.1% by weight to 20% by weight, in particular 0.5 Wt .-% to 10 wt .-%, each based on the weight of the ready-to-use By means, in the agent according to the invention contain.

It may be preferred according to the invention be, the agent of the invention with the proviso to provide that the compounds used in the agent according to the invention, selected from the aldehydes and / or the ketones, from those aldehydes or ketones must differ, from which those sulfinic acids derived in the agent of the invention indeed are included.

It is also preferred according to the invention, when the agent according to the invention additionally contains at least one reductone. A reductone is understood by the person skilled in the art to be reductive endiol compounds which by substitution in α-position are stabilized and subject to tautomerism. The most important can be used according to the invention Reductones are ascorbic acid, isoascorbic acid, 2,3-dihydroxy-2-propendial and 2,3-dihydroxy-2-cyclopentenone.

The Reductones are preferred according to the invention in an amount of 0.1% by weight to 20% by weight, in particular 0.5 Wt .-% to 10 wt .-%, each based on the weight of the ready-to-use By means, in the agent according to the invention contain.

When carrier for the inventive agent are preferably liquid Media in which the sulfinic acid derivative according to the invention is preferably soluble, such as water or organic solvents. It is preferred according to the invention if the carrier a cosmetic carrier is.

When cosmetic carriers are especially creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations, especially for the application on the hair are suitable. But it is also conceivable the ingredients in a powdered or tablet-like formulation which is dissolved in water before use. The cosmetic carrier can especially watery or watery-alcoholic be.

One aqueous cosmetic carrier contains at least 50% by weight of water.

For the purposes of the present invention, aqueous-alcoholic cosmetic carriers 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. Other alcoholic solvents are, for example, methoxybutanol, benzyl alcohol, 2-phenoxyethanol, ethyldiglycol or 1,2-propylene glycol. In a preferred embodiment, the inventive composition additionally contains, as solvent, at least one (C ₂ to C ₆ ) -alkyl monoalcohol and / or a (C ₂ to C ₆ ) -alkanediol, in particular ethanol, isopropanol and / or 1,2-propylene glycol.

The inventive agent preferably has a pH of pH 1 to pH 9, in particular from pH 1.5 to pH 6.

One second object of the invention is the use of the agent according to the first Subject of the invention for decolorization of substrates that are natural and / or synthetic dyes are colored.

The Contains substrate preferably synthetic fibers and / or natural fibers.

The natural Fibers are preferably selected from cellulosic fibers, in particular cotton, and keratin-containing Fibers, in particular wool or animal or human hair, most preferably from human hair.

The Synthetic fibers will preferably be selected from polyester, polyamide (such as nylon), elastane, viscose or polyacrylic.

The to decolorize Substrates are preferred with oxidation dyes and / or substantive dyes, as a representative of synthetic dyes, dyed.

When for coloring The developer components used in the substrate may in principle be subsequent developer components serve.

wobei

• – G¹ steht für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen 4'-Aminophenylrest oder einen C₁- bis C₄-Alkylrest, der mit einer stickstoffhaltigen Gruppe, einem Phenyl- oder einem 4'-Aminophenylrest substituiert ist;
• – G² steht für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest oder einen C₁- bis C₄-Alkylrest, der mit einer stickstoffhaltigen Gruppe substituiert ist;
• – G³ steht für ein Wasserstoffatom, ein Halogenatom, wie ein Chlor-, Brom-, Iod- oder Fluoratom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Hydroxyalkoxyrest, einen C₁- bis C₄-Acetylaminoalkoxyrest, einen C₁- bis C₄-Mesylaminoalkoxyrest oder einen C₁- bis C₄-Carbamoylaminoalkoxyrest;
• – G⁴ steht für ein Wasserstoffatom, ein Halogenatom oder einen C₁- bis C₄-Alkylrest oder
• – wenn G³ und G⁴ in ortho-Stellung zueinander stehen, können sie gemeinsam eine verbrückende α,ω-Alkylendioxogruppe, wie beispielsweise eine Ethylendioxygruppe bilden.

Particular preference is given to p-phenylenediamine derivatives of the formula (E1)

in which

• G ¹ represents a hydrogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ alkoxy radical (C ₁ - to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;
• G ² represents a hydrogen atom, a C ₁ -C ₄ -alkyl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a C ₁ -C ₄ -alkoxy radical (C ₁ - to C ₄ ) -alkyl radical or a C ₁ - to 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 - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl, C ₁ - to C ₄ -hydroxyalkoxy, C ₁ - to C ₄ -acetylaminoalkoxy, C ₁ - to C ₄ -mesylaminoalkoxy or C ₁ - to C ₄ -carbamoylaminoalkoxy;
• - G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ - to C ₄ -alkyl radical or
• When G ³ and G ⁴ are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.

Especially 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- (α, β-dihydroxyethyl) -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, N- (4-amino-3-methylphenyl) -N- [3- (1H -imidazol-1-yl) propyl] amine and 5,8-diaminobenzo-1,4-dioxane and their physiologically acceptable Salt.

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

It may further be preferred according to the invention for coloring the substrate, as a developer Kompo nente compounds containing at least two aromatic nuclei, which are substituted with amino and / or hydroxyl groups.

wobei:

• – Z¹ und Z² stehen unabhängig voneinander für einen Hydroxyl- oder NH₂-Rest, der gegebenenfalls durch einen C₁- bis C₄-Alkylrest, durch einen C₁- bis C₄-Hydroxyalkylrest und/oder durch eine Verbrückung Y substituiert ist oder der gegebenenfalls Teil eines verbrückenden Ringsystems ist,
• – die Verbrückung Y steht für eine Alkylengruppe mit 1 bis 14 Kohlenstoffatomen, wie beispielsweise eine lineare oder verzweigte Alkylenkette oder einen Alkylenring, die von einer oder mehreren stickstoffhaltigen Gruppen und/oder einem oder mehreren Heteroatomen wie Sauerstoff-, Schwefel- oder Stickstoffatomen unterbrochen oder beendet sein kann und eventuell durch einen oder mehrere Hydroxyl- oder C₁- bis C₈-Alkoxyreste substituiert sein kann, oder eine direkte Bindung,
• – G⁵ und G⁶ stehen unabhängig voneinander für ein Wasserstoff- oder Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest oder eine direkte Verbindung zur Verbrückung Y,
• – G⁷, G⁸, G⁹, G¹⁰, G¹¹ und G¹² stehen unabhängig voneinander für ein Wasserstoffatom, eine direkte Bindung zur Verbrückung Y oder einen C₁- bis C₄-Alkylrest, mit der Maßgabe, dass die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten.

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 are a hydroxyl or NH ₂ radical which is optionally substituted by a C ₁ - to C ₄ -alkyl radical, by a C ₁ - to C ₄ -hydroxyalkyl radical and / or by a bridge Y. or 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 and may be substituted by one or more hydroxyl or C ₁ - to C ₈ alkoxy, or a direct bond,
• G ⁵ and G ⁶ independently of one another are a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a direct compound for bridging Y,
• - G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² are each independently a hydrogen atom, a direct bond to the bridge Y or a C ₁ - to C ₄ alkyl radical, with the proviso that the compounds of the Formula (E2) contain only one bridge Y per molecule.

The used in formula (E2) substituents are analogous to the invention to the above statements Are 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) tetramethylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-diethyl-N, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine, Bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1,4-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 tolerable Salts.

All 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, 1,3-bis- (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4-aminophenyl) -1,4-diazacycloheptane and 1,10-bis (2,5-diaminophenyl) -1,4,7,10-tetraoxadecane or one their physiologically compatible Salts.

wobei:

• – G¹³ steht für ein Wasserstoffatom, ein Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest, einen Hydroxy-(C₁- bis C₄)-alkylaminorest, einen C₁- bis C₄-Hydroxyalkoxyrest, einen C₁- bis C₄-Hydroxyalkyl-(C₁- bis C₄)-aminoalkylrest oder einen (Di-C₁- bis C₄-Alkylamino)-(C₁- bis C₄)-alkylrest, und
• – G¹⁴ steht für ein Wasserstoff- oder Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest oder einen C₁- bis C₄-Cyanoalkylrest,
• – G¹⁵ steht für Wasserstoff, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen Phenylrest oder einen Benzylrest, und
• – G¹⁶ steht für Wasserstoff oder ein Halogenatom.

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 for coloring the substrate to be decolored. 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 - to C ₄ alkyl, C ₁ - to C ₄ monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ Alkoxy (C ₁ to C ₄ ) alkyl, C ₁ to C ₄ aminoalkyl, hydroxy (C ₁ to C ₄ ) alkylamino, C ₁ to C ₄ hydroxyalkoxy, C ₁ - to C ₄ -hydroxyalkyl- (C ₁ - to C ₄ ) -aminoalkyl or a (di-C ₁ - to C ₄ -alkylamino) - (C ₁ - to C ₄ ) -alkyl, and
• - G ¹⁴ represents a hydrogen or halogen atom, a C ₁ - to C ₄ alkyl, C ₁ - to C ₄ monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ Alkoxy (C ₁ to C ₄ ) alkyl, C ₁ to C ₄ aminoalkyl or C ₁ to C ₄ cyanoalkyl,
• G ¹⁵ is hydrogen, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and
• - G ¹⁶ is hydrogen or a halogen atom.

The used in formula (E3) substituents are analogous to the invention to the above statements Are 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-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino-2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) phenol, 4-amino-2- (α, β-dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) -phenol as well as their physiologically tolerable Salts.

All particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) -phenol and 4-amino-2- (diethylaminomethyl) -phenol.

Further For example, the developer component can be selected from o-aminophenol and its derivatives, such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

Farther For example, the developer component may be selected from heterocyclic Developer components, such as the pyridine, pyrimidine, Pyrazole, pyrazole pyrimidine derivatives and their physiologically tolerable Salt.

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 pyrimidine derivatives are in particular the compounds described in the German patent DE 23 59 399 , the Japanese Patent Application JP 02019576 A2 or in the laid-open specification WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino 4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.

Preferred pyrazole derivatives are in particular the compounds described in the patents DE 38 43 892 . DE 41 33 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 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-me ethylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'- methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4.5 Diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (β-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole , 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole.

wobei:

• – G¹⁷, G¹⁸, G¹⁹ und G²⁰ unabhängig voneinander stehen für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest, der gegebenenfalls durch ein Acetyl-Ureid- oder einen Sulfonyl-Rest geschützt sein kann, einen (C₁- bis C₄)-Alkylamino-(C₁- bis C₄)-alkylrest, einen Di-[(C₁- bis C₄)-alkyl]-(C₁- bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁- bis C₄-Hydroxyalkyl- oder einen Di-(C₁- bis C₄)-[Hydroxyalkyl]-(C₁- bis C₄)-aminoalkylrest,
• – die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest, einen (C₁- bis C₄)-Alkylamino-(C₁- bis C₄)-alkylrest, einen Di-[(C₁- bis C₄)alkyl]-(C₁- bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁- bis C₄-Hydroxyalkyl- oder einen Di-(C₁- bis C₄-hydroxyalkyl)-aminoalkylrest, einen Aminorest, einen C₁- bis C₄-Alkyl- oder Di-(C₁- bis C₄-hydroxyalkyl)-aminorest, ein Halogenatom, eine Carboxylsäuregruppe oder eine Sulfonsäuregruppe,
• – i hat den Wert 0, 1, 2 oder 3,
• – p hat den Wert 0 oder 1,
• – q hat den Wert 0 oder 1 und
• – n hat den Wert 0 oder 1, mit der Maßgabe, dass
• – die Summe aus p + q ungleich 0 ist,
• – wenn p + q gleich 2 ist, n den Wert 0 hat, und die Gruppen NG¹⁷G¹⁸ und NG¹⁹G²⁰ belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);
• – wenn p + q gleich 1 ist, n den Wert 1 hat, und die Gruppen NG¹⁷G¹⁸ (oder NG¹⁹G²⁰) und die Gruppe OH belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);

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

in which:

• - G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ -Polyhydroxyalkylrest a (C ₁ - to C ₄ ) alkoxy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -Aminoalkylrest, optionally protected by an acetyl-ureide or a sulfonyl radical may be a (C ₁ to C ₄ ) alkylamino (C ₁ to C ₄ ) alkyl radical, a di - [(C ₁ to C ₄ ) alkyl] - (C ₁ to C ₄ ) aminoalkyl radical, wherein the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C ₁ - to C ₄ ) aminoalkyl radical,
• - The X radicals independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl, a (C ₁ - to C ₄ ) -alkylamino- (C ₁ - to C ₄ ) -alkyl, a di - [(C ₁ - to C ₄ ) alkyl] - (C ₁ - bis 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 - to C ₄ -hydroxyalkyl or a di- (C ₁ - to C ₄ -hydroxyalkyl) aminoalkyl radical , an amino radical, a C ₁ - to C ₄ -alkyl or di- (C ₁ - to C ₄ -hydroxyalkyl) -amino radical, a halogen atom, a carboxylic acid group or a 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 used in formula (E4) substituents are analogous to the invention to the above statements Are 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 represented, for example, in the following scheme:

• – Pyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 2,5-Dimethylpyrazolo[1,5-a]-pyrimidin-3,7-diamin;
• – Pyrazolo[1,5-a]pyrimidin-3,5-diamin;
• – 2,7-Dimethyl-pyrazolo[1,5-a]pyrimidin-3,5-diamin;
• – 3-Aminopyrazolo[1,5-a]pyrimidin-7-ol;
• – 3-Aminopyrazolo[1,5-a]pyrimidin-5-ol;
• – 2-(3-Aminopyrazolo[1,5-a]pyrimidin-7-ylamino)-ethanol;
• – 2-(7-Aminopyrazolo[1,5-a]pyrimidin-3-ylamino)-ethanol;
• – 2-[(3-Aminopyrazolo[1,5-a]pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 2-[(7-Aminopyrazolo[1,5-a]pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 5,6-Dimethylpyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 2,6-Dimethylpyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 3-Amino-7-dimethylamino-2,5-dimethylpyrazolo[1,5-a]pyrimidin;

sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomeres Gleichgewicht vorhanden ist.In particular, among the pyrazolo [1,5-a] pyrimidines of the above formula (E4):

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

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

The Pyrazolo1,5-a] pyrimidines of the above formula (E4) can as described in the literature by cyclization starting from a Aminopyrazole or produced from hydrazine.

In a further preferred embodiment were to be decolored Substrates with an oxidative dye colored, which in addition to at least one developer component additionally at least one Coupler component contains.

When Coupler components are usually m-phenylenediamine derivatives, Naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives used. Particularly suitable coupling agents are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, Resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2 ', 4'-diaminophenoxy) propane, 2-chloro-resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

• – m-Aminophenol und dessen Derivate wie beispielsweise 5-Amino-2-methylphenol, N-Cyclopentyl-3-aminophenol, 3-Amino-2-chlor-6-methylphenol, 2-Hydroxy-4-aminophenoxyethanol, 2,6-Dimethyl-3-aminophenol, 3-Trifluoroacetylamino-2-chlor-6-methylphenol, 5-Amino-4-chlor-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)-benzol, 3-Ethylamino-4-methylphenol und 2,4-Dichlor-3-aminophenol,
• – o-Aminophenol und dessen Derivate,
• – m-Diaminobenzol und dessen Derivate wie beispielsweise 2,4-Diaminophenoxy-ethanol, 1,3-Bis-(2',4'-diaminophenoxy)-propan, 1-Methoxy-2-amino-4-(2'-hydroxyethylamino)benzol, 1,3-Bis-(2',4'-diaminophenyl)-propan, 2,6-Bis-(2'-hydroxyethylamino)-1-methylbenzol, 2-({3-[(2-Hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol, 2-({3-[(2-Hydroxyethyl)amino]-2-methoxy-5-methylphenyl}amino)ethanol, 2-[3-Morpholin-4-ylphenyl)amino]ethanol, 3-Amino-4-(2-methoxyethoxy)-5-methylphenylamin und 1-Amino-3-bis-(2'-hydroxyethyl)-aminobenzol,
• – o-Diaminobenzol und dessen Derivate wie beispielsweise 3,4-Diaminobenzoesäure und 2,3-Diamino-1-methylbenzol,
• – Di-beziehungsweise Trihydroxybenzolderivate wie beispielsweise Resorcin, Resorcinmonomethylether, 2-Methylresorcin, 5-Methylresorcin, 2,5-Dimethylresorcin, 2-Chlorresorcin, 4-Chlorresorcin, Pyrogallol und 1,2,4-Trihydroxybenzol,
• – Pyridinderivate wie beispielsweise 2,6-Dihydroxypyridin, 2-Amino-3-hydroxypyridin, 2-Amino-5-chlor-3-hydroxypyridin, 3-Amino-2-methylamino-6-methoxypyridin, 2,6-Dihydroxy-3,4-dimethylpyridin, 2,6-Dihydroxy-4-methylpyridin, 2,6-Diaminopyridin, 2,3-Diamino-6-methoxypyridin und 3,5-Diamino-2,6-dimethoxypyridin,
• – Naphthalinderivate wie beispielsweise 1-Naphthol, 2-Methyl-1-naphthol, 2-Hydroxymethyl-1-naphthol, 2-Hydroxyethyl-1-naphthol, 1,5-Dihydroxynaphthalin, 1,6-Dihydroxynaphthalin, 1,7-Dihydroxynaphthalin, 1,8-Dihydroxynaphthalin, 2,7-Dihydroxynaphthalin und 2,3-Dihydroxynaphthalin,
• – Morpholinderivate wie beispielsweise 6-Hydroxybenzomorpholin und 6-Amino-benzomorpholin,
• – Chinoxalinderivate wie beispielsweise 6-Methyl-1,2,3,4-tetrahydrochinoxalin,
• – Pyrazolderivate wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on,
• – Indolderivate wie beispielsweise 4-Hydroxyindol, 6-Hydroxyindol und 7-Hydroxyindol,
• – Pyrimidinderivate, wie beispielsweise 4,6-Diaminopyrimidin, 4-Amino-2,6-dihydroxypyrimidin, 2,4- Diamino-6-hydroxypyrimidin, 2,4,6-Trihydroxypyrimidin, 2-Amino-4-methylpyrimidin, 2-Amino-4-hydroxy-6-methylpyrimidin und 4,6-Dihydroxy-2-methylpyrimidin, oder
• – Methylendioxybenzolderivate wie beispielsweise 1-Hydroxy-3,4-methylendioxybenzol, 1-Amino-3,4-methylendioxybenzol und 1-(2'-Hydroxyethyl)-amino-3,4-methylendioxybenzol

sowie deren physiologisch verträglichen Salze.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 2,4-diaminophenoxy-ethanol, 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, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2- [3-morpholine-4 -ylphenyl) amino] ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine 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, for example, resorcinol, resorcinomonomethyl 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-aminobenzomorpholine,
• 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 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene

and their physiologically acceptable salts.

Particularly according to the invention preferred coupler components are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, Resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

In addition, the to decolorize Substrates with precursors of natural dyes preferred under Be colored with the aid of such indoles and indolines, which are preferred at least two hydroxy or amino groups, preferably as a substituent on the six-membered ring. These groups can bear further substituents, for. B. in the form of an etherification or Esterification of the hydroxy group or alkylation of the amino group.

in der unabhängig voneinander

• – G²¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxy-alkylgruppe,
• – G²² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• – G²³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• – G²⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-G²⁶, in der G²⁶ steht für eine C₁-C₄-Alkylgruppe, und
• – G²⁵ steht für eine der unter G²⁴ genannten Gruppen,

sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.Particularly suitable as precursors of natural-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula XIIIa,

in the independently of each other

• G ²¹ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxy-alkyl group,
• G ²² is hydrogen or a -COOH group, where the -COOH group may also be in the form of a salt with a physiologically compatible cation,
• G ²³ is hydrogen or a C ₁ -C ₄ -alkyl group,
• - G ²⁴ is hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-G ²⁶ , in which G ²⁶ is a C ₁ -C ₄ alkyl group, and
• - G ²⁵ stands for one of the groups mentioned under G ²⁴ ,

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

Especially 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, 6-aminoindoline and 4-aminoindoline.

Especially 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 in particular the 5,6-dihydroxyindoline.

in der unabhängig voneinander

• – G²⁷ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxyalkylgruppe,
• – G²⁸ steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• – G²⁹ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• – G³⁰ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-G³², in der G³² steht für eine C₁-C₄-Alkylgruppe, und
• – G³¹ steht für eine der unter G³⁰ genannten Gruppen,
• – sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.

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

in the independently of each other

• G ²⁷ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxyalkyl group,
• G ²⁸ is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
• G ²⁹ is hydrogen or a C ₁ -C ₄ -alkyl group,
• G ³⁰ is hydrogen, a C ₁ -C ₄ -alkyl group or a group -CO-G ³² , in which G ³² is a C ₁ -C ₄ -alkyl group, and
• - G ³¹ stands for one of the groups mentioned in G ³⁰ ,
• - As well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

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

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

The to be decolourised Substrate may also have been dyed with substantive dyes be. As substantive dyes are in particular nitrophenylenediamines, Nitroaminophenols, azo dyes, anthraquinones or indophenols in question. Preferred substantive dyes are those of the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 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.

• (a) kationische Triphenylmethanfarbstoffe, wie beispielsweise Basic Blue 7, Basic Blue 26, Basic Violet 2 und Basic Violet 14,
• (b) aromatischen Systeme, die mit einer quaternären Stickstoffgruppe substituiert sind, wie beispielsweise Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 und Basic Brown 17, sowie
• (c) direktziehende Farbstoffe, die einen Heterocyclus enthalten, der mindestens ein quaternäres Stickstoffatom aufweist, wie sie beispielsweise in der EP-A2-998 908, auf die an dieser Stelle explizit Bezug genommen wird, in den Ansprüchen 6 bis 11 genannt werden.

Further, the substrates to be decolored may preferably be colored with a cationic substantive dye. 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 Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as
• (C) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as mentioned for example in EP-A2-998 908, to which reference is explicitly made at this point in claims 6 to 11 are called.

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

The compounds of the formulas (DZ1), (DZ3) and (DZ5) are very particularly preferred cationic substantive dyes of group (c). The cationic direct dyes, which are sold under the trademark Arianor ^® are, according to the invention particularly preferred substantive dyes.

Farther can the to be decolored Substrates also with naturally occurring, natural dyes, as in red henna, henna neutral, henna black, Chamomile, Sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and Alkana root are colored.

One third subject of the invention is a process for reductive discoloration with natural and / or colored synthetic dyes Substrates in which a means of the first subject of the invention on the colored Substrate is applied and rinsed again after a contact time.

The Exposure time is preferably 1 to 60 minutes, preferably 5 to 30 minutes. The impact the agent according to the invention can not only at room temperature, but preferably in a temperature range from 15 to 60 ° C, in particular from 25 to 60 ° C respectively.

To Expiry of the exposure time, the hair is rinsed, preferably a surfactant-containing Agents, such as a cleanser or a shampoo, Application finds. Optionally, the substrate can be rinsed out several times, or be treated several times with the surfactant-containing agent.

The Surfactant-containing agent for rinsing or after-treatment contains preferably in a carrier at least one surfactant selected from anionic, zwitterionic, ampholytic, nonionic or cationic surfactants, especially nonionic surfactants.

• – lineare Fettsäuren mit 10 bis 22 C-Atomen (Seifen),
• – Ethercarbonsäuren der Formel R-O-(CH₂-CH₂O)_x-CH₂-COOH, in der R eine lineare Alkylgruppe mit 10 bis 22 C-Atomen und x = 0 oder 1 bis 16 ist,
• – Acylsarcoside mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Acyltauride mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Acylisethionate mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Sulfobernsteinsäuremono- und -dialkylester mit 8 bis 18 C-Atomen in der Alkylgruppe und Sulfobernsteinsäuremono-alkylpolyoxyethylester mit 8 bis 18 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen,
• – lineare Alkansulfonate mit 12 bis 18 C-Atomen,
• – lineare Alpha-Olefinsulfonate mit 12 bis 18 C-Atomen,
• – Alpha-Sulfofettsäuremethylester von Fettsäuren mit 12 bis 18 C-Atomen,
• – Alkylsulfate und Alkylpolyglykolethersulfate der Formel R-O(CH₂-CH₂O)_x-SO₃H, in der R eine bevorzugt lineare Alkylgruppe mit 10 bis 18 C-Atomen und x = 0 oder 1 bis 12 ist,
• – Gemische oberflächenaktiver Hydroxysulfonate gemäß DE-A-37 25 030,
• – sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether gemäß DE-A-37 23 354,
• – Sulfonate ungesättigter Fettsäuren mit 12 bis 24 C-Atomen und 1 bis 6 Doppelbindungen gemäß DE-A-39 26 344,
• – Ester der Weinsäure und Zitronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2–15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen darstellen.

Suitable anionic surfactants in the surface-active compositions according to the invention for rinsing or aftertreatment are all anionic surface-active substances which are suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. As a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 C-Ato men. 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,
• Sulfosuccinic acid mono- and dialkyl esters having 8 to 18 C atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters having 8 to 18 C 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 hydroxyalkylpolyethylene and / or hydroxyalkylene-propylene glycol ethers 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 which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 carbon 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 ,

Zwitterionic surfactants are those surface-active compounds which carry in the molecule at least one quaternary ammonium group and at least one -COO ^(-) or -SO ₃ ^(-) group. 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 having in each case 8 to 18 C atoms in the alkyl or acyl group, and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are understood as meaning those surface-active compounds which, apart from a C _8-18 -alkyl or -acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-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, cocoacylaminoethylaminopropionate and C _12-18 acylsarcosine.

• – Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• – C_12-22-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin,
• – C_8-22-Alkylmono- und -oligoglycoside und deren ethoxylierte Analoga,
• – Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl,
• – Anlagerungeprodukte von Ethylenoxid an Sorbitanfettsäureester
• – Anlagerungsprodukte von Ethylenoxid an Fettsäurealkanolamide.

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

• Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide onto linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids containing 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,
• C _12-22 fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol,
• C _{8-22 alkyl} mono- and oligoglycosides and their ethoxylated analogs,
• Adducts of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil,
• - Addition products of ethylene oxide to sorbitan fatty acid esters
• - Addition products of ethylene oxide to fatty acid alkanolamides.

Examples for the in the surfactant-containing according to the invention Means for rinsing or post-treatment cationic surfactants are particularly quaternary Ammonium compounds. Preference is given to ammonium halides such as alkyltrimethylammonium chlorides, Dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, z. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, Distearyldimethylammonium chloride, lauryldimethylammonium chloride, Lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Further usable according to the invention cationic surfactants are the quaternized protein hydrolysates represents.

Also suitable in the present invention are cationic silicone oils such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a 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).

Alkylamidoamines, in particular fatty acid amidoamines, such as the ^{stearylamidopropyldimethylamine} obtainable under the name Tego ^Amid® S 18, are distinguished not only by a good conditioning action but also by their good biodegradability.

Also very good biodegradability are quaternary Esterverbindungen, so-called "esterquats", hydroxyalkyldialkoyloxyalkylammoniummethosulfate methyl-such as those sold under the trademark Stepantex ^®.

An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ^® 100, according to CTFA nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

at the compounds used as surfactants with alkyl groups each are uniform substances. However, it is usually preferred in the preparation of these substances of native vegetable or animal raw materials, so that you substance mixtures obtained with different, depending on the raw material alkyl chain lengths.

The Surfactants are preferably used in concentrations of from 0.5 to 30% by weight, based on the weight of the composition, in the surfactant-containing Means for rinsing or post-treatment used.

In addition, the surfactant-containing rinse or aftertreatment agent has a pH of less than pH 7. This pH is preferably kept constant by the addition of a buffer during the rinsing or aftertreatment step. Suitable buffer systems according to the invention are the phosphate buffer (PO ₄ ^3- / HPO ₄ ^2- / H ₂ PO ₄ ^- / H ₃ PO ₄ ), acetic acid / acetate buffer, citric acid / citrate buffer, KCl / HCl buffer, monophthalate / HCl buffer or monophthalate / NaOH buffer.

To rinsing out it may be advantageous to use the substrate with an oxidant-containing To treat composition. Preference is given to hydrogen peroxide as oxidizing agent, preferably in concentrations of 0.5 to 6 Wt .-%, used. The exposure time is preferably 1 to 30 minutes, more preferably 1 to 10 minutes. After expiry of the exposure time the oxidant-containing composition is rinsed out.

When preferred colored Substrates are those defined in the second subject of the invention were.

When preferred natural or synthetic dyes were preferred those dyes used, they were defined in the second subject of the invention.

Of the Subject of the invention is exemplified by the following statements explained become.

Examples

The decolorizing agents according to the invention according to Table 1 were provided. The following raw materials were used:

The Raw materials were gradually mixed in 75 wt% water with stirring. Subsequently the pH was adjusted and possibly with water to 100 wt .-% refilled.

Table 1: Decolorizing agent

Method 1:

The following procedure was carried out for all decolorizers of Table 1:
A strand of hair (natural hair, Fa. Kerling) was with a commercial oxidative hair color (Igora ^® Royal (Schwarzkopf), coloring cream natural clay in a weight ratio of 1 to 1 with the developer Oxigenta ^® (6 wt .-% hydrogen peroxide, Schwarzkopf) over a contact time After being dyed for 30 minutes at room temperature, rinsed and stored for 24 hours, the tress was immersed in 30 mL of a decolorizer of Table 1 for 30 minutes at room temperature, then rinsed with plenty of water and air dried.

All strands of hair showed after the decolorization procedure an excellent lightening and a small hair damage. The hair strands experienced no darkening even after 2 weeks of storage.

Method 2:

The following procedure was carried out for all decolorizers of Table 1:
A hair tress dyed with the oxidative hair color according to Experiment 1 (natural hair, Messrs. Kerling) was immersed in 30 mL of one of the decolorizing agents of Table 1 over an exposure time of 30 minutes at room temperature. In contrast to experiment 1, however, the tress was then washed for 2 minutes in 50 ml of one of the surfactant-containing rinsing agents according to Table 2, rinsed under running water for less than 1 minute and dried in air.

Table 2: surfactant-containing rinse

All strands of hair showed with each of the agents B1 to B3 after rinsing one improved lightening compared to a strand of hair Method 1, which was rinsed with water only. The hair damage is low. The hair strands experienced no darkening even after 2 weeks of storage.

Claims (24)

Reductive color proofing agent comprising in a carrier at least one sulfinic acid derivative of the formula (I)

wherein M is a hydrogen atom or one equivalent of a mono- or polyvalent cation, R is derived from a peptide or is a radical according to one of the formulas (II) to (VI),

wherein Y and Y 'independently represent a hydroxy group, an -NH ₂ group or a group -NR ³ R ⁴ , wherein R ³ and R ⁴ independently of one another represent a (C ₁ to C ₆ ) -alkyl group, a (C ₂ to C ₆ ) alkenyl group, a (C ₁ to C ₆ ) hydroxyalkyl group, a (C ₂ to C ₆ ) polyhydroxyalkyl group, an aryl group or an aryl (C ₁ to C ₆ ) alkyl group, M 'independently of M the features listed under M, X is a direct bond or an organic radical having two free valencies, R ¹ and R ^{14 are} independently a hydrogen atom, a (C ₁ to C ₆ ) alkyl group or a carboxyalkyl group - (CH ₂ ) _m -COOM ^II in which M ^{II represents} a hydrogen atom or one equivalent of a mono- or polyvalent cation and m is the number 0, 1 or 2, R ^{2 is} a hydrogen atom, a (C ₁ to C ₆ ) alkyl group, a carboxyalkyl radical - (CH ₂ ) _n -COOM ^III with M ^III = hydrogen atom or one equivalent of a mono- or polyvalent cation and n is a gan ze number 0, 1, 2, 3, 4, 5 or 6, a (C ₁ to C ₆ ) alkyloxycarbonyl, a sulfonic group, a carbamoyl group, an N, N-di [(C ₁ to C ₆ ) alkyl] carbamoyl group, an N, N, N-tri [(C ₁ to C ₆ ) alkyl] ammonium (C ₁ to C ₆ ) alkyl group, a carboxy (C ₂ to C ₆ ) alkenyl group, a cyano (C ₁ to C ₆ ) alkyl group or a (C ₁ to C ₆ ) alkoxycarbonyl (C ₁ to C ₆ ) alkyl group, an aliphatic or aromatic heterocycle which may be substituted, or a radical of formula (IV) or R ² together with R ¹ and the remainder of the molecule forms an aliphatic 5-, 6- or 7-membered ring containing at least one cationic, quaternized nitrogen atom as heteroatom, the cationic charge optionally being compensated by one equivalent of a monovalent or polyvalent anion R ^{7 is} a carboxy group, a sulfonic acid group, a (C ₁ to C ₆ ) alkoxycarbonyl group, a sulfonamide group, a cyano group, a nitro group, a carboxy (C ₁ to C ₆ ) -alkyl group, a carboxy (C ₁ to C ₆ ) -alkoxy group or a group -N ⁺ R ^I R ^II R ^III with R ^I , R ^II and R ^III independently of one another represent a (C ₁ to C ₆ ) Alkyl group, a (C ₂ to C ₆ ) alkenyl group, an aryl (C ₁ to C ₆ ) alkyl group or a (C ₁ to C ₆ ) hydroxyalkyl group, R ⁸ and R ⁹ independently represent a hydrogen atom, a (C ₁ to C ₆ ) -alkyl group, a (C ₂ to C ₆ ) -alkenyl group, a (C ₁ to C ₆ ) -hydroxyalkyl group, a (C ₂ to C ₆ ) -polyhydroxyalkyl group, a (C ₁ to C ₆ ) - Alkoxy group, hydroxy group, amino group, carboxy group, nitro group, cyano group or halogen atom, R ^{10 is} (C ₁ to C ₆ ) alkyl group, optionally substituted aryl group, optionally substituted heteroaryl group, carboxy (C ₁ to C ₆ ) alkyl group, a carboxy (C ₂ to C ₆ ) alkenyl group, a (C ₁ to C ₆ ) -alkoxycarbonyl group or a (C ₁ to C ₆ ) -alkoxycarbonyl (C ₁ to C ₆ ) -alkyl group, R ¹¹ , R ¹² and R ¹³ independently of one another represent a hydrogen atom, a (C ₁ to C ₆ ) - Alkyl group, a (C ₂ to C ₆ ) alkenyl group, a perfluoro (C ₁ to C ₆ ) alkyl group, a (C ₃ to C ₆ ) cycloalkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, a (C ₁ to C ₆ ) hydroxyalkyl group, a (C ₂ to C ₆ ) polyhydroxyalkyl group, an aryl (C ₁ to C ₆ ) alkyl group, a carboxy (C ₁ to C ₆ ) alkyl group, a carboxy (C ₂ to C ₆ ) alkenyl group or a (C ₁ to C ₆ ) alkoxycarbonyl (C ₁ to C ₆ ) alkyl group, with the proviso that in formula (II) R ¹ and R ^{2 are} not simultaneously a hydrogen atom , in combination with at least one compound possessing at least one quaternary nitrogen atom. Composition according to Claim 1, characterized in that in formula (I) M, M ', M ^II and M ^III independently of one another represent a hydrogen atom, an ammonium ion, an alkali metal ion, half a equivalent of an alkaline earth metal ion or one half equivalent of a zinc ion, in particular for a hydrogen atom, an ammonium ion, a sodium ion, a potassium ion, ½ calcium ion, ½ magnesium ion or ½ zinc ion. Agent according to one of claims 1 or 2, characterized in that according to formula (I) the radicals Y of the formula (II) or the formula (III) and Y 'of the formula (III) independently of one another a hydroxy group or a group -NH ₂ mean. Agent according to one of claims 1 to 3, characterized that the Rest R for a group of formula (II) stands. Agent according to one of Claims 1 to 3, characterized in that it contains at least one of the following sulfinic acids or salts thereof: 2-furyl (amino) methanesulfinic acid, amino (thien-2-yl) methanesulfinic acid, amino (1H-imidazole-2-amino) yl) methanesulfinic acid, amino (1,3-thiazol-2-yl) methanesulfinic acid, amino (1,3-oxarol-2-yl) methanesulfinic acid, amino (1H-pyrrol-2-yl) methanesulfinic acid, amino (pyridine-2-yl) yl) methanesulfinic acid, amino (pyridin-4-yl) methanesulfinic acid, amino [3-hydroxy-5- (hydroxymethyl) -2-methylpyridin-4-yl] methanesulfinic acid, amino (quinolin-2-yl) methanesulfinic acid, amino (quinoline) 4-yl) methanesulfinic acid, 1H-benzimidazol-2-yl (amino) methanesulfinic acid, 1,3-benzothiazol-2-yl (amino) methanesulfinic acid, 1,3-benzoxazol-2-yl (amino) methanesulfinic acid, hydroxy (thienyl) 2-yl) methanesulfinic acid, hydroxy (thien-3-yl) methanesulfinic acid (3-bromothien-2-yl) (hydroxy) methanesulfinic acid, hydroxy (1H-imidazol-2-yl) methanesulfinic acid, hydroxy (1H-imidazol-5-yl ) methanesulfinic acid, hydroxy (1-methyl-5-nitr o-1H-imidazol-2-yl) methanesulfinic acid, hydroxy (1,3-thiazol-2-yl) methanesulfinic acid, hydroxy (1,3-oxazol-2-yl) methanesulfinic acid, hydroxy (1H-pyrrol-2-yl) methanesulfinic acid, hydroxy (pyridin-2-yl) methanesulfinic acid, hydroxy (pyridin-4-yl) methanesulfinic acid, hydroxy [3-hydroxy-5- (hydroxymethyl) -2-methylpyridin-4-yl] methanesulfinic acid, hydroxy (quinoline-2-) yl) methanesulfinic acid, hydroxy (quinolin-4-yl) methanesulfinic acid, 1H-benzimidazol-2-yl (hydroxy) methanesulfinic acid, 1,3-benzothiazol-2-yl (hydroxy) methanesulfinic acid, 1,3-benzoxazol-2-yl ( hydroxy) methanesulfinic acid, 1,2-dihydroxyethane-1,2-disulfinic acid, 1,3-dihydroxypropane-1,3-disulfinic acid, hydroxy {4- [hydroxy- (sulfino) methyl] phenyl} methanesulfinic acid, {2-chloro-3- [hydroxy (sulfino) methyl] cyclohexyl} (hydroxy) methanesulfinic acid, {2-chloro-3- [hydroxy (sulfino) methyl] cyclopentyl} (hydroxy) methanesulfinic acid, Hydroxy {5- [hydroxy (sulfino) methyl] thien-2-yl} methanesulfinic acid, hydroxy {2- [hydroxy (sulfino) methyl] phenyl} methanesulfinic acid, hydroxy {3- [hydroxy (sulfino) methyl] phenyl} methanesulfinic acid, 1 , 5-Dihydroxypentane-1,5-disulfinic acid, 4-hydroxy-4-sulfinobutyric acid, 1-hydroxy-4-methoxy-4-oxobutane-1-sulfinic acid, 1-hydroxy-4-ethoxy-4-oxobutane-1-sulfinic acid , 4-hydroxy-4-sulfinopentanoic acid, 2-hydroxy-5-methoxy-5-oxopentane-2-sulfinic acid, 2-hydroxy-5-ethoxy-5-oxopentane-2-sulfinic acid, 4-hydroxy-4-sulfinobut-2 -enoic acid, 1-hydroxy-4-methoxy-4-oxobut-2-en-1-sulfinic acid, 1-hydroxy-4-ethoxy-4-oxobut-2-en-1-sulfinic acid, 4-hydroxy-4-sulfinopent -2-enoic acid, 2-hydroxy-5-methoxy-5-oxopent-3-ene-2-sulfinic acid, 2-hydroxy-5-ethoxy-5-oxopent-3-ene-2-sulfinic acid, 5-hydroxy-5 sulfinopentanoic acid, 1-hydroxy-5-methoxy-5-oxopentane-1-sulfinic acid, 1-hydroxy-5-ethoxy-5-oxopentane-1-sulfinic acid, 5-hydroxy-5-sulfinohexanoic acid, 2-hydroxy-6-methoxy 6-oxohexane-2-sulfinic acid, 2-hydroxy-6-ethoxy-6-oxohexane-2-sulfinic acid Re, 4- [hydroxy (sulfino) methyl] benzoic acid, 4- [amino (sulfino) methyl] benzoic acid, {4- [hydroxy (sulfo) methyl] phenoxy} acetic acid, {4- (amino (sulfino) methyl] phenoxy } -acetic acid, 3-hydroxy-4- [hydroxy (sulfino) methyl] benzoic acid, 3-hydroxy-4- [amino (sulfino) methyl] benzoic acid, (4-cyanophenyl) (hydroxy) methanesulfinic acid, (4-cyanophenyl) (amino) -methanesulfinic acid, (4-nitrophenyl) (hydroxy) -methanesulfinic acid, (4-nitrophenyl) (amino) -methanesulfinic acid, salt of 4-hydroxy-1,1-dimethyl-4-sulfinopiperidinium, salt of 1-allyl 4-hydroxy-1-methyl-4-sulfinopiperidinium, 4-hydroxy-1,1-dimethylpiperidinium-4-sulfinate, 1-allyl-4-hydroxy-1-methylpiperidinium-4-sulfinate, [(2-methoxy-2- oxoethyl) amino] (oxo) methanesulfinic acid, [(methylsulfonyl) amino] methanesulfinic acid, [(trifluoroethylsulfonyl) amino] methanesulfinic acid, 1-hydroxy-2- (trimethylammonio) ethanesulfinate, hydroxy [4- (trimethylammonio) phenyl] methanesulfinate, 4- [ Hydroxy (sulfino) methyl] benzenesulfonic acid, 2- [hydroxy (sulfino) methyl] benzenesulfonic acid, 2-Hydroxy-2-sulfo-acetic acid, 2-Amino-2-sulfino-acetic acid 2-Hydroxy-2-sulfinopropionic acid 2-Amino-2-sulfinopropionic acid 3-Hydroxy-3-sulfinato-propionic acid 3-Amino 3-sulfinato-propionic acid 2-hydroxy-2-sulfinato-acetic acid ethyl ester 2-amino-2-sulfinato-acetic acid ethyl ester 1-hydroxy-2-methoxy-2-oxoethanesulfinic acid 1-hydroxy-2-ethoxy-2-oxoethanesulfinic acid 2-amino-1 -hydroxy-2-oxoethanesulfinic acid 2- (Dimethylamino) -1-hydroxy-2-oxoethanesulfinic acid Hydroxy (sulfin) methanesulfonic acid Hydroxy (phenyl) methanesulfinic acid Hydroxy (4-hydroxyphenyl) methanesulfinic acid Hydroxy (4-methoxyphenyl) methanesulfinic acid. Agent according to one of claims 1 to 5, characterized that it the sulfinic acid derivative in an amount of 0.01 to 20 wt .-%, particularly preferably of 1 to 20 wt .-%, each based on the weight of the composition contains. Agent according to one of claims 1 to 6, characterized that the Compounds having at least one quaternary nitrogen selected from the group formed from compounds having a quaternary nitrogen atom, Compounds with two quaternaries Nitrogen atoms, compounds with three quaternary nitrogen atoms, organic N-oxides and polymers derived from a monomer containing at least a quaternary Nitrogen atom. Agent according to one of Claims 1 to 7, characterized in that the compounds containing at least one quaternary nitrogen atom are selected from compounds of the formula (Q1),

wherein R ¹ and R ² independently represent a linear or branched (C ₁ to C ₃₀ ) alkyl group, a (C ₂ to C ₃₀ ) acyl group or a group -A ¹ -A ² -A ³ -R ⁵ wherein R ⁵ denotes a linear or branched (C ₈ to C ₃₀ ) -alkyl group, a linear or branched (C ₈ to C ₃₀ ) -alkenyl group, a hydroxy (C ₈ to C ₃₀ ) -alkyl group or an oligohydroxy- (C ₈ - to C ₃₀ ) alkyl group, A ^{1 is} a direct bond or a carbonyl group, A ^{2 is} a direct bond, a group NH or an oxygen atom, A ^{3 is} a (C ₂ to C ₄ ) alkylene group or a (C ₂ to C ₄ ) -hydroxyalkylene group, R ^{3 represents} a linear or branched (C ₈ to C ₃₀ ) alkyl group, a (C ₈ to C ₃₀ ) -hydroxyalkyl group, a (C ₂ to C ₃₀ ) -acyl group, a (C ₂ to C ₄ ) -hydroxyalkyl group or an aryl- (C ₁ to C ₆ ) -alkyl group, R ⁴ a (C ₁ to C ₄ ) -alkyl group or a (C ₂ to C ₄ ) -hydroxyalkyl group, X ^- a physiologically acceptable organic or anor ganic anion. Composition according to Claim 8, characterized in that the compounds of formula (Q1) are selected from among at least one compound from the group formed from compounds of the formulas (Q1-a), (Q1-b) and (Q1-b) c)

(R ¹⁰⁾ _y (Me) _(4-y) N ⁺ X ^- (Q1-c) in which R ⁵ denotes a linear or branched (C ₈ - to C ₃₀ ) -alkyl group, a linear or branched (C ₈ - to C ₃₀ ) -alkenyl group, a hydroxy (C ₈ - to C ₃₀ ) -alkyl group or an oligohydroxy group (C ₈ - to C ₃₀ ) -alkyl group, - R ^{5 *} denotes a linear or branched (C ₈ to C ₃₀ ) -alkyl group or a linear or branched (C ₈ to C ₃₀ ) -alkenyl group, - R ⁶ and R ⁷ independently of one another is a (C ₂ to C ₃₀ ) -acyl group or a linear or branched (C ₁ to C ₃₀ ) -alkyl group, - R ⁸ and R ^{9 are} independently of one another a (C ₁ to C ₄ ) -alkyl group or (C ₂ - to C ₄ ) -hydroxyalkyl group - R ¹⁰ independently of one another is a (C ₈ - to C ₃₀ ) -alkyl group, - A ^{1 is} a direct bond or a carbonyl group, - A ^{1 * is} a carbonyl group - A ^{2 is} a direct bond, an NH or a group Is oxygen, - A ^{2 * is} a group NH or an oxygen atom, - A ^{3 is} a (C ₂ - to C ₄ ) -alkylene group, a (C ₂ - to C ₄ ) -hydroxyalkylene group, - y is 1 or 2 and - X ^- is a physiologically compatible organic or inorganic anion, with the proviso that in formula (Q1-a) a ³ is a (C ₂ - to C ₄₎ means hydroxyalkylene, if a ¹ and a ² is a direct bond stand. Agent according to one of claims 1 to 9, characterized that it additionally Contains compounds of the aldehydes or ketones selected from at least one representative from the group - Oxocarboxylic acids or their salts, - oxocarboxylic acid ester, - cyclic, linear or branched aliphatic aldehydes, - cyclic, linear or branched aliphatic ketones, - mono- to polyhydroxy-functionalized aldehydes, - mono- to polyhydroxy-functionalized ketones, - alicyclic, aromatic or heterocyclic ketones as well - alicyclic, aromatic or heterocyclic aldehydes. Agent according to claim 10, characterized in that that the Connections selected from aldehydes or ketones in an amount of 0.1% by weight to 20% Wt .-%, in particular from 0.5 wt .-% to 10 wt .-%, each based on the weight of the ready-to-use agent. Agent according to one of claims 1 to 11, characterized that it a pH from pH 1 to pH 9, in particular from pH 1.5 to pH 6, owns. Agent according to one of claims 1 to 12, characterized that it additionally contains at least one reductone. Agent according to one of claims 1 to 13, characterized in that it additionally contains as solvent at least one (C ₂ to C ₆ ) -alkyl monoalcohol and / or (C ₂ to C ₆ ) -alkanediol, in particular ethanol, isopropanol and / or 1 , 2-propylene glycol. Use of an agent according to one of claims 1 to 14 for decolorization of substrates that are natural and / or synthetic dyes are colored. Use according to claim 15, characterized that this Substrate contains synthetic fibers and / or natural fibers. Use according to one of claims 15 or 16, characterized that the natural Fibers selected are made of cellulosic fibers, especially cotton, and keratin-containing fibers, in particular animal or human Hair. Use according to one of claims 15 to 17, characterized that the selected synthetic fibers are made of polyester, polyamide, elastane, viscose or polyacrylic. Use according to one of Claims 15 to 18, characterized that the to be decolored substrates dyed with oxidation dyes and / or substantive dyes. Method of reductive decolorization of natural and / or synthetic dyes colored substrates, characterized the existence Means according to one the claims 1 to 14 on the colored Substrate is applied and rinsed again after a contact time. Method according to claim 20, characterized in that that this Substrate contains synthetic fibers and / or natural fibers. Method according to claim 21, characterized that the natural Fibers selected are made of cellulosic fibers, especially cotton, and keratin-containing fibers, in particular animal or human Hair. Method according to one of claims 20 to 22, characterized that the selected synthetic fibers are made of polyester, polyamide, elastane, viscose or polyacrylic. Method according to one of claims 20 to 23, characterized that the to be decolored substrates dyed with oxidation dyes and / or direct dyes.